Water Quality
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Nanotechnology for a Safe and Sustainable use of Water Resources
We work on overcoming some of the most challenging issues in the water environment making responsible use of the great opportunities that nanotechnology offers. The Water Quality research group focuses on three main activities:
- Nanotech-based sensors for water quality monitoring; we fully develop portable and/or remote biosensors for water biological and chemical contaminants.
- Nanotechnology for cleaner water; we design, fabricate and test nanomaterials for the selective capture of water contaminants and biotoxins; and micro/nanostructured surfaces to control bacterial adhesion and biofilm formation.
- Environmental risk assessment of nanomaterials; we develop and carry out tests to evaluate nanomaterials’ modification, fate, bioaccumulation and ecotoxicity. We make special emphasis on implementing the safety-by-design concept to the in house produced nanomaterials and from collaborators.
ONGOING RESEARCH PROJECTS
AIHABs is a multidisciplinary innovative initiative aimed at developing an integrated evaluation system to forecast the risk derived from the presence of emerging cyanotoxins in inland and coastal ecosystems. The innovation of this proposal resides at merging tools as last generation Artificial Intelligence (AI), remote sensing, nanosensors, hydrodynamic modelling and massive genetic sequencing with the joint purpose of providing an early warning system to decision making authorities in terms of risk to the population. The predicting modelling effort will allow a timely action to minimize the risks of consuming surface waters or using them as recreational resources when the waterbodies are prone to produce toxic cyanobacterial blooms.
New technologies to analyse the smallest fractions from environmental SMNPs and their additives, as well as new methodologies in remote sensing for meso- and macroplastics.
Investigate, develop and validate an integrated solution for monitoring critical biological and environmental parameters to support the demedicalization of agricultural holdings.
Develop a new IIoT/IoRT (Industrial Internet of Things/Internet of Robotic Things) ecosystem applicable to the process of visual inspection and quality control in complex production lines of the automotive industry, including environmental and energy monitoring, waste water and gas treatment.
Methods and tools to obtain the relevant data encompassing the specific properties that differentiate nanomaterials from chemicals, paying special attention to the differential needs of the diverse impact and application in the environment area.
Close knowledge gap by digitalization of parameters and processes in RAS, which in turn will lead to more sustainable production under special attention of fish health and welfare.
Development of a validated rapid hazard profiling module, coupled to a new exposure-driven modelling framework to reduce toxicity.
Investigate the effects of engineered nanoparticles (ENPs) on aquaculture products, their bioaccumulation and assess its impact in human intake, and develop SERS-based sensors for these ENPs.
Advance in the knowledge of the possible toxic effects of metallic nanoparticles (NPs) of titanium dioxide and silver in aquatic ecosystems related to the aquaculture sector, as well as in the study of possible effects in the growth and welfare of cultured fish and molluscs.
PREVIOUS PROJECTS
Biofilm prevention in Reverse Osmosis (OI) systems, with a focus on reducing the direct use of biocidal agents.
BDevelop a portable quantification system for priority substances such as pesticides, herbicides and Polycyclic Aromatic Hydrocarbons (PAHs).
- AntiBACSURF: apply nanotechnology tools and concepts to develop innovative antibacterial nano-enabled surfaces to efficiently eradicate biofilms, providing complete antibacterial control;
- SERSPharma: to design plasmonic devices for SERS sensing to detect aromatic pharmaceuticals via diazonium chemistry.
- Detection system for Aeromonas salmonicida: development a portable quantification system for Aeromonas salmonicida.
- Antifouling surfaces for water monitoring device: development antifouling surfaces for the prevention of the adhesion of microorganisms in the manifold of water monitoring device
- Development of innovative systems for greywater purification and highly efficient water heating.
- Microcantilever Sensors for Air Quality Monitoring: bio/chemical functionalization and application of packaged microcantilever sensors for air quality monitoring.
- Implementation of Moving Bed Biofilm Reactor technology: development of nanocellulose-based composite for the biomass carriers for wastewater treatment.
Development of devices able to monitor in real time using SERS the production of carbon dioxide (CO2) by photodegradation of organic contaminants in urban wastewater.
Development of the lab-on-a-chip prototypes for fast detection of the (a) diarrheic shellfish poisoning toxins (okadaic acid) and (b) emerging toxins Ostreocins (Palytoxin) in fish and seafood.
Advanced web tools for enhancing the implementation of nanotechnology and the safe use of nanomaterials in the plastic industrial sector.
Industrial application of protocols for the mussel and pectinides detoxification using processing or depuration by microencapsulated agents. Nanotechnology enabled systems for aquacultured seafood contamination forecast.
Research on nanotechnologies applied to the environmental control in the water cycle.
New systems for water contaminants capture by means of novel tailored nanomaterials and biosensing devices to detect and quantify the presence of water contaminants.
Nanoporous COFs as modulable platforms for monitoring and analysis of pollutants in marine environment.
FOR MORE INFORMATION
PUBLICATIONS
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2022
Vanesa Romero, Isela Lavilla, Alicia Álvarez, Carlos Bendicho, Begoña Espiña, Laura M Salonen
ANALYTICA CHIMICA ACTA, 1191 (339293), 2022.
@article{Romero2022,
title = {Covalent organic framework as adsorbent for ultrasound-assisted dispersive (micro)solid phase extraction of polycyclic synthetic fragrances from seawater followed by fluorescent determination},
author = {Vanesa Romero, Isela Lavilla, Alicia Álvarez, Carlos Bendicho, Begoña Espiña, Laura M Salonen},
url = {https://doi.org/10.1016/j.aca.2021.339293},
doi = {10.1016/j.aca.2021.339293},
year = {2022},
date = {2022-01-25},
journal = {ANALYTICA CHIMICA ACTA},
volume = {1191},
number = {339293},
abstract = {In this work, a new analytical approach based on ultrasound-assisted dispersive (micro)solid phase extraction (US-D-μSPE) using TpBD-Me2 covalent organic framework (COF) as adsorbent for simple, rapid and selective fluorescent determination of two polycyclic synthetic fragrances in seawater, i.e., 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-(γ)-2-benzopyran (HHCB), branded galaxolide®, and 7-acetyl-1,1,3,4,4,6-hexamethyltetralin (AHTN), branded tonalide®, is proposed. Different parameters involved in both adsorption and desorption steps were optimized in order to obtain the best results. High adsorption efficiencies in the range of 91.2-97.8% were achieved for both analytes. Desorption efficiencies of ∼98% for AHTN and HHCB were obtained using methanol as solvent, rendering the material recyclable with merely minor losses in adsorption efficiency after five consecutive cycles of adsorption/desorption. Limits of detection (LODs) were 0.082 μg L-1 and 0.070 μg L-1 for AHTN and HHCB, respectively. The proposed method was successfully applied for the analysis of seawater without the need for a previous sample treatment, e.g., pH adjustment. Recoveries in the range of 90.4-101.2% with a relative standard deviation of 5.8% were obtained for both fragrances. The results proved the great capacity of TpBD-Me2 COF for the selective sorption of polycyclic fragrances in combination with fluorescent detection, being highly promising for application to environmental monitoring of other emerging organic pollutants.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}In this work, a new analytical approach based on ultrasound-assisted dispersive (micro)solid phase extraction (US-D-μSPE) using TpBD-Me2 covalent organic framework (COF) as adsorbent for simple, rapid and selective fluorescent determination of two polycyclic synthetic fragrances in seawater, i.e., 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-(γ)-2-benzopyran (HHCB), branded galaxolide®, and 7-acetyl-1,1,3,4,4,6-hexamethyltetralin (AHTN), branded tonalide®, is proposed. Different parameters involved in both adsorption and desorption steps were optimized in order to obtain the best results. High adsorption efficiencies in the range of 91.2-97.8% were achieved for both analytes. Desorption efficiencies of ∼98% for AHTN and HHCB were obtained using methanol as solvent, rendering the material recyclable with merely minor losses in adsorption efficiency after five consecutive cycles of adsorption/desorption. Limits of detection (LODs) were 0.082 μg L-1 and 0.070 μg L-1 for AHTN and HHCB, respectively. The proposed method was successfully applied for the analysis of seawater without the need for a previous sample treatment, e.g., pH adjustment. Recoveries in the range of 90.4-101.2% with a relative standard deviation of 5.8% were obtained for both fragrances. The results proved the great capacity of TpBD-Me2 COF for the selective sorption of polycyclic fragrances in combination with fluorescent detection, being highly promising for application to environmental monitoring of other emerging organic pollutants.Jessica Caldwell, Patricia Taladriz-Blanco, Roman Lehnera, Andriy Lubskyy, Roberto Diego Ortuso, Barbara Rothen-Rutishauser, Alke Petri-Finkad
The micro-, submicron-, and nanoplastic hunt: A review of detection methods for plastic particles Journal Article
Chemosphere, 293 , pp. 133514, 2022.
@article{Caldwell2022,
title = {The micro-, submicron-, and nanoplastic hunt: A review of detection methods for plastic particles},
author = {Jessica Caldwell, Patricia Taladriz-Blanco, Roman Lehnera, Andriy Lubskyy, Roberto Diego Ortuso, Barbara Rothen-Rutishauser, Alke Petri-Finkad},
url = {https://doi.org/10.1016/j.chemosphere.2022.133514},
doi = {10.1016/j.chemosphere.2022.133514},
year = {2022},
date = {2022-01-25},
journal = {Chemosphere},
volume = {293},
pages = {133514},
abstract = {Plastic particle pollution has been shown to be almost completely ubiquitous within our surrounding environment. This ubiquity in combination with a variety of unique properties (e.g. density, hydrophobicity, surface functionalization, particle shape and size, transition temperatures, and mechanical properties) and the ever-increasing levels of plastic production and use has begun to garner heightened levels of interest within the scientific community. However, as a result of these properties, plastic particles are often reported to be challenging to study in complex (i.e. real) environments. Therefore, this review aims to summarize research generated on multiple facets of the micro- and nanoplastics field; ranging from size and shape definitions to detection and characterization techniques to generating reference particles; in order to provide a more complete understanding of the current strategies for the analysis of plastic particles. This information is then used to provide generalized recommendations for researchers to consider as they attempt to study plastics in analytically complex environments; including method validation using reference particles obtained via the presented creation methods, encouraging efforts towards method standardization through the reporting of all technical details utilized in a study, and providing analytical pathway recommendations depending upon the exact knowledge desired and samples being studied.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Plastic particle pollution has been shown to be almost completely ubiquitous within our surrounding environment. This ubiquity in combination with a variety of unique properties (e.g. density, hydrophobicity, surface functionalization, particle shape and size, transition temperatures, and mechanical properties) and the ever-increasing levels of plastic production and use has begun to garner heightened levels of interest within the scientific community. However, as a result of these properties, plastic particles are often reported to be challenging to study in complex (i.e. real) environments. Therefore, this review aims to summarize research generated on multiple facets of the micro- and nanoplastics field; ranging from size and shape definitions to detection and characterization techniques to generating reference particles; in order to provide a more complete understanding of the current strategies for the analysis of plastic particles. This information is then used to provide generalized recommendations for researchers to consider as they attempt to study plastics in analytically complex environments; including method validation using reference particles obtained via the presented creation methods, encouraging efforts towards method standardization through the reporting of all technical details utilized in a study, and providing analytical pathway recommendations depending upon the exact knowledge desired and samples being studied. -
2021
Ana M. Milosevic, Laetitia Haeni, Liliane Ackermann Hirschi, Stefano Vanni, Pablo Campomanes-Ramos, Barbara Rothen-Rutishauser, Laura Rodriguez-Lorenzo, Alke Petri-Fink
The Choice of Nanoparticle Surface-Coupled Fluorescent Dyes Impacts Cellular Interaction Journal Article
CHEMNANOMAT, 2021.
@article{Milosevic2021,
title = {The Choice of Nanoparticle Surface-Coupled Fluorescent Dyes Impacts Cellular Interaction},
author = {Ana M. Milosevic, Laetitia Haeni, Liliane Ackermann Hirschi, Stefano Vanni, Pablo Campomanes-Ramos, Barbara Rothen-Rutishauser, Laura Rodriguez-Lorenzo, Alke Petri-Fink},
url = {https://doi.org/10.1002/cnma.202100443},
doi = {10.1002/cnma.202100443},
year = {2021},
date = {2021-11-11},
journal = {CHEMNANOMAT},
abstract = {Fluorescently-labelled nanoparticles show great promise for nanoparticle tracking and detection in biological or medical applications. However, these fluorescent molecules functionalized on the surface of the nanoparticles can impact the interaction of nanoparticles with biomolecules, cells, and subsequently influence their uptake. To explore the extent of these interactions, PEGylated gold nanoparticles were functionalized with six structurally different fluorescent dyes to demonstrate that the presence of the dye alters nanoparticle behavior, in particular interactions with bovine serum albumin, which consequently influenced their cellular uptake.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Fluorescently-labelled nanoparticles show great promise for nanoparticle tracking and detection in biological or medical applications. However, these fluorescent molecules functionalized on the surface of the nanoparticles can impact the interaction of nanoparticles with biomolecules, cells, and subsequently influence their uptake. To explore the extent of these interactions, PEGylated gold nanoparticles were functionalized with six structurally different fluorescent dyes to demonstrate that the presence of the dye alters nanoparticle behavior, in particular interactions with bovine serum albumin, which consequently influenced their cellular uptake.Jessica Caldwell, Patricia Taladriz-Blanco, Barbara Rothen-Rutishauser, Alke Petri-Fink
Additional Commentary on the Detection and Quantification of Plastic Micro- and Nanoparticles in Tea Samples Journal Article
CHIMIA, 75 (10), pp. 882-885, 2021.
@article{Caldwell2021,
title = {Additional Commentary on the Detection and Quantification of Plastic Micro- and Nanoparticles in Tea Samples},
author = {Jessica Caldwell, Patricia Taladriz-Blanco, Barbara Rothen-Rutishauser, Alke Petri-Fink},
url = {https://doi.org/10.2533/chimia.2021.882},
doi = {10.2533/chimia.2021.882},
year = {2021},
date = {2021-10-27},
journal = {CHIMIA},
volume = {75},
number = {10},
pages = {882-885},
abstract = {The study of plastic particles, particularly those in the micro-, sub-micro-, and nano-size ranges, within food and beverages has gained increasing interest within recent years. However, many analytical techniques have limits of detection which hinder their use for the study of these particles in these sample matrices. In addition, remaining contaminants from the matrices can interfere with the signals from plastic particles. Thus, great care must be given to sample preparation and data interpretation to ensure accurate results. This study proposes the use of sample purification through chemical digestion protocols to facilitate the study of plastic particles present in tea samples, and serves to highlight technical limitations which must be overcome in future studies.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}The study of plastic particles, particularly those in the micro-, sub-micro-, and nano-size ranges, within food and beverages has gained increasing interest within recent years. However, many analytical techniques have limits of detection which hinder their use for the study of these particles in these sample matrices. In addition, remaining contaminants from the matrices can interfere with the signals from plastic particles. Thus, great care must be given to sample preparation and data interpretation to ensure accurate results. This study proposes the use of sample purification through chemical digestion protocols to facilitate the study of plastic particles present in tea samples, and serves to highlight technical limitations which must be overcome in future studies.Maria Rita Ortega Vega, Estela Kerstner Baldin, Daniela Pavulack Pereira, Martha Cestari Silva Martins, Patricia Pranke, Fabiana Horn, Ivone Pinheiro, Ana Vieira, Begoña Espiña, Silvana Mattedi, Célia de Fraga Malfatti
Toxicity of oleate-based amino protic ionic liquids towards Escherichia coli, Danio rerio embryos and human skin cells Journal Article
Journal of Hazardous Materials, 422 (126896), 2021.
@article{Vega2021,
title = {Toxicity of oleate-based amino protic ionic liquids towards Escherichia coli, Danio rerio embryos and human skin cells},
author = {Maria Rita Ortega Vega, Estela Kerstner Baldin, Daniela Pavulack Pereira, Martha Cestari Silva Martins, Patricia Pranke, Fabiana Horn, Ivone Pinheiro, Ana Vieira, Begoña Espiña, Silvana Mattedi, Célia de Fraga Malfatti},
url = {https://doi.org/10.1016/j.jhazmat.2021.126896 },
doi = {10.1016/j.jhazmat.2021.126896 },
year = {2021},
date = {2021-08-11},
journal = {Journal of Hazardous Materials},
volume = {422},
number = {126896},
abstract = {Protic ionic liquids (PILs) have been widely employed with the label of “green solvents'' in different sectors of technology and industry. The studied PILs are promising for corrosion inhibition and lubrication applications in industry. Industrial use of the PILs can transform them in wastes, due to accidental spill or drag in water due to washing, that can reach water bodies. In addition, the handling of the product by the workers can expose them to accidental contact. Thus, the aim of this work is to evaluate the toxicity of PILs 2-hydroxyethylammonium oleate (2-HEAOl), N-methyl-2-hydroxyethylammonium oleate (m-2HEAOl) and bis-2-hydroxyethylammonium oleate (BHEAOl) towards Escherichia coli, zebrafish embryos, model organisms that can be present in water, and human skin cells. This is the first work reporting toxicity results for these PILs, which constitutes its novelty. Results showed that the studied PILs did not inhibit E. coli bacterial growth but could cause human skin cells death at the concentrations of use. LC50 values for zebrafish eggs were 40.21 mg/L for 2HEAOl, 12.92 mg/L for BHEAOl and 32.74 mg/L for m-2HEAOl, with sublethal effects at lower concentrations, such as hatching retarding, low heart rate and absence of free swimming.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Protic ionic liquids (PILs) have been widely employed with the label of “green solvents'' in different sectors of technology and industry. The studied PILs are promising for corrosion inhibition and lubrication applications in industry. Industrial use of the PILs can transform them in wastes, due to accidental spill or drag in water due to washing, that can reach water bodies. In addition, the handling of the product by the workers can expose them to accidental contact. Thus, the aim of this work is to evaluate the toxicity of PILs 2-hydroxyethylammonium oleate (2-HEAOl), N-methyl-2-hydroxyethylammonium oleate (m-2HEAOl) and bis-2-hydroxyethylammonium oleate (BHEAOl) towards Escherichia coli, zebrafish embryos, model organisms that can be present in water, and human skin cells. This is the first work reporting toxicity results for these PILs, which constitutes its novelty. Results showed that the studied PILs did not inhibit E. coli bacterial growth but could cause human skin cells death at the concentrations of use. LC50 values for zebrafish eggs were 40.21 mg/L for 2HEAOl, 12.92 mg/L for BHEAOl and 32.74 mg/L for m-2HEAOl, with sublethal effects at lower concentrations, such as hatching retarding, low heart rate and absence of free swimming.Monica Quarato, Ivone Pinheiro, Ana Vieira, Begoña Espiña and Laura Rodriguez-Lorenzo
Detection of Silver Nanoparticles in Seawater Using Surface-Enhanced Raman Scattering Journal Article
Nanomaterials 2021, 1711 (11(7)), 2021.
@article{Quarato2021,
title = {Detection of Silver Nanoparticles in Seawater Using Surface-Enhanced Raman Scattering},
author = {Monica Quarato, Ivone Pinheiro, Ana Vieira, Begoña Espiña and Laura Rodriguez-Lorenzo },
url = {https://doi.org/10.3390/nano11071711},
doi = {10.3390/nano11071711},
year = {2021},
date = {2021-06-29},
journal = {Nanomaterials 2021},
volume = {1711},
number = {11(7)},
abstract = {Nanomaterials significantly contribute to the development of new solutions to improve consumer products properties. Silver nanoparticles (AgNPs) are one of the most used, and as human exposure to such NPs increases, there is a growing need for analytical methods to identify and quantify nanoparticles present in the environment. Here we designed a detection strategy for AgNPs in seawater using surface-enhanced Raman Scattering (SERS). Three commercial AgNPs coated with polyvinylpyrrolidone (PVP) were used to determine the relative impact of size (PVP-15nmAgNPs and PVP-100nmAgNPs) and aggregation degree (predefined Ag aggregates, PVP-50–80nmAgNPs) on the SERS-based detection method. The study of colloidal stability and dissolution of selected AgNPs into seawater was carried out by dynamic light scattering and UV-vis spectroscopy. We showed that PVP-15nmAgNPs and PVP-100nmAgNPs remained colloidally stable, while PVP-50–80nmAgNPs formed bigger aggregates. We demonstrated that the SERS-based method developed here have the capacity to detect and quantify single and aggregates of AgNPs in seawater. The size had almost no effect on the detection limit (2.15 ± 1.22 mg/L for PVP-15nmAgNPs vs. 1.51 ± 0.71 mg/L for PVP-100nmAgNPs), while aggregation caused an increase of 2.9-fold (6.08 ± 1.21 mg/L). Our results demonstrate the importance of understanding NPs transformation in seawater since this can influence the detection method performance.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Nanomaterials significantly contribute to the development of new solutions to improve consumer products properties. Silver nanoparticles (AgNPs) are one of the most used, and as human exposure to such NPs increases, there is a growing need for analytical methods to identify and quantify nanoparticles present in the environment. Here we designed a detection strategy for AgNPs in seawater using surface-enhanced Raman Scattering (SERS). Three commercial AgNPs coated with polyvinylpyrrolidone (PVP) were used to determine the relative impact of size (PVP-15nmAgNPs and PVP-100nmAgNPs) and aggregation degree (predefined Ag aggregates, PVP-50–80nmAgNPs) on the SERS-based detection method. The study of colloidal stability and dissolution of selected AgNPs into seawater was carried out by dynamic light scattering and UV-vis spectroscopy. We showed that PVP-15nmAgNPs and PVP-100nmAgNPs remained colloidally stable, while PVP-50–80nmAgNPs formed bigger aggregates. We demonstrated that the SERS-based method developed here have the capacity to detect and quantify single and aggregates of AgNPs in seawater. The size had almost no effect on the detection limit (2.15 ± 1.22 mg/L for PVP-15nmAgNPs vs. 1.51 ± 0.71 mg/L for PVP-100nmAgNPs), while aggregation caused an increase of 2.9-fold (6.08 ± 1.21 mg/L). Our results demonstrate the importance of understanding NPs transformation in seawater since this can influence the detection method performance.Marisa P. Sárria, Ana Vieira, Ângela Lima, Soraia P. S. Fernandes, Ivo Lopes, Anabela Gonçalves, Andreia C. Gomes, Laura M. Salonen and Begoña Espiña
Acute ecotoxicity assessment of a covalent organic framework Journal Article
ACS Appl. Mater. Environ. Sci.: Nano, 2021, 6 , 2021.
@article{Sárria2021,
title = {Acute ecotoxicity assessment of a covalent organic framework},
author = {Marisa P. Sárria, Ana Vieira, Ângela Lima, Soraia P. S. Fernandes, Ivo Lopes, Anabela Gonçalves, Andreia C. Gomes, Laura M. Salonen and Begoña Espiña},
url = {DOI https://doi.org/10.1039/D0EN01059F},
doi = {10.1039/D0EN01059F},
year = {2021},
date = {2021-05-04},
journal = {ACS Appl. Mater. Environ. Sci.: Nano, 2021},
volume = {6},
abstract = {Covalent organic frameworks (COFs) have recently attracted increasing interest for applications in the environmental field, and to this end, the evaluation of their potential toxicity is of importance prior to deploying these materials in the environment. Herein, we report for the first time the acute toxicity assessment of a COF using a zebrafish embryotoxicity test. We studied a TpBD-Me2 COF, a material that we recently showed to efficiently adsorb water pollutants. The COF induced moderate toxicity in the early developmental stages of zebrafish embryos at low concentrations (0.001 μg mL−1), which can be attributed mainly to its particulate size and shape rather than its chemical nature, as demonstrated in the scanning electron microscopy studies performed on the chorions of exposed eggs and by confocal fluorescence imaging of eggs that were exposed to a fluorescent-labeled TpBD-Me2. This study reinforces the relevance of performing acute toxicity tests in complex organisms to attend to the environmental risk of material exposure, and the necessity of developing supported formulations to prevent significant material release into the water.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Covalent organic frameworks (COFs) have recently attracted increasing interest for applications in the environmental field, and to this end, the evaluation of their potential toxicity is of importance prior to deploying these materials in the environment. Herein, we report for the first time the acute toxicity assessment of a COF using a zebrafish embryotoxicity test. We studied a TpBD-Me2 COF, a material that we recently showed to efficiently adsorb water pollutants. The COF induced moderate toxicity in the early developmental stages of zebrafish embryos at low concentrations (0.001 μg mL−1), which can be attributed mainly to its particulate size and shape rather than its chemical nature, as demonstrated in the scanning electron microscopy studies performed on the chorions of exposed eggs and by confocal fluorescence imaging of eggs that were exposed to a fluorescent-labeled TpBD-Me2. This study reinforces the relevance of performing acute toxicity tests in complex organisms to attend to the environmental risk of material exposure, and the necessity of developing supported formulations to prevent significant material release into the water.Soraia P.S.Fernandes, Vanessa F. Fonseca, Vanesa Romero, Irina A. Duarte, Andreia Freitas, Jorge Barbosa, Patrick Reis-Santos, Laura M. Salonen and Begoña Espiña
Study on the efficiency of a covalent organic framework as adsorbent for the screening of pharmaceuticals in estuary waters Journal Article
Chemosphere , 278 , 2021.
@article{P.S.Fernandes2021,
title = {Study on the efficiency of a covalent organic framework as adsorbent for the screening of pharmaceuticals in estuary waters},
author = {Soraia P.S.Fernandes, Vanessa F. Fonseca, Vanesa Romero, Irina A. Duarte, Andreia Freitas, Jorge Barbosa, Patrick Reis-Santos, Laura M. Salonen and Begoña Espiña },
url = {https://doi.org/10.1016/j.chemosphere.2021.130364},
doi = {10.1016/j.chemosphere.2021.130364},
year = {2021},
date = {2021-03-29},
journal = {Chemosphere },
volume = {278},
abstract = {Herein, we demonstrate, for the first time, that covalent organic frameworks (COFs) can be efficient adsorbents for the screening of pharmaceuticals in real water samples, obtaining highly representative data on their occurrence and avoiding the cost of carrying high volume samples and tedious and costly clean-up and preconcentration steps. Of the 23 pharmaceuticals found present in the water samples from the Tagus river estuary using state-of-the-art solid-phase extraction (SPE), 22 were also detected (adsorbed and recovered for analysis) using a COF as the adsorbent material with adsorption efficiency of over 80% for nearly all compounds. In specific cases, acidification of the water samples was identified to lead to a dramatic loss of adsorption efficiency, underlining the effect of sample pre-treatment on the results. The COF efficiently adsorbed (>80%) 19 pharmaceuticals without acid treatment of the sample, highlighting the potential of this class of materials for representative in situ passive adsorption of pharmaceuticals, making this material suitable for being used in water monitoring programs as a simple and cost-efficient sample preparation procedure. In the case of α-hydroxyalprazolam and diclofenac, the COF outperformed the SPE procedure in the recovery efficiency. Although further efforts should be made in tailoring the desorption of the pharmaceuticals from the COF by using different solvents or solvent mixtures, we propose COFs as convenient adsorbent for broad-scope screening and as an efficient adsorbent material to target specific classes of pharmaceuticals. To the best of our knowledge, this is the first study on the use of COFs for contaminant screening in real, naturally contaminated water samples.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Herein, we demonstrate, for the first time, that covalent organic frameworks (COFs) can be efficient adsorbents for the screening of pharmaceuticals in real water samples, obtaining highly representative data on their occurrence and avoiding the cost of carrying high volume samples and tedious and costly clean-up and preconcentration steps. Of the 23 pharmaceuticals found present in the water samples from the Tagus river estuary using state-of-the-art solid-phase extraction (SPE), 22 were also detected (adsorbed and recovered for analysis) using a COF as the adsorbent material with adsorption efficiency of over 80% for nearly all compounds. In specific cases, acidification of the water samples was identified to lead to a dramatic loss of adsorption efficiency, underlining the effect of sample pre-treatment on the results. The COF efficiently adsorbed (>80%) 19 pharmaceuticals without acid treatment of the sample, highlighting the potential of this class of materials for representative in situ passive adsorption of pharmaceuticals, making this material suitable for being used in water monitoring programs as a simple and cost-efficient sample preparation procedure. In the case of α-hydroxyalprazolam and diclofenac, the COF outperformed the SPE procedure in the recovery efficiency. Although further efforts should be made in tailoring the desorption of the pharmaceuticals from the COF by using different solvents or solvent mixtures, we propose COFs as convenient adsorbent for broad-scope screening and as an efficient adsorbent material to target specific classes of pharmaceuticals. To the best of our knowledge, this is the first study on the use of COFs for contaminant screening in real, naturally contaminated water samples.Soraia P. S. Fernandes, Petr Kovář, Milan Pšenička, Artur M. S. Silva, Laura M. Salonen, Begoña Espiña
Selection of Covalent Organic Framework Pore Functionalities for Differential Adsorption of Microcystin Toxin Analogues Journal Article
ACS Appl. Mater. Interfaces 2021, 13 (13), pp. 15053–15063, 2021.
@article{Fernandes2021,
title = {Selection of Covalent Organic Framework Pore Functionalities for Differential Adsorption of Microcystin Toxin Analogues},
author = {Soraia P. S. Fernandes, Petr Kovář, Milan Pšenička, Artur M. S. Silva, Laura M. Salonen, Begoña Espiña},
url = {https://pubs.acs.org/doi/10.1021/acsami.0c18808},
doi = {10.1021/acsami.0c18808},
year = {2021},
date = {2021-03-24},
journal = {ACS Appl. Mater. Interfaces 2021},
volume = {13},
number = {13},
pages = {15053–15063},
abstract = {Microcystins (MCs), produced by Microcystis sp, are the most commonly detected cyanotoxins in freshwater, and due to their toxicity, worldwide distribution, and persistence in water, an improvement in the monitoring programs for their early detection and removal from water is necessary. To this end, we investigate the performance of three covalent organic frameworks (COFs), TpBD-(CF3)2, TpBD-(NO2)2, and TpBD-(NH2)2, for the adsorption of the most common and/or toxic MC derivatives, MC-LR, MC-RR, MC-LA, and MC-YR, from water. While MC-LR and MC-YR can be efficiently adsorbed using all three COF derivatives, high adsorption efficiencies were found for the most lipophilic toxin, MC-LA, with TpBD-(NH2)2, and the most hydrophilic one, MC-RR, with TpBD-(NO2). Theoretical calculations revealed that MC-LA and MC-RR have a tendency to be located mainly on the COF surface, interacting through hydrogen bonds with the amino and nitro functional groups of TpBD-(NH2)2 and TpBD-(NO2)2, respectively. TpBD-(NO2)2 outperforms the adsorbent materials reported for the capture of MC-RR, resulting in an increase in the maximum adsorption capacity by one order of magnitude. TpBD-(NH2)2 is reported as the first efficient adsorbent material for the capture of MC-LA. Large differences in desorption efficiencies were observed for the MCs with different COFs, highlighting the importance of COF–adsorbate interactions in the material recovery. Herein we show that efficient capture of these toxins from water can be achieved through the proper selection of the COF material. More importantly, this study demonstrates that by careful choice of COF functionalities, specific compounds can be targeted or excluded from a group of analogues, providing insight into the design of more efficient and selective adsorbent materials.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Microcystins (MCs), produced by Microcystis sp, are the most commonly detected cyanotoxins in freshwater, and due to their toxicity, worldwide distribution, and persistence in water, an improvement in the monitoring programs for their early detection and removal from water is necessary. To this end, we investigate the performance of three covalent organic frameworks (COFs), TpBD-(CF3)2, TpBD-(NO2)2, and TpBD-(NH2)2, for the adsorption of the most common and/or toxic MC derivatives, MC-LR, MC-RR, MC-LA, and MC-YR, from water. While MC-LR and MC-YR can be efficiently adsorbed using all three COF derivatives, high adsorption efficiencies were found for the most lipophilic toxin, MC-LA, with TpBD-(NH2)2, and the most hydrophilic one, MC-RR, with TpBD-(NO2). Theoretical calculations revealed that MC-LA and MC-RR have a tendency to be located mainly on the COF surface, interacting through hydrogen bonds with the amino and nitro functional groups of TpBD-(NH2)2 and TpBD-(NO2)2, respectively. TpBD-(NO2)2 outperforms the adsorbent materials reported for the capture of MC-RR, resulting in an increase in the maximum adsorption capacity by one order of magnitude. TpBD-(NH2)2 is reported as the first efficient adsorbent material for the capture of MC-LA. Large differences in desorption efficiencies were observed for the MCs with different COFs, highlighting the importance of COF–adsorbate interactions in the material recovery. Herein we show that efficient capture of these toxins from water can be achieved through the proper selection of the COF material. More importantly, this study demonstrates that by careful choice of COF functionalities, specific compounds can be targeted or excluded from a group of analogues, providing insight into the design of more efficient and selective adsorbent materials.Ana Castanheira, Marília Barreiros dos Santos, Laura Rodriguez-Lorenzo, Raquel Queirós and Begoña Espiña
A novel microfluidic system for the sensitive and cost-effective detection of okadaic acid in mussels Journal Article
Analyst , 8 , 2021.
@article{Castanheira2021,
title = {A novel microfluidic system for the sensitive and cost-effective detection of okadaic acid in mussels},
author = {Ana Castanheira, Marília Barreiros dos Santos, Laura Rodriguez-Lorenzo, Raquel Queirós and Begoña Espiña},
url = {DOI https://doi.org/10.1039/D0AN02092C},
doi = {10.1039/D0AN02092C},
year = {2021},
date = {2021-02-09},
journal = {Analyst },
volume = {8},
abstract = {Okadaic acid (OA) is produced by marine dinoflagellates and it can be easily accumulated in shellfish, causing intoxications when consumed by humans. Consequently, there is a need for sensitive, reliable and cost-effective methods to detect OA in real samples. In this work, we developed a novel and affordable microfluidic system to detect OA based on the protein phosphatase 1 inhibition colorimetric assay. This enzyme was immobilized in a microfluidic chamber by physisorption in an alumina sol–gel. The results show good enzyme stability over time when maintained at 4 °C. The developed system was sensitive for OA standard solutions, presenting a limit of detection (LOD) of 11.6 nM over a large linear range (43.4 to 3095.8 nM). Our method revealed an LOD as low as 0.2 μg kg−1 and a linear range between 1.47 and 506 μg kg−1 for extracted mussel matrix, detecting OA concentrations in contaminated mussels much lower than the regulated limit (160 μg kg−1). The enzyme stability and reusability along with the simplicity and low cost associated with microfluidics systems make this method very interesting from a commercial point of view.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Okadaic acid (OA) is produced by marine dinoflagellates and it can be easily accumulated in shellfish, causing intoxications when consumed by humans. Consequently, there is a need for sensitive, reliable and cost-effective methods to detect OA in real samples. In this work, we developed a novel and affordable microfluidic system to detect OA based on the protein phosphatase 1 inhibition colorimetric assay. This enzyme was immobilized in a microfluidic chamber by physisorption in an alumina sol–gel. The results show good enzyme stability over time when maintained at 4 °C. The developed system was sensitive for OA standard solutions, presenting a limit of detection (LOD) of 11.6 nM over a large linear range (43.4 to 3095.8 nM). Our method revealed an LOD as low as 0.2 μg kg−1 and a linear range between 1.47 and 506 μg kg−1 for extracted mussel matrix, detecting OA concentrations in contaminated mussels much lower than the regulated limit (160 μg kg−1). The enzyme stability and reusability along with the simplicity and low cost associated with microfluidics systems make this method very interesting from a commercial point of view.Maraja Riechers, Lucia Fanini, Annalisa Apicella, Carolina Batista Galván, Elise Blondel, Begoña Espiña, Simone Kefer, Tristan Keroullé, Katja Klun, Tania R. Pereira, Francesca Ronchi, Pedro Ruiz Rodríguez, Haritz Sardon, Alexandra Viana Silva, Maris Stulgis, Nagore Ibarra-González
Plastics in our ocean as transdisciplinary challenge Conference
164 (2021), 2021.
@conference{Riechers2021,
title = {Plastics in our ocean as transdisciplinary challenge},
author = {Maraja Riechers, Lucia Fanini, Annalisa Apicella, Carolina Batista Galván, Elise Blondel, Begoña Espiña, Simone Kefer, Tristan Keroullé, Katja Klun, Tania R. Pereira, Francesca Ronchi, Pedro Ruiz Rodríguez, Haritz Sardon, Alexandra Viana Silva, Maris Stulgis, Nagore Ibarra-González},
url = {https://doi.org/10.1016/j.marpolbul.2021.112051},
doi = {10.1016/j.marpolbul.2021.112051},
year = {2021},
date = {2021-01-27},
journal = {Marine Pollution Bulletin},
volume = {164},
number = {2021},
pages = {112051},
abstract = {This conference report summarizes the current challenges of researching microplastics pollution in the ocean as debated by international experts and stakeholders at a workshop held in San Sebastián, Spain, 1–2 October 2019. The transdisciplinary, co-learning approach of this report stressed the need to incorporate multiple perspective in solving the problem of microplastics and resulted in three proposed actions: (i) filtering microplastics from waste waters; (ii) mandatory ecolabels on plastic products packages; and (iii) circular economy of packaging plastics.},
keywords = {},
pubstate = {published},
tppubtype = {conference}
}This conference report summarizes the current challenges of researching microplastics pollution in the ocean as debated by international experts and stakeholders at a workshop held in San Sebastián, Spain, 1–2 October 2019. The transdisciplinary, co-learning approach of this report stressed the need to incorporate multiple perspective in solving the problem of microplastics and resulted in three proposed actions: (i) filtering microplastics from waste waters; (ii) mandatory ecolabels on plastic products packages; and (iii) circular economy of packaging plastics. -
2020
Espiña, B.; Prado, M.; Santos, M.B.; Salonen, L.M.; Queirós, R.B.; Fernandes, S.P.S.; Vial, S.; Martins, V.C.
New techniques in environment monitoring Book Chapter
pp. 35-106, De Gruyter , 2nd, 2020.
@inbook{Espiña2020,
title = {New techniques in environment monitoring},
author = {Espiña, B.; Prado, M.; Santos, M.B.; Salonen, L.M.; Queirós, R.B.; Fernandes, S.P.S.; Vial, S.; Martins, V.C.},
url = {https://doi.org/10.1515/9783110625738-002},
doi = {10.1515/9783110625738-002},
year = {2020},
date = {2020-12-16},
pages = {35-106},
publisher = {De Gruyter },
edition = {2nd},
keywords = {},
pubstate = {published},
tppubtype = {inbook}
}Jarju, J.J.; Lavender, A. M.; Espiña, B; Romero, V; Salonen, L. M.
Covalent Organic Framework Composites: Synthesis and Analytical Applications Journal Article
Molecules 2020, 25(22) (5404), 2020.
@article{Jarju2020,
title = {Covalent Organic Framework Composites: Synthesis and Analytical Applications},
author = {Jarju, J.J.; Lavender, A. M.; Espiña, B; Romero, V; Salonen, L. M.},
url = {https://doi.org/10.3390/molecules25225404},
doi = {10.3390/molecules25225404},
year = {2020},
date = {2020-11-18},
journal = {Molecules 2020},
volume = {25(22)},
number = {5404},
abstract = {In the recent years, composite materials containing covalent organic frameworks (COFs) have raised increasing interest for analytical applications. To date, various synthesis techniques have emerged that allow for the preparation of crystalline and porous COF composites with various materials. Herein, we summarize the most common methods used to gain access to crystalline COF composites with magnetic nanoparticles, other oxide materials, graphene and graphene oxide, and metal nanoparticles. Additionally, some examples of stainless steel, polymer, and metal-organic framework composites are presented. Thereafter, we discuss the use of these composites for chromatographic separation, environmental remediation, and sensing.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}In the recent years, composite materials containing covalent organic frameworks (COFs) have raised increasing interest for analytical applications. To date, various synthesis techniques have emerged that allow for the preparation of crystalline and porous COF composites with various materials. Herein, we summarize the most common methods used to gain access to crystalline COF composites with magnetic nanoparticles, other oxide materials, graphene and graphene oxide, and metal nanoparticles. Additionally, some examples of stainless steel, polymer, and metal-organic framework composites are presented. Thereafter, we discuss the use of these composites for chromatographic separation, environmental remediation, and sensing.Steinmetz, L.; Geers, C.; Balog, S.; Bonmarin, M; Rodriguez-Lorenzo, L.; Taladriz-Blanco, P.; Rothen-Rutishauser, B.; Petri-Fink, A.
A comparative study of silver nanoparticle dissolution under physiological conditions Journal Article
Nanoscale Advances, (12), pp. 5760-5768, 2020.
@article{Steinmetz2020,
title = {A comparative study of silver nanoparticle dissolution under physiological conditions},
author = {Steinmetz, L.; Geers, C.; Balog, S.; Bonmarin, M; Rodriguez-Lorenzo, L.; Taladriz-Blanco, P.; Rothen-Rutishauser, B.; Petri-Fink, A.},
url = {https://doi.org/10.1039/D0NA00733A},
doi = {10.1039/D0NA00733A},
year = {2020},
date = {2020-10-20},
journal = {Nanoscale Advances},
number = {12},
pages = {5760-5768},
abstract = {Upon dissolution of silver nanoparticles, silver ions are released into the environment, which are known to induce adverse effects. However, since dissolution studies are predominantly performed in water and/or at room temperature, the effects of biological media and physiologically relevant temperature on the dissolution rate are not considered. Here, we investigate silver nanoparticle dissolution trends based on their plasmonic properties under biologically relevant conditions, i.e. in biological media at 37 °C over a period of 24 h. The studied nanoparticles, surface-functionalized with polyvinylpyrrolidone, beta-cyclodextrin/polyvinylpyrrolidone, and starch/polyvinylpyrrolidone, were analysed by UV-Vis spectroscopy, lock-in thermography and depolarized dynamic light scattering to evaluate the influence of these coatings on silver nanoparticle dissolution. Transmission electron microscopy was employed to visualize the reduction of the nanoparticle core diameters. Consequently, the advantages and limitations of these analytical techniques are discussed. To assess the effects of temperature on the degree of dissolution, the results of experiments performed at biological temperature were compared to those obtained at room temperature. Dissolution is often enhanced at elevated temperatures, but has to be determined individually for every specific condition. Furthermore, we evaluated potential nanoparticle aggregation. Our results highlight that additional surface coatings do not necessarily hinder the dissolution or aggregation of silver nanoparticles.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Upon dissolution of silver nanoparticles, silver ions are released into the environment, which are known to induce adverse effects. However, since dissolution studies are predominantly performed in water and/or at room temperature, the effects of biological media and physiologically relevant temperature on the dissolution rate are not considered. Here, we investigate silver nanoparticle dissolution trends based on their plasmonic properties under biologically relevant conditions, i.e. in biological media at 37 °C over a period of 24 h. The studied nanoparticles, surface-functionalized with polyvinylpyrrolidone, beta-cyclodextrin/polyvinylpyrrolidone, and starch/polyvinylpyrrolidone, were analysed by UV-Vis spectroscopy, lock-in thermography and depolarized dynamic light scattering to evaluate the influence of these coatings on silver nanoparticle dissolution. Transmission electron microscopy was employed to visualize the reduction of the nanoparticle core diameters. Consequently, the advantages and limitations of these analytical techniques are discussed. To assess the effects of temperature on the degree of dissolution, the results of experiments performed at biological temperature were compared to those obtained at room temperature. Dissolution is often enhanced at elevated temperatures, but has to be determined individually for every specific condition. Furthermore, we evaluated potential nanoparticle aggregation. Our results highlight that additional surface coatings do not necessarily hinder the dissolution or aggregation of silver nanoparticles.Valerio, A.; Sarria, M. P.; Rodriguez-Lorenzo, L; Hotza, D; Espiña, B.; González, S.Y.G.
Are TiO2 nanoparticles safe for photocatalysis in aqueous media? Journal Article
Nanoscale Advances, (2), pp. 4951-4960, 2020.
@article{Valerio2020,
title = {Are TiO2 nanoparticles safe for photocatalysis in aqueous media?},
author = {Valerio, A.; Sarria, M. P.; Rodriguez-Lorenzo, L; Hotza, D; Espiña, B.; González, S.Y.G.},
url = {https://doi.org/10.1039/D0NA00584C},
doi = {10.1039/D0NA00584C},
year = {2020},
date = {2020-09-15},
journal = {Nanoscale Advances},
number = {2},
pages = {4951-4960},
abstract = {Although environmental and toxicity concerns are inherently linked, catalysis using photoactive nanoparticles and their hazardous potential are usually addressed independently. A toxicological assessment under the application framework is particularly important, given the pristine nanoparticles tend to change characteristics during several processes used to incorporate them into products. Herein, an efficient TiO2-functionalized macroporous structure was developed using widely adopted immobilization procedures. The relationships between photocatalysis, catalyst release and associated potential environmental hazards were assessed using zebrafish embryonic development as a proxy. Immobilized nanoparticles demonstrated the safest approach to the environment, as the process eliminates remnant additives while preventing the release of nanoparticles. However, as acute sublethal effects were recorded in zebrafish embryos at different stages of development, a completely safe release of TiO2 nanoparticles into the aquatic environment cannot be advocated.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Although environmental and toxicity concerns are inherently linked, catalysis using photoactive nanoparticles and their hazardous potential are usually addressed independently. A toxicological assessment under the application framework is particularly important, given the pristine nanoparticles tend to change characteristics during several processes used to incorporate them into products. Herein, an efficient TiO2-functionalized macroporous structure was developed using widely adopted immobilization procedures. The relationships between photocatalysis, catalyst release and associated potential environmental hazards were assessed using zebrafish embryonic development as a proxy. Immobilized nanoparticles demonstrated the safest approach to the environment, as the process eliminates remnant additives while preventing the release of nanoparticles. However, as acute sublethal effects were recorded in zebrafish embryos at different stages of development, a completely safe release of TiO2 nanoparticles into the aquatic environment cannot be advocated.Romenro, V.; Fernandes, S. P. S.; Kovář, P.; Pšenička, M.; Kolen'ko, Y.V.; Salonen, L.M.; Espiña, B.
Efficient adsorption of endocrine-disrupting pesticides from water with a reusable magnetic covalent organic framework Journal Article
Microporous and Mesoporous Materials Journal , 307 , 2020.
@article{Romenro2020,
title = {Efficient adsorption of endocrine-disrupting pesticides from water with a reusable magnetic covalent organic framework},
author = {Romenro, V.; Fernandes, S. P. S.; Kovář, P.; Pšenička, M.; Kolen'ko, Y.V.; Salonen, L.M.; Espiña, B.},
url = {https://doi.org/10.1016/j.micromeso.2020.110523},
doi = {10.1016/j.micromeso.2020.110523},
year = {2020},
date = {2020-07-29},
journal = {Microporous and Mesoporous Materials Journal },
volume = {307},
abstract = {A magnetic covalent organic framework (COF) is applied for the first time as adsorbent for the extraction of endocrine-disrupting pesticides from water. High adsorption efficiencies were found for lipophilic chlorpyrifos and atrazine, with calculated maximum adsorption capacities of 270 mg g−1 and 54 mg g−1, respectively, outperforming reported adsorbents, such as activated carbon, graphene, or metal−organic frameworks. Polar diquat showed very poor adsorption efficiency, indicating that hydrophobic interactions play a role in the adsorption. Calculations revealed that the interactions between the COF and the pesticides are mainly based on van der Waals interactions. Finally, recycling experiments showed that both pesticides can be recovered with an efficiency of over 90% using acetonitrile as solvent, with merely minor losses in adsorption capacity after five consecutive cycles of adsorption/desorption. The present study promotes further exploration of the possible application of COFs for the extraction and pre-concentration of pesticides in environmental matrices.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}A magnetic covalent organic framework (COF) is applied for the first time as adsorbent for the extraction of endocrine-disrupting pesticides from water. High adsorption efficiencies were found for lipophilic chlorpyrifos and atrazine, with calculated maximum adsorption capacities of 270 mg g−1 and 54 mg g−1, respectively, outperforming reported adsorbents, such as activated carbon, graphene, or metal−organic frameworks. Polar diquat showed very poor adsorption efficiency, indicating that hydrophobic interactions play a role in the adsorption. Calculations revealed that the interactions between the COF and the pesticides are mainly based on van der Waals interactions. Finally, recycling experiments showed that both pesticides can be recovered with an efficiency of over 90% using acetonitrile as solvent, with merely minor losses in adsorption capacity after five consecutive cycles of adsorption/desorption. The present study promotes further exploration of the possible application of COFs for the extraction and pre-concentration of pesticides in environmental matrices.Abalde-Cela, S.; Rebelo, R; Wu, L.; Barbosa, A.I.; Rodríguez-Lorenzo, L.; Kant, K.; Reis, R.L.; Correlo, V. M. and Diéguez, L.
A SERS-based 3D nanobiosensor: towards cell metabolite monitoring Journal Article
Mater. Adv., 1 , pp. 1613-1621, 2020.
@article{Abalde-Cela2020,
title = {A SERS-based 3D nanobiosensor: towards cell metabolite monitoring},
author = {Abalde-Cela, S.; Rebelo, R; Wu, L.; Barbosa, A.I.; Rodríguez-Lorenzo, L.; Kant, K.; Reis, R.L.; Correlo, V. M. and Diéguez, L.},
url = {https://doi.org/10.1039/D0MA00121J},
doi = {10.1039/D0MA00121J},
year = {2020},
date = {2020-07-27},
journal = {Mater. Adv.},
volume = {1},
pages = {1613-1621},
abstract = {The development of surface-enhanced Raman scattering (SERS) spectroscopy as an analytical technique has been mainly focused on improving detection limits, nanoparticle (NP) stability and reproducibility. However, a step further on the functionalities of these promising sensing platforms is needed to enable their integration as in situ biosensors able to continuously monitor the cellular microenvironment and cell communication. Herein, we developed a biocompatible SERS hybrid material, by embedding gold-based nanostructures into gellan gum “sponge-like” hydrogels. This novel material was used as a SERS substrate for biochemical detection of disease associated cell metabolites. The optical and morphological characterisation of these 3D plasmonic sensors demonstrated the efficient incorporation of gold nanostars and silver coated gold nanorods, as well as their homogeneous distribution within the hydrogel matrices. By using these 3D plasmonic polymeric matrices we were able to prove the detection of two cancer-cell-related extracellular metabolites, lactate and thiocyanate. The SERS detection of these two small molecules is not trivial and was only possible due to the extra SERS enhancement offered by both types of anisotropic NPs. Further, the use of the gellan gum scaffold to support the NPs enables the potential use of these novel SERS platforms for the in situ growth and metabolism monitoring of 3D cell models.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}The development of surface-enhanced Raman scattering (SERS) spectroscopy as an analytical technique has been mainly focused on improving detection limits, nanoparticle (NP) stability and reproducibility. However, a step further on the functionalities of these promising sensing platforms is needed to enable their integration as in situ biosensors able to continuously monitor the cellular microenvironment and cell communication. Herein, we developed a biocompatible SERS hybrid material, by embedding gold-based nanostructures into gellan gum “sponge-like” hydrogels. This novel material was used as a SERS substrate for biochemical detection of disease associated cell metabolites. The optical and morphological characterisation of these 3D plasmonic sensors demonstrated the efficient incorporation of gold nanostars and silver coated gold nanorods, as well as their homogeneous distribution within the hydrogel matrices. By using these 3D plasmonic polymeric matrices we were able to prove the detection of two cancer-cell-related extracellular metabolites, lactate and thiocyanate. The SERS detection of these two small molecules is not trivial and was only possible due to the extra SERS enhancement offered by both types of anisotropic NPs. Further, the use of the gellan gum scaffold to support the NPs enables the potential use of these novel SERS platforms for the in situ growth and metabolism monitoring of 3D cell models.Fernandes, S. P. S.; Mellah, A.; Kovar, P.; Sárria, M.P.; Psenicka, M.; Djamila, H.; Salonen, L.M.; Espiña, B.
Extraction of Ibuprofen from Natural Waters Using a Covalent Organic Framework Journal Article
Molecules 2020, 25 (14), pp. 3132, 2020.
@article{Fernandes2020b,
title = {Extraction of Ibuprofen from Natural Waters Using a Covalent Organic Framework},
author = {Fernandes, S. P. S.; Mellah, A.; Kovar, P.; Sárria, M.P.; Psenicka, M.; Djamila, H.; Salonen, L.M.; Espiña, B.},
url = {https://doi.org/10.3390/molecules25143132},
doi = {10.3390/molecules25143132},
year = {2020},
date = {2020-07-08},
journal = {Molecules 2020},
volume = {25},
number = {14},
pages = {3132},
abstract = {Ibuprofen is one of the most widely used pharmaceuticals, and due to its inefficient removal by conventional wastewater treatment, it can be found in natural surface waters at high concentrations. Recently, we demonstrated that the TpBD-(CF3)2 covalent organic framework (COF) can adsorb ibuprofen from ultrapure water with high efficiency. Here, we investigate the performance of the COF for the extraction of ibuprofen from natural water samples from a lake, river, and estuary. In general, the complexity of the natural water matrix induced a reduction in the adsorption efficiency of ibuprofen as compared to ultrapure water. The best performance, with over 70% adsorption efficiency, was found in lake water, the sample which featured the lowest pH. According to the theoretical calculations, ibuprofen more favorably interacts with the COF pores in the protonated form, which could partially account for the enhanced adsorption efficiency found in lake water. In addition, we explored the effect of the presence of competing pharmaceuticals, namely, acetaminophen and phenobarbital, on the ibuprofen adsorption as binary mixtures. Acetaminophen and phenobarbital were adsorbed by TpBD-(CF3)2 with low efficiency and their presence led to an increase in ibuprofen adsorption in the binary mixtures. Overall, this study demonstrates that TpBD-(CF3)2 is an efficient adsorbent for the extraction of ibuprofen from natural waters as well.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Ibuprofen is one of the most widely used pharmaceuticals, and due to its inefficient removal by conventional wastewater treatment, it can be found in natural surface waters at high concentrations. Recently, we demonstrated that the TpBD-(CF3)2 covalent organic framework (COF) can adsorb ibuprofen from ultrapure water with high efficiency. Here, we investigate the performance of the COF for the extraction of ibuprofen from natural water samples from a lake, river, and estuary. In general, the complexity of the natural water matrix induced a reduction in the adsorption efficiency of ibuprofen as compared to ultrapure water. The best performance, with over 70% adsorption efficiency, was found in lake water, the sample which featured the lowest pH. According to the theoretical calculations, ibuprofen more favorably interacts with the COF pores in the protonated form, which could partially account for the enhanced adsorption efficiency found in lake water. In addition, we explored the effect of the presence of competing pharmaceuticals, namely, acetaminophen and phenobarbital, on the ibuprofen adsorption as binary mixtures. Acetaminophen and phenobarbital were adsorbed by TpBD-(CF3)2 with low efficiency and their presence led to an increase in ibuprofen adsorption in the binary mixtures. Overall, this study demonstrates that TpBD-(CF3)2 is an efficient adsorbent for the extraction of ibuprofen from natural waters as well.Septiadi, D.; Lee, A.; Spuch-Calvar, M.; Moore, T.; Spiaggia, G.; Abdussalam, W.; Rodriguez-Lorenzo, L.; Taladriz-Blanco, P.; Rothen-Rutishauser, B.; Petri-Fink, A.
Particle Surfaces to Study Macrophage Adherence, Migration, and Clearance Journal Article
Advanced Functional Materials 2020, 30 (34), 2020.
@article{Septiadi2020,
title = {Particle Surfaces to Study Macrophage Adherence, Migration, and Clearance},
author = {Septiadi, D.; Lee, A.; Spuch-Calvar, M.; Moore, T.; Spiaggia, G.; Abdussalam, W.; Rodriguez-Lorenzo, L.; Taladriz-Blanco, P.; Rothen-Rutishauser, B.; Petri-Fink, A.},
url = {https://doi.org/10.1002/adfm.202002630},
doi = {10.1002/adfm.202002630},
year = {2020},
date = {2020-07-02},
journal = {Advanced Functional Materials 2020},
volume = {30},
number = {34},
abstract = {Nanoparticle adsorption to substrates pose a unique challenge to understand uptake mechanisms as it involves the organization of complex cytoskeletal components by cells to perform endocytosis/phagocytosis. In particular, it is not well-understood from a cell mechanics perspective how the adhesion of particles on substrate will influence the ease of material clearance. By using a particle model, key contributing factors underlying cell adhesion on nonporous silica particle surfaces, migration and engulfment, are simulated and studied. Following a 24 h incubation period, monocyte-derived macrophages and A549 epithelial cells are able to adhere and remove particles in their local vicinity through induction of adhesive pulling arise from cell traction forces and phagocytic/endocytic mechanisms, in a size-dependent manner. It is observed that such particle-decorated surfaces can be used to address the influence of surface topography on cell behavior. Substrates which presented 480 nm silica particles are able to induce greater development and maturation of focal adhesions, which play an important role in cellular mechanoregulation. Moreover, under a chemotactic influence, in the presence of 30% fetal bovine serum, macrophages are able to uptake the particles and be directed to translocate along a concentration gradient, indicating that local mechanical effects do not substantially impair normal physiological functions.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Nanoparticle adsorption to substrates pose a unique challenge to understand uptake mechanisms as it involves the organization of complex cytoskeletal components by cells to perform endocytosis/phagocytosis. In particular, it is not well-understood from a cell mechanics perspective how the adhesion of particles on substrate will influence the ease of material clearance. By using a particle model, key contributing factors underlying cell adhesion on nonporous silica particle surfaces, migration and engulfment, are simulated and studied. Following a 24 h incubation period, monocyte-derived macrophages and A549 epithelial cells are able to adhere and remove particles in their local vicinity through induction of adhesive pulling arise from cell traction forces and phagocytic/endocytic mechanisms, in a size-dependent manner. It is observed that such particle-decorated surfaces can be used to address the influence of surface topography on cell behavior. Substrates which presented 480 nm silica particles are able to induce greater development and maturation of focal adhesions, which play an important role in cellular mechanoregulation. Moreover, under a chemotactic influence, in the presence of 30% fetal bovine serum, macrophages are able to uptake the particles and be directed to translocate along a concentration gradient, indicating that local mechanical effects do not substantially impair normal physiological functions.Vilas-Boas, V.; Carvalho, F.; Espiña, B.
Magnetic Hyperthermia for Cancer Treatment: Main Parameters Affecting the Outcome of In Vitro and In Vivo Studies Journal Article
Molecules 2020, 25 (12), pp. 2874, 2020.
@article{Vilas-Boas2020,
title = {Magnetic Hyperthermia for Cancer Treatment: Main Parameters Affecting the Outcome of In Vitro and In Vivo Studies},
author = {Vilas-Boas, V.; Carvalho, F.; Espiña, B.},
url = {https://doi.org/10.3390/molecules25122874},
doi = {10.3390/molecules25122874},
year = {2020},
date = {2020-06-22},
journal = {Molecules 2020},
volume = {25},
number = {12},
pages = {2874},
abstract = {Magnetic hyperthermia (MHT) is being investigated as a cancer treatment since the 1950s. Recent advancements in the field of nanotechnology have resulted in a notable increase in the number of MHT studies. Most of these studies explore MHT as a stand-alone treatment or as an adjuvant therapy in a preclinical context. However, despite all the scientific effort, only a minority of the MHT-devoted nanomaterials and approaches made it to clinical context. The outcome of an MHT experiment is largely influenced by a number of variables that should be considered when setting up new MHT studies. This review highlights and discusses the main parameters affecting the outcome of preclinical MHT, aiming to provide adequate assistance in the design of new, more efficient MHT studies.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Magnetic hyperthermia (MHT) is being investigated as a cancer treatment since the 1950s. Recent advancements in the field of nanotechnology have resulted in a notable increase in the number of MHT studies. Most of these studies explore MHT as a stand-alone treatment or as an adjuvant therapy in a preclinical context. However, despite all the scientific effort, only a minority of the MHT-devoted nanomaterials and approaches made it to clinical context. The outcome of an MHT experiment is largely influenced by a number of variables that should be considered when setting up new MHT studies. This review highlights and discusses the main parameters affecting the outcome of preclinical MHT, aiming to provide adequate assistance in the design of new, more efficient MHT studies.Belekbir, S; El Azzouzi, M.; El Hamidi, A.; Rodríguez-Lorenzo, L.; Arturo Santaballa, J.; Canle, M.
Improved Photocatalyzed Degradation of Phenol, as a Model Pollutant, over Metal-Impregnated Nanosized TiO2 Journal Article
Nanomaterials 2020, 10 (5), pp. 996, 2020.
@article{Belekbir2020,
title = {Improved Photocatalyzed Degradation of Phenol, as a Model Pollutant, over Metal-Impregnated Nanosized TiO2},
author = {Belekbir, S; El Azzouzi, M.; El Hamidi, A.; Rodríguez-Lorenzo, L.; Arturo Santaballa, J.; Canle, M.},
url = {https://doi.org/10.3390/nano10050996},
doi = {10.3390/nano10050996},
year = {2020},
date = {2020-05-22},
journal = {Nanomaterials 2020},
volume = {10},
number = {5},
pages = {996},
abstract = {Photocatalyzed degradation of phenol in aqueous solution over surface impregnated TiO2 (M = Cu, Cr, V) under UV-Vis (366 nm) and UV (254 nm) irradiation is described. Nanosized photocatalyts were prepared from TiO2-P25 by wet impregnation, and characterized by X-ray diffraction, X-ray fluorescence, transmission electron microscopy, UV-Vis diffuse reflectance spectroscopy, Raman spectroscopy, and adsorption studies. No oxide phases of the metal dopants were found, although their presence in the TiO2-P25 lattice induces tensile strain in Cu-impregnated TiO2-P25, whereas compressive strain in Cr- and V-impregnated TiO2-P25. Experimental evidences support chemical and mechanical stability of the photocatalysts. Type IV N2 adsorption–desorption isotherms, with a small H3 loop near the maximum relative pressure were observed. Metal surface impregnated photocatalysts are mesoporous with a similar surface roughness, and a narrow pore distribution around ca. 25 Å. They were chemically stable, showing no metal lixiviation. Their photocatalytic activity was followed by UV-Vis spectroscopy and HPLC–UV. A first order kinetic model appropriately fitted the experimental data. The fastest phenol degradation was obtained with M (0.1%)/TiO2-P25, the reactivity order being Cu > V >> Cr > TiO2-P25 under 366 nm irradiation, while TiO2-P25 > Cu > V > Cr, when using 254 nm radiation. TOC removal under 366 nm irradiation for 300 min showed almost quantitative mineralization for all tested materials, while 254 nm irradiation for 60 min led to maximal TOC removal (ca. 30%). Photoproducts and intermediate photoproducts were identified by HPLC–MS, and appropriate reaction pathways are proposed. The energy efficiency of the process was analysed, showing UV lamps are superior to UVA lamps, and that the efficiency of the surface impregnated catalyst varies in the order Cu > V > Cr.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Photocatalyzed degradation of phenol in aqueous solution over surface impregnated TiO2 (M = Cu, Cr, V) under UV-Vis (366 nm) and UV (254 nm) irradiation is described. Nanosized photocatalyts were prepared from TiO2-P25 by wet impregnation, and characterized by X-ray diffraction, X-ray fluorescence, transmission electron microscopy, UV-Vis diffuse reflectance spectroscopy, Raman spectroscopy, and adsorption studies. No oxide phases of the metal dopants were found, although their presence in the TiO2-P25 lattice induces tensile strain in Cu-impregnated TiO2-P25, whereas compressive strain in Cr- and V-impregnated TiO2-P25. Experimental evidences support chemical and mechanical stability of the photocatalysts. Type IV N2 adsorption–desorption isotherms, with a small H3 loop near the maximum relative pressure were observed. Metal surface impregnated photocatalysts are mesoporous with a similar surface roughness, and a narrow pore distribution around ca. 25 Å. They were chemically stable, showing no metal lixiviation. Their photocatalytic activity was followed by UV-Vis spectroscopy and HPLC–UV. A first order kinetic model appropriately fitted the experimental data. The fastest phenol degradation was obtained with M (0.1%)/TiO2-P25, the reactivity order being Cu > V >> Cr > TiO2-P25 under 366 nm irradiation, while TiO2-P25 > Cu > V > Cr, when using 254 nm radiation. TOC removal under 366 nm irradiation for 300 min showed almost quantitative mineralization for all tested materials, while 254 nm irradiation for 60 min led to maximal TOC removal (ca. 30%). Photoproducts and intermediate photoproducts were identified by HPLC–MS, and appropriate reaction pathways are proposed. The energy efficiency of the process was analysed, showing UV lamps are superior to UVA lamps, and that the efficiency of the surface impregnated catalyst varies in the order Cu > V > Cr.Garrido-Maestu, A.; Azinheiro, S.; Carvalho, J.; Espiña, B.; Prado, M.
Journal of Food Science and Technology 2020, 57 , pp. 4143–4151, 2020.
@article{Garrido-Maestu2020b,
title = {Evaluation and implementation of commercial antibodies for improved nanoparticle-based immunomagnetic separation and real-time PCR for faster detection of Listeria monocytogenes},
author = {Garrido-Maestu, A.; Azinheiro, S.; Carvalho, J.; Espiña, B.; Prado, M.},
url = {https://doi.org/10.1007/s13197-020-04450-1},
doi = {10.1007/s13197-020-04450-1},
year = {2020},
date = {2020-04-24},
journal = {Journal of Food Science and Technology 2020},
volume = {57},
pages = {4143–4151},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Teixeira, A; Paris, J.L., Roumani, F.; Diéguez, L.; Prado, M.; Espiña, B.; Abalde-Cela, S.; Garrido-Maestu, A.; Rodriguez-Lorenzo, L.
Multifuntional Gold Nanoparticles for the SERS Detection of Pathogens Combined with a LAMP–in–Microdroplets Approach Journal Article
Materials 2020, 13 (8), pp. 1934, 2020.
@article{Teixeira2020b,
title = {Multifuntional Gold Nanoparticles for the SERS Detection of Pathogens Combined with a LAMP–in–Microdroplets Approach},
author = {Teixeira, A; Paris, J.L., Roumani, F.; Diéguez, L.; Prado, M.; Espiña, B.; Abalde-Cela, S.; Garrido-Maestu, A.; Rodriguez-Lorenzo, L.},
url = {https://doi.org/10.3390/ma13081934},
doi = {10.3390/ma13081934},
year = {2020},
date = {2020-04-20},
journal = {Materials 2020},
volume = {13},
number = {8},
pages = {1934},
abstract = {We developed a droplet-based optofluidic system for the detection of foodborne pathogens. Specifically, the loop-mediated isothermal amplification (LAMP) technique was combined with surface-enhanced Raman scattering (SERS), which offers an excellent method for DNA ultradetection. However, the direct SERS detection of DNA compromises the simplicity of data interpretation due to the variability of its SERS fingerprints. Therefore, we designed an indirect SERS detection method using multifunctional gold nanoparticles (AuNPs) based on the formation of pyrophosphate generated during the DNA amplification by LAMP. Towards this goal, we prepared multifunctional AuNPs involving three components with key roles: (1) thiolated poly(ethylene glycol) as stabilizing agent, (2) 1-naphthalenethiol as Raman reporter, and (3) glutathione as a bioinspired chelating agent of magnesium (II) ions. Thus, the variation in the SERS signal of 1-naphthalenethiol was controlled by the aggregation of AuNPs triggered by the complexation of pyrophosphate and glutathione with free magnesium ions. Using this strategy, we detected Listeria monocytogenes, not only in buffer, but also in a food matrix (i.e., ultra-high temperaturemilk) enabled by the massive production of hotspots as a result of the self-assemblies that enhanced the SERS signal. This allowed the development of a microdroplet-LAMP-SERS platform with isothermal amplification and real-time identification capabilities.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}We developed a droplet-based optofluidic system for the detection of foodborne pathogens. Specifically, the loop-mediated isothermal amplification (LAMP) technique was combined with surface-enhanced Raman scattering (SERS), which offers an excellent method for DNA ultradetection. However, the direct SERS detection of DNA compromises the simplicity of data interpretation due to the variability of its SERS fingerprints. Therefore, we designed an indirect SERS detection method using multifunctional gold nanoparticles (AuNPs) based on the formation of pyrophosphate generated during the DNA amplification by LAMP. Towards this goal, we prepared multifunctional AuNPs involving three components with key roles: (1) thiolated poly(ethylene glycol) as stabilizing agent, (2) 1-naphthalenethiol as Raman reporter, and (3) glutathione as a bioinspired chelating agent of magnesium (II) ions. Thus, the variation in the SERS signal of 1-naphthalenethiol was controlled by the aggregation of AuNPs triggered by the complexation of pyrophosphate and glutathione with free magnesium ions. Using this strategy, we detected Listeria monocytogenes, not only in buffer, but also in a food matrix (i.e., ultra-high temperaturemilk) enabled by the massive production of hotspots as a result of the self-assemblies that enhanced the SERS signal. This allowed the development of a microdroplet-LAMP-SERS platform with isothermal amplification and real-time identification capabilities. -
2019
Septiadi, D.; Rodriguez-Lorenzo, L; Balog, S.; Spuch-Calvar, M.; Spiaggia, G.; Taladriz-Blanco, P.; Barosova, H.; Chortarea, S.; Clift, M. J. D.; Teeguarden, J.; Sharma, M.; Petri-Fink, A.; Rothen-Rutishauser, B.
Quantification of Carbon Nanotube Doses in Adherent Cell Culture Assays Using UV-VIS-NIR Spectroscopy Journal Article
Nanomaterials 2019, 9 (12), pp. 1765, 2019.
@article{Septiadi2019,
title = {Quantification of Carbon Nanotube Doses in Adherent Cell Culture Assays Using UV-VIS-NIR Spectroscopy},
author = {Septiadi, D.; Rodriguez-Lorenzo, L; Balog, S.; Spuch-Calvar, M.; Spiaggia, G.; Taladriz-Blanco, P.; Barosova, H.; Chortarea, S.; Clift, M. J. D.; Teeguarden, J.; Sharma, M.; Petri-Fink, A.; Rothen-Rutishauser, B.},
url = {https://doi.org/10.3390/nano9121765},
doi = {10.3390/nano9121765},
year = {2019},
date = {2019-12-11},
journal = {Nanomaterials 2019},
volume = {9},
number = {12},
pages = {1765},
abstract = {The overt hazard of carbon nanotubes (CNTs) is often assessed using in vitro methods, but determining a dose–response relationship is still a challenge due to the analytical difficulty of quantifying the dose delivered to cells. An approach to accurately quantify CNT doses for submerged in vitro adherent cell culture systems using UV-VIS-near-infrared (NIR) spectroscopy is provided here. Two types of multi-walled CNTs (MWCNTs), Mitsui-7 and Nanocyl, which are dispersed in protein rich cell culture media, are studied as tested materials. Post 48 h of CNT incubation, the cellular fractions are subjected to microwave-assisted acid digestion/oxidation treatment, which eliminates biological matrix interference and improves CNT colloidal stability. The retrieved oxidized CNTs are analyzed and quantified using UV-VIS-NIR spectroscopy. In vitro imaging and quantification data in the presence of human lung epithelial cells (A549) confirm that up to 85% of Mitsui-7 and 48% for Nanocyl sediment interact (either through internalization or adherence) with cells during the 48 h of incubation. This finding is further confirmed using a sedimentation approach to estimate the delivered dose by measuring the depletion profile of the CNTs.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}The overt hazard of carbon nanotubes (CNTs) is often assessed using in vitro methods, but determining a dose–response relationship is still a challenge due to the analytical difficulty of quantifying the dose delivered to cells. An approach to accurately quantify CNT doses for submerged in vitro adherent cell culture systems using UV-VIS-near-infrared (NIR) spectroscopy is provided here. Two types of multi-walled CNTs (MWCNTs), Mitsui-7 and Nanocyl, which are dispersed in protein rich cell culture media, are studied as tested materials. Post 48 h of CNT incubation, the cellular fractions are subjected to microwave-assisted acid digestion/oxidation treatment, which eliminates biological matrix interference and improves CNT colloidal stability. The retrieved oxidized CNTs are analyzed and quantified using UV-VIS-NIR spectroscopy. In vitro imaging and quantification data in the presence of human lung epithelial cells (A549) confirm that up to 85% of Mitsui-7 and 48% for Nanocyl sediment interact (either through internalization or adherence) with cells during the 48 h of incubation. This finding is further confirmed using a sedimentation approach to estimate the delivered dose by measuring the depletion profile of the CNTs.Rodríguez-Lorenzo,L.; Garrido-Maestu, A.; Bhunia, A. K.; Espiña, B.; Prado, M.; Diéguez, L; Abalde-Cela, S.
Gold Nanostars for the Detection of Foodborne Pathogens via Surface-Enhanced Raman Scattering Combined with Microfluidics Journal Article
ACS Appl. Nano Mater., 2 (10), pp. 6081–6086, 2019.
@article{Rodríguez-Lorenzo2019,
title = {Gold Nanostars for the Detection of Foodborne Pathogens via Surface-Enhanced Raman Scattering Combined with Microfluidics},
author = {Rodríguez-Lorenzo,L.; Garrido-Maestu, A.; Bhunia, A. K.; Espiña, B.; Prado, M.; Diéguez, L; Abalde-Cela, S.},
url = {https://doi.org/10.1021/acsanm.9b01223},
doi = {10.1021/acsanm.9b01223},
year = {2019},
date = {2019-09-20},
journal = {ACS Appl. Nano Mater.},
volume = {2},
number = {10},
pages = {6081–6086},
abstract = {Herein, we demonstrated the potential of surface-enhanced Raman scattering (SERS) spectroscopy combined with microfluidics for the detection and discrimination of foodborne pathogens. SERS-tagged gold nanostars were functionalized with a monoclonal antibody specific for Listeria monocytogenes. In the presence of L. monocytogenes, a SERS signal corresponding to the SERS tag paired to the antibody was detected in real time and in continuous flow, enabling the discrimination of L. monocytogenes and Listeria innocua in just 100 s. To the best of our knowledge, this is the first time that SERS tags have been used for the in-flow detection of living organisms.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Herein, we demonstrated the potential of surface-enhanced Raman scattering (SERS) spectroscopy combined with microfluidics for the detection and discrimination of foodborne pathogens. SERS-tagged gold nanostars were functionalized with a monoclonal antibody specific for Listeria monocytogenes. In the presence of L. monocytogenes, a SERS signal corresponding to the SERS tag paired to the antibody was detected in real time and in continuous flow, enabling the discrimination of L. monocytogenes and Listeria innocua in just 100 s. To the best of our knowledge, this is the first time that SERS tags have been used for the in-flow detection of living organisms.Santos, M.B.; Queirós, R.B.; Geraldes, A.; Marques, C; Vilas-Boas, V.; Dieguez, L.; Paz, E.; Ferreira, R.; Morais, J.; Vasconcelos, V.; Piteira, J.; Freitas, P.P.; Espiña, B.
Biosensors & Bioelectronics, 142 , pp. 111550, 2019.
@article{Santos2019,
title = {Portable sensing system based on electrochemical impedance spectroscopy for the simultaneous quantification of free and total microcystin-LR in freshwaters},
author = {Santos, M.B.; Queirós, R.B.; Geraldes, A.; Marques, C; Vilas-Boas, V.; Dieguez, L.; Paz, E.; Ferreira, R.; Morais, J.; Vasconcelos, V.; Piteira, J.; Freitas, P.P.; Espiña, B.},
doi = {https://doi.org/10.1016/j.bios.2019.111550},
year = {2019},
date = {2019-07-30},
journal = {Biosensors & Bioelectronics},
volume = {142},
pages = {111550},
abstract = {Microcystins are the most worldwide extended and common toxins produced by cyanobacteria in freshwater. Microcystin-leucine arginine (MC-LR), associated with the most toxic incidents involving microcystins, are within the cyanobacteria (intracellular) until released into the surrounding waters (extracellular) during cell lysis. Therefore, the relationship between intracellular and extracellular cyanotoxins will allow a comprehensive risk of cyanobacteria-containing waters, preventing disease and improving human safety. In this work, we present the development of a novel portable microfluidic sensing platform for the simultaneous detection of free (extracellular) and total MC-LR (intracellular and extracellular). The integrated system contains the sample processing and detection modules capable of performing the chemical lysis, filtration, sample mixing with antibodies, and electrochemical detection of MC-LR based on an indirect strategy. The performance of the immunosensors was evaluated by electrochemical impedance spectroscopy, showing a linear dynamic range between 3.3 × 10−4 and 10−7 g L−1 and a limit of detection of 5.7 × 10−10 g L−1. The results demonstrate the potential of the developed portable biosensor platform and its suitable application for the analysis of MC-LR at regulated levels for drinking water. Finally, the integrated system was able to simultaneously detect the free and total MC-LR on a Microcystis aeruginosa culture. To the best of our knowledge this is the first described system that can differentiate between intracellular and extracellular concentration of MC-LR. This novel electrochemical sensing platform avoids the multiple processing steps typically needed for standard MC-LR analysis in the laboratory and provides an early warning system for MC-LR remote monitoring in water.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Microcystins are the most worldwide extended and common toxins produced by cyanobacteria in freshwater. Microcystin-leucine arginine (MC-LR), associated with the most toxic incidents involving microcystins, are within the cyanobacteria (intracellular) until released into the surrounding waters (extracellular) during cell lysis. Therefore, the relationship between intracellular and extracellular cyanotoxins will allow a comprehensive risk of cyanobacteria-containing waters, preventing disease and improving human safety. In this work, we present the development of a novel portable microfluidic sensing platform for the simultaneous detection of free (extracellular) and total MC-LR (intracellular and extracellular). The integrated system contains the sample processing and detection modules capable of performing the chemical lysis, filtration, sample mixing with antibodies, and electrochemical detection of MC-LR based on an indirect strategy. The performance of the immunosensors was evaluated by electrochemical impedance spectroscopy, showing a linear dynamic range between 3.3 × 10−4 and 10−7 g L−1 and a limit of detection of 5.7 × 10−10 g L−1. The results demonstrate the potential of the developed portable biosensor platform and its suitable application for the analysis of MC-LR at regulated levels for drinking water. Finally, the integrated system was able to simultaneously detect the free and total MC-LR on a Microcystis aeruginosa culture. To the best of our knowledge this is the first described system that can differentiate between intracellular and extracellular concentration of MC-LR. This novel electrochemical sensing platform avoids the multiple processing steps typically needed for standard MC-LR analysis in the laboratory and provides an early warning system for MC-LR remote monitoring in water.Fong, W.-K.; Moore, T. L.; Balog, S.; Vanhecke, D.; Rodriguez-Lorenzo, L.; Rothen-Rutishauser, B.; Lattuada, M.; Petri-Fink, A.
Springer International Publishing, 2019.
@inbook{Fong2019,
title = {Nanoparticle Behaviour in Complex Media: Methods for Characterizing Physicochemical Properties, Evaluating Protein Corona Formation, and Implications for Biological Studies},
author = {Fong, W.-K.; Moore, T. L.; Balog, S.; Vanhecke, D.; Rodriguez-Lorenzo, L.; Rothen-Rutishauser, B.; Lattuada, M.; Petri-Fink, A.},
url = {https://www.springerprofessional.de/en/nanoparticle-behaviour-in-complex-media-methods-for-characterizi/16660714},
year = {2019},
date = {2019-07-30},
journal = {Biosensors & Bioelectronics},
publisher = {Springer International Publishing},
abstract = {The transformation of nanoparticles (NPs) in physiological milieu is a dynamic phenomenon that is the subject of intense investigation. When introduced into the body, NPs can undergo a variety of changes, such as, protein adsorption, dissolution, agglomeration/aggregation, structural deformities and redox reactions. It is these changes that subsequently determine the uptake, bioavailability, translocation and fate of NPs, which ultimately determine their therapeutic efficiency, diagnostic efficacy or toxicity. This chapter will consider the colloidal interactions at the interface of NPs with the contents of biological milieu, the practical and theoretical considerations required to modify analytical and imaging techniques to detect and, if possible, quantify NPs in this complex environment, and the requirement for a highly interdisciplinary approach to understand the behaviour at the bio-nano interface.},
keywords = {},
pubstate = {published},
tppubtype = {inbook}
}The transformation of nanoparticles (NPs) in physiological milieu is a dynamic phenomenon that is the subject of intense investigation. When introduced into the body, NPs can undergo a variety of changes, such as, protein adsorption, dissolution, agglomeration/aggregation, structural deformities and redox reactions. It is these changes that subsequently determine the uptake, bioavailability, translocation and fate of NPs, which ultimately determine their therapeutic efficiency, diagnostic efficacy or toxicity. This chapter will consider the colloidal interactions at the interface of NPs with the contents of biological milieu, the practical and theoretical considerations required to modify analytical and imaging techniques to detect and, if possible, quantify NPs in this complex environment, and the requirement for a highly interdisciplinary approach to understand the behaviour at the bio-nano interface.Crippa, F.; Rodriguez-Lorenzo, L.; Hua, X.; Goris, B.; Bals, S.; Garitaonandia, J. S.; Balog, S.; Burnand, D.; Hirt, A. M.; Haeni, L.; Lattuada, M.; Rothen-Rutishauser, B.; Petri-Fink, A.
Phase Transformation of Superparamagnetic Iron Oxide Nanoparticles via Thermal Annealing: Implications for Hyperthermia Applications Journal Article
ACS Appl. Nano Mater., 2 (7), pp. 4462–4470, 2019.
@article{Crippa2019,
title = {Phase Transformation of Superparamagnetic Iron Oxide Nanoparticles via Thermal Annealing: Implications for Hyperthermia Applications},
author = {Crippa, F.; Rodriguez-Lorenzo, L.; Hua, X.; Goris, B.; Bals, S.; Garitaonandia, J. S.; Balog, S.; Burnand, D.; Hirt, A. M.; Haeni, L.; Lattuada, M.; Rothen-Rutishauser, B.; Petri-Fink, A.},
url = {https://doi.org/10.1021/acsanm.9b00823},
doi = {10.1021/acsanm.9b00823},
year = {2019},
date = {2019-06-27},
journal = {ACS Appl. Nano Mater.},
volume = {2},
number = {7},
pages = {4462–4470},
abstract = {Magnetic hyperthermia has the potential to play an important role in cancer therapy and its efficacy relies on the nanomaterials selected. Superparamagnetic iron oxide nanoparticles (SPIONs) are excellent candidates due to the ability of producing enough heat to kill tumor cells by thermal ablation. However, their heating properties depend strongly on crystalline structure and size, which may not be controlled and tuned during the synthetic process; therefore, a postprocessing is needed. We show how thermal annealing can be simultaneously coupled with ligand exchange to stabilize the SPIONs in polar solvents and to modify their crystal structure, which improves hyperthermia behavior. Using high-resolution transmission electron microscopy, X-ray diffraction, Mössbauer spectroscopy, vibrating sample magnetometry, and lock-in thermography, we systematically investigate the impact of size and ligand exchange procedure on crystallinity, their magnetism, and heating ability. We describe a valid and simple approach to optimize SPIONs for hyperthermia by carefully controlling the size, colloidal stability, and crystallinity.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Magnetic hyperthermia has the potential to play an important role in cancer therapy and its efficacy relies on the nanomaterials selected. Superparamagnetic iron oxide nanoparticles (SPIONs) are excellent candidates due to the ability of producing enough heat to kill tumor cells by thermal ablation. However, their heating properties depend strongly on crystalline structure and size, which may not be controlled and tuned during the synthetic process; therefore, a postprocessing is needed. We show how thermal annealing can be simultaneously coupled with ligand exchange to stabilize the SPIONs in polar solvents and to modify their crystal structure, which improves hyperthermia behavior. Using high-resolution transmission electron microscopy, X-ray diffraction, Mössbauer spectroscopy, vibrating sample magnetometry, and lock-in thermography, we systematically investigate the impact of size and ligand exchange procedure on crystallinity, their magnetism, and heating ability. We describe a valid and simple approach to optimize SPIONs for hyperthermia by carefully controlling the size, colloidal stability, and crystallinity.Bossert, D.; Urban, D. A.; Maceroni, M.; Ackermann-Hirschi, L.; Haeni, L.; Yajan, P.; Spuch-Calvar, M.; Rothen-Rutishauser, B.; Rodriguez-Lorenzo, L.; Petri-Fink, A.; Schwab, F.
A hydrofluoric acid-free method to dissolve and quantify silica nanoparticles in aqueous and solid matrices Journal Article
Scientific Reports 2019, 9 (1), pp. 7938, 2019.
@article{Bossert2019,
title = {A hydrofluoric acid-free method to dissolve and quantify silica nanoparticles in aqueous and solid matrices},
author = {Bossert, D.; Urban, D. A.; Maceroni, M.; Ackermann-Hirschi, L.; Haeni, L.; Yajan, P.; Spuch-Calvar, M.; Rothen-Rutishauser, B.; Rodriguez-Lorenzo, L.; Petri-Fink, A.; Schwab, F.},
url = {https://dx.doi.org/10.1038%2Fs41598-019-44128-z},
doi = {10.1038/s41598-019-44128-z},
year = {2019},
date = {2019-05-28},
journal = {Scientific Reports 2019},
volume = {9},
number = {1},
pages = {7938},
abstract = {As the commercial use of synthetic amorphous silica nanomaterials (SiO2-NPs) increases, their effects on the environment and human health have still not been explored in detail. An often-insurmountable obstacle for SiO2-NP fate and hazard research is the challenging analytics of solid particulate silica species, which involves toxic and corrosive hydrofluoric acid (HF). We therefore developed and validated a set of simple hydrofluoric acid-free sample preparation methods for the quantification of amorphous SiO2 micro- and nanoparticles. To circumvent HF, we dissolved the SiO2-NPs by base-catalyzed hydrolysis at room temperature or under microwave irradiation using potassium hydroxide, replacing the stabilizing fluoride ions with OH−, and exploiting the stability of the orthosilicic acid monomer under a strongly basic pH. Inductively coupled plasma – optical emission spectroscopy (ICP-OES) or a colorimetric assay served to quantify silicon. The lowest KOH: SiO2 molar ratio to effectively dissolve and quantify SiO2-NPs was 1.2 for colloidal Stöber SiO2-NPs at a pH >12. Fumed SiO2-NPs (Aerosil®) or food grade SiO2 (E551) containing SiO2-NPs were degradable at higher KOH: SiO2 ratios >8000. Thus, hydrofluoric acid-free SiO2-NP digestion protocols based on KOH present an effective (recoveries of >84%), less hazardous, and easy to implement alternative to current methods.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}As the commercial use of synthetic amorphous silica nanomaterials (SiO2-NPs) increases, their effects on the environment and human health have still not been explored in detail. An often-insurmountable obstacle for SiO2-NP fate and hazard research is the challenging analytics of solid particulate silica species, which involves toxic and corrosive hydrofluoric acid (HF). We therefore developed and validated a set of simple hydrofluoric acid-free sample preparation methods for the quantification of amorphous SiO2 micro- and nanoparticles. To circumvent HF, we dissolved the SiO2-NPs by base-catalyzed hydrolysis at room temperature or under microwave irradiation using potassium hydroxide, replacing the stabilizing fluoride ions with OH−, and exploiting the stability of the orthosilicic acid monomer under a strongly basic pH. Inductively coupled plasma – optical emission spectroscopy (ICP-OES) or a colorimetric assay served to quantify silicon. The lowest KOH: SiO2 molar ratio to effectively dissolve and quantify SiO2-NPs was 1.2 for colloidal Stöber SiO2-NPs at a pH >12. Fumed SiO2-NPs (Aerosil®) or food grade SiO2 (E551) containing SiO2-NPs were degradable at higher KOH: SiO2 ratios >8000. Thus, hydrofluoric acid-free SiO2-NP digestion protocols based on KOH present an effective (recoveries of >84%), less hazardous, and easy to implement alternative to current methods.Hocevar, S.; Milosevic, A.; Rodriguez-Lorenzo, L.; Ackermann-Hirschi, L.; Mottas, I.; Petri-Fink, A.; Rothen-Rutishauser, B.; Bourquin, C.; Clift, M. J. D.
Polymer-Coated Gold Nanospheres Do Not Impair the Innate Immune Function of Human B Lymphocytes in Vitro Journal Article
ACS Nano 2019, 13 (6), pp. 6790–6800, 2019.
@article{Hocevar2019,
title = {Polymer-Coated Gold Nanospheres Do Not Impair the Innate Immune Function of Human B Lymphocytes in Vitro},
author = {Hocevar, S.; Milosevic, A.; Rodriguez-Lorenzo, L.; Ackermann-Hirschi, L.; Mottas, I.; Petri-Fink, A.; Rothen-Rutishauser, B.; Bourquin, C.; Clift, M. J. D.},
url = {https://doi.org/10.1021/acsnano.9b01492},
doi = {10.1021/acsnano.9b01492},
year = {2019},
date = {2019-05-22},
journal = {ACS Nano 2019},
volume = {13},
number = {6},
pages = {6790–6800},
abstract = {Gold nanoparticles (GNPs) are intended for use within a variety of biomedical applications due to their physicochemical properties. Although, in general, biocompatibility of GNPs with immune cells such as macrophages and dendritic cells is well established, the impact of GNPs on B lymphocyte immune function remains to be determined. Since B lymphocytes play an important role in health and disease, the suitability of GNPs as a B cell-targeting tool is of high relevance. Thus, we provide information on the interactions of GNPs with B lymphocytes. Herein, we exposed freshly isolated human B lymphocytes to a set of well-characterized and biomedically relevant GNPs with distinct surface (polyethylene glycol (PEG), PEG/poly(vinyl alcohol) (PEG/PVA)) and shape (spheres, rods) characteristics. Polymer-coated GNPs poorly interacted with B lymphocytes, in contrast to uncoated GNPs. Importantly, none of the GNPs significantly affected cell viability, even at the highest concentration of 20 μg/mL over a 24 h suspension exposure period. Furthermore, none of the nanosphere formulations affected the expression of activation markers (CD69, CD86, MHC II) of the naive B lymphocytes, nor did they cause an increase in the secretion of pro-inflammatory cytokines (i.e. , IL-6, IL-1β). However, the absence of polymer coating on the sphere GNPs and the rod shape caused a decrease in IL-6 cytokine production by activated B lymphocytes, suggesting a functional impairment. With these findings, the present study contributes imperative knowledge toward the safe-by-design approaches being conducted to benefit the development of nanomaterials, specifically those as theranostic tools.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Gold nanoparticles (GNPs) are intended for use within a variety of biomedical applications due to their physicochemical properties. Although, in general, biocompatibility of GNPs with immune cells such as macrophages and dendritic cells is well established, the impact of GNPs on B lymphocyte immune function remains to be determined. Since B lymphocytes play an important role in health and disease, the suitability of GNPs as a B cell-targeting tool is of high relevance. Thus, we provide information on the interactions of GNPs with B lymphocytes. Herein, we exposed freshly isolated human B lymphocytes to a set of well-characterized and biomedically relevant GNPs with distinct surface (polyethylene glycol (PEG), PEG/poly(vinyl alcohol) (PEG/PVA)) and shape (spheres, rods) characteristics. Polymer-coated GNPs poorly interacted with B lymphocytes, in contrast to uncoated GNPs. Importantly, none of the GNPs significantly affected cell viability, even at the highest concentration of 20 μg/mL over a 24 h suspension exposure period. Furthermore, none of the nanosphere formulations affected the expression of activation markers (CD69, CD86, MHC II) of the naive B lymphocytes, nor did they cause an increase in the secretion of pro-inflammatory cytokines (i.e. , IL-6, IL-1β). However, the absence of polymer coating on the sphere GNPs and the rod shape caused a decrease in IL-6 cytokine production by activated B lymphocytes, suggesting a functional impairment. With these findings, the present study contributes imperative knowledge toward the safe-by-design approaches being conducted to benefit the development of nanomaterials, specifically those as theranostic tools.Rodriguez Lorenzo Kolen'ko Yu Espiña Salonen S P S ; L ; V ; B ; L M Romero V.; Fernandes
Recyclable magnetic covalent organic framework for the extraction of marine biotoxins Journal Article
Nanoscale, 2019.
@article{Romero2019,
title = {Recyclable magnetic covalent organic framework for the extraction of marine biotoxins},
author = {Rodriguez Lorenzo Kolen'ko Yu Espiña Salonen S P S ; L ; V ; B ; L M Romero V.; Fernandes},
doi = {10.1039/C9NR00388F},
year = {2019},
date = {2019-03-04},
journal = {Nanoscale},
abstract = {A novel procedure for the preparation of magnetic covalent organic frameworks (COFs) is reported. In situ functionalization of Fe3O4 with dopamine rapidly afforded amino-functionalized magnetic nanoparticles, which after decoration with a COF building block and subsequent COF growth gave access to magnetic composite mTpBD-Me2. The optimized synthesis conditions yielded crystalline and superparamagnetic material with no loss in surface area as compared to bulk COF. The composite material was employed for the first time in magnetic solid-phase extraction of marine biotoxins from seawater with high efficiency, where calculated maximum adsorption capacities of 812 mg g–1 and 830 mg g–1 were found for okadaic acid (OA) and dinophysistoxin-1 (DTX-1), respectively, corresponding to an increase of ~500 fold for OA and ~300-fold for DTX-1 as compared to the commonly used non-magnetic macroporous resins. Nearly quantitative desorption efficiency of both biotoxins was obtained using 2-propanol as solvent, rendering the composite materials recyclable with merely minor losses in adsorption capacity after five consecutive cycles of adsorption/desorption. In addition, retention of crystallinity after the adsorption cycles highlights the stability of the composite in seawater. These results illustrate the great efficiency of the novel material in biotoxin adsorption and show great promise for its application in environmental monitoring programs.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}A novel procedure for the preparation of magnetic covalent organic frameworks (COFs) is reported. In situ functionalization of Fe3O4 with dopamine rapidly afforded amino-functionalized magnetic nanoparticles, which after decoration with a COF building block and subsequent COF growth gave access to magnetic composite mTpBD-Me2. The optimized synthesis conditions yielded crystalline and superparamagnetic material with no loss in surface area as compared to bulk COF. The composite material was employed for the first time in magnetic solid-phase extraction of marine biotoxins from seawater with high efficiency, where calculated maximum adsorption capacities of 812 mg g–1 and 830 mg g–1 were found for okadaic acid (OA) and dinophysistoxin-1 (DTX-1), respectively, corresponding to an increase of ~500 fold for OA and ~300-fold for DTX-1 as compared to the commonly used non-magnetic macroporous resins. Nearly quantitative desorption efficiency of both biotoxins was obtained using 2-propanol as solvent, rendering the composite materials recyclable with merely minor losses in adsorption capacity after five consecutive cycles of adsorption/desorption. In addition, retention of crystallinity after the adsorption cycles highlights the stability of the composite in seawater. These results illustrate the great efficiency of the novel material in biotoxin adsorption and show great promise for its application in environmental monitoring programs.Marisa Sárria Ivone Pinheiro Vânia Vilas-Boas Joao Peixoto Begoña Espiña P Cindy Dias Nagamalai Vasimalai
Biocompatibility and Bioimaging Potential of Fruit-Based Carbon Dots Journal Article
Nanomaterials (Basel), 9 (2), pp. E199, 2019.
@article{Dias2019,
title = {Biocompatibility and Bioimaging Potential of Fruit-Based Carbon Dots},
author = {Marisa Sárria Ivone Pinheiro Vânia Vilas-Boas Joao Peixoto Begoña Espiña P Cindy Dias Nagamalai Vasimalai},
doi = {10.3390/nano9020199},
year = {2019},
date = {2019-02-03},
journal = {Nanomaterials (Basel)},
volume = {9},
number = {2},
pages = {E199},
abstract = {Photo-luminescent carbon dots (CD) have become promising nanomaterials and their synthesis from natural products has attracted attention by the possibility of making the most of affordable, sustainable and, readily-available carbon sources. Here, we report on the synthesis, characterization and bioimaging potential of CDs produced from diverse extensively produced fruits: kiwi, avocado and pear. The in vitro cytotoxicity and anticancer potential of those CDs were assessed by comparing human epithelial cells from normal adult kidney and colorectal adenocarcinoma cells. In vivo toxicity was evaluated using zebrafish embryos given their peculiar embryogenesis, with transparent embryos developing ex-utero, allowing a real-time analysis. In vitro and in vivo experiments revealed that the synthesized CD presented toxicity only at concentrations of ≥1.5 mg mL-1. Kiwi CD exhibited the highest toxicity to both cells lines and zebrafish embryos, presenting lower LD50 values. Interestingly, despite inducing lower cytotoxicity in normal cells than the other CDs, black pepper CDs resulted in higher toxicity in vivo. The bio-distribution of CD in zebrafish embryos upon uptake was investigated using fluorescence microscopy. We observed a higher accumulation of CD in the eye and yolk sac, avocado CD being the ones more retained, indicating their potential usefulness in bio-imaging applications. This study shows the action of fruit-based CDs from kiwi, avocado and pear. However the compounds present in these fruit-based CDs and their mechanism of action as a bioimaging agent need to be further explored.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Photo-luminescent carbon dots (CD) have become promising nanomaterials and their synthesis from natural products has attracted attention by the possibility of making the most of affordable, sustainable and, readily-available carbon sources. Here, we report on the synthesis, characterization and bioimaging potential of CDs produced from diverse extensively produced fruits: kiwi, avocado and pear. The in vitro cytotoxicity and anticancer potential of those CDs were assessed by comparing human epithelial cells from normal adult kidney and colorectal adenocarcinoma cells. In vivo toxicity was evaluated using zebrafish embryos given their peculiar embryogenesis, with transparent embryos developing ex-utero, allowing a real-time analysis. In vitro and in vivo experiments revealed that the synthesized CD presented toxicity only at concentrations of ≥1.5 mg mL-1. Kiwi CD exhibited the highest toxicity to both cells lines and zebrafish embryos, presenting lower LD50 values. Interestingly, despite inducing lower cytotoxicity in normal cells than the other CDs, black pepper CDs resulted in higher toxicity in vivo. The bio-distribution of CD in zebrafish embryos upon uptake was investigated using fluorescence microscopy. We observed a higher accumulation of CD in the eye and yolk sac, avocado CD being the ones more retained, indicating their potential usefulness in bio-imaging applications. This study shows the action of fruit-based CDs from kiwi, avocado and pear. However the compounds present in these fruit-based CDs and their mechanism of action as a bioimaging agent need to be further explored.Burnand Lemal Crippa Monnier Christophe Rodriguez-Lorenzo Petri-Fink Rothen-Rutishauser J; D; P; F; A ; L ; A ; B MilosevicAc A; Bourquin
Artificial Lysosomal Platform to Study Nanoparticle Long-term Stability Journal Article
Chimia, 73 (1), pp. 55-58, 2019.
@article{MilosevicAc2019b,
title = {Artificial Lysosomal Platform to Study Nanoparticle Long-term Stability},
author = {Burnand Lemal Crippa Monnier Christophe Rodriguez-Lorenzo Petri-Fink Rothen-Rutishauser J; D; P; F; A ; L ; A ; B MilosevicAc A; Bourquin},
doi = {https://doi.org/10.2533/chimia.2019.55},
year = {2019},
date = {2019-02-01},
journal = {Chimia},
volume = {73},
number = {1},
pages = {55-58},
abstract = {Nanoparticles (NPs) possess unique properties useful for designing specific functionalities for biomedi- cal applications. A prerequisite of a safe-by-design and effective use in any biomedical application is to study NP–cell interactions to gain a better understanding of cellular consequences upon exposure. Cellular uptake of NPs results mainly in the localization of NPs in the complex environment of lysosomes, a compartment which can be mimicked by artificial lysosomal fluid. In this work we showed the applicability of lysosomal fluid as a platform for a fast assessment of gold, iron oxide and silica NP stability over 24 h in a relevant biological fluid, by using multiple analytical methods.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Nanoparticles (NPs) possess unique properties useful for designing specific functionalities for biomedi- cal applications. A prerequisite of a safe-by-design and effective use in any biomedical application is to study NP–cell interactions to gain a better understanding of cellular consequences upon exposure. Cellular uptake of NPs results mainly in the localization of NPs in the complex environment of lysosomes, a compartment which can be mimicked by artificial lysosomal fluid. In this work we showed the applicability of lysosomal fluid as a platform for a fast assessment of gold, iron oxide and silica NP stability over 24 h in a relevant biological fluid, by using multiple analytical methods.Rafiee Rodriguez-Lorenzo List Rothen-Rutishauser Mayer Petri-Fink C ; S ; L ; J ; B ; M ; A Ruegg C.; Reis
A Bio-Inspired Amplification Cascade for the Detection of Rare Cancer Cells Journal Article
Chimia, 73 (1), pp. 63-68, 2019.
@article{Ruegg2019b,
title = {A Bio-Inspired Amplification Cascade for the Detection of Rare Cancer Cells},
author = {Rafiee Rodriguez-Lorenzo List Rothen-Rutishauser Mayer Petri-Fink C ; S ; L ; J ; B ; M ; A Ruegg C.; Reis},
doi = {https://doi.org/10.2533/chimia.2019.63},
year = {2019},
date = {2019-02-01},
journal = {Chimia},
volume = {73},
number = {1},
pages = {63-68},
abstract = {The main cause of cancer-related death is due to cancer cell spreading and formation of secondary tumors in distant organs, the so-called metastases. Metastatic cancer cells are detectable in the blood of cancer patients as circulating tumor cells (CTC) and may be exploited for prognostic and monitoring purposes, including in breast cancer. Due to their very low frequency, however, their quantitative detection remains a challenge in clinical practice. Nature has developed mechanisms to amplify rare biological events or weak signals, such as intracellular signaling pathways, cytokine networks or the coagulation cascades. At the National Center for Competence in Research (NCCR) in Bio-Inspired Materials we are coupling gold nanoparticle-based strategies with fibrinogen and DNA bio-inspired amplification cascades to develop an in vitro test to specifically and sensitively detect CTCs in patients' blood. In this article, we describe the biological context, the concept of bio-inspired amplification, and the approaches chosen. We also discuss limitations, open questions and further potential biomedical applications of such an approach.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}The main cause of cancer-related death is due to cancer cell spreading and formation of secondary tumors in distant organs, the so-called metastases. Metastatic cancer cells are detectable in the blood of cancer patients as circulating tumor cells (CTC) and may be exploited for prognostic and monitoring purposes, including in breast cancer. Due to their very low frequency, however, their quantitative detection remains a challenge in clinical practice. Nature has developed mechanisms to amplify rare biological events or weak signals, such as intracellular signaling pathways, cytokine networks or the coagulation cascades. At the National Center for Competence in Research (NCCR) in Bio-Inspired Materials we are coupling gold nanoparticle-based strategies with fibrinogen and DNA bio-inspired amplification cascades to develop an in vitro test to specifically and sensitively detect CTCs in patients' blood. In this article, we describe the biological context, the concept of bio-inspired amplification, and the approaches chosen. We also discuss limitations, open questions and further potential biomedical applications of such an approach.Moore, T.L.; Urban, D.A.; Rodriguez-Lorenzo, L.; Milosevic, A.; Crippa, F.; Spuch-Calvar, M.; Balog, S.; Rothen-Rutishauser, B.; Lattuada, M.; Petri-Fink,
Nanoparticle administration method in cell culture alters particle-cell interaction Journal Article
Scientific Reports, 9 (900), 2019.
@article{Moore2019,
title = {Nanoparticle administration method in cell culture alters particle-cell interaction},
author = {Moore, T.L.; Urban, D.A.; Rodriguez-Lorenzo, L.; Milosevic, A.; Crippa, F.; Spuch-Calvar, M.; Balog, S.; Rothen-Rutishauser, B.; Lattuada, M.; Petri-Fink, },
url = {https://doi.org/10.1038/s41598-018-36954-4},
doi = {10.1038/s41598-018-36954-4},
year = {2019},
date = {2019-01-29},
journal = {Scientific Reports},
volume = {9},
number = {900},
abstract = {As a highly interdisciplinary field, working with nanoparticles in a biomedical context requires a robust understanding of soft matter physics, colloidal behaviors, nano-characterization methods, biology, and bio-nano interactions. When reporting results, it can be easy to overlook simple, seemingly trivial experimental details. In this context, we set out to understand how in vitro technique, specifically the way we administer particles in 2D culture, can influence experimental outcomes. Gold nanoparticles coated with poly(vinylpyrrolidone) were added to J774A.1 mouse monocyte/macrophage cultures as either a concentrated bolus, a bolus then mixed via aspiration, or pre-mixed in cell culture media. Particle-cell interaction was monitored via inductively coupled plasma-optical emission spectroscopy and we found that particles administered in a concentrated dose interacted more with cells compared to the pre-mixed administration method. Spectroscopy studies reveal that the initial formation of the protein corona upon introduction to cell culture media may be responsible for the differences in particle-cell interaction. Modeling of particle deposition using the in vitro sedimentation, diffusion and dosimetry model helped to clarify what particle phenomena may be occurring at the cellular interface. We found that particle administration method in vitro has an effect on particle-cell interactions (i.e. cellular adsorption and uptake). Initial introduction of particles in to complex biological media has a lasting effect on the formation of the protein corona, which in turn mediates particle-cell interaction. It is of note that a minor detail, the way in which we administer particles in cell culture, can have a significant effect on what we observe regarding particle interactions in vitro.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}As a highly interdisciplinary field, working with nanoparticles in a biomedical context requires a robust understanding of soft matter physics, colloidal behaviors, nano-characterization methods, biology, and bio-nano interactions. When reporting results, it can be easy to overlook simple, seemingly trivial experimental details. In this context, we set out to understand how in vitro technique, specifically the way we administer particles in 2D culture, can influence experimental outcomes. Gold nanoparticles coated with poly(vinylpyrrolidone) were added to J774A.1 mouse monocyte/macrophage cultures as either a concentrated bolus, a bolus then mixed via aspiration, or pre-mixed in cell culture media. Particle-cell interaction was monitored via inductively coupled plasma-optical emission spectroscopy and we found that particles administered in a concentrated dose interacted more with cells compared to the pre-mixed administration method. Spectroscopy studies reveal that the initial formation of the protein corona upon introduction to cell culture media may be responsible for the differences in particle-cell interaction. Modeling of particle deposition using the in vitro sedimentation, diffusion and dosimetry model helped to clarify what particle phenomena may be occurring at the cellular interface. We found that particle administration method in vitro has an effect on particle-cell interactions (i.e. cellular adsorption and uptake). Initial introduction of particles in to complex biological media has a lasting effect on the formation of the protein corona, which in turn mediates particle-cell interaction. It is of note that a minor detail, the way in which we administer particles in cell culture, can have a significant effect on what we observe regarding particle interactions in vitro.Yury Kolen’ko Manuel Bañobre-López Marina Brito Verónica Martins José Alberto Duarte Dmitri Petrovykh Paulo Freitas Félix Carvalho V Y Vânia Vilas-Boas Begoña Espiña
Effectiveness and Safety of a Nontargeted Boost for a CXCR4-Targeted Magnetic Hyperthermia Treatment of Cancer Cells Journal Article
ACS omega, 4 (1), pp. 1931–1940, 2019.
@article{Vilas-Boas2019b,
title = {Effectiveness and Safety of a Nontargeted Boost for a CXCR4-Targeted Magnetic Hyperthermia Treatment of Cancer Cells},
author = {Yury Kolen’ko Manuel Bañobre-López Marina Brito Verónica Martins José Alberto Duarte Dmitri Petrovykh Paulo Freitas Félix Carvalho V Y Vânia Vilas-Boas Begoña Espiña},
doi = {10.1021/acsomega.8b02199},
year = {2019},
date = {2019-01-25},
journal = {ACS omega},
volume = {4},
number = {1},
pages = {1931–1940},
abstract = {We investigate the effectiveness and safety of a novel magnetic hyperthermia (MHT) protocol, whereby a pretreatment with nontargeted magnetic nanoparticles (MNPs) is used to boost the subsequent iron loading of cancer cells by the targeted immuno-modified MNPs. As a model example, LN229 cancer cells express specific cell-surface receptors (CXCR4) at levels sufficient for diagnostic identification but insufficient for achieving 100% effective monotherapeutic MHT based on CXCR4-targeted MNPs. The nontargeted boost of the iron content overcomes this limitation of the targeted loading and is positively correlated with the maximum temperature reached during MHT treatment of LN229 cells. The effectiveness of the dual-population MHT strategy is validated by achieving a 100% lethal outcome for LN229 cancer cells 72 h after the treatment, while its safety is confirmed by the minimal cytotoxicity observed in control experiments with normal HK-2 cells or with an isotype-control targeting antibody. Systematic in vitro measurements thus demonstrate that the magnetic loading by targeted MNPs can be significantly increased by the nontargeted boost, even to double the iron concentration, while improving the effectiveness and maintaining the safety of MHT. This validation of the dual-population MHT strategy opens a novel materials-based pathway, unassisted by highly and nonselectively cytotoxic chemotherapeutic agents, to overcome the limited effectiveness of MHT for treating cancer cells that express only moderate levels of cell-surface receptors.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}We investigate the effectiveness and safety of a novel magnetic hyperthermia (MHT) protocol, whereby a pretreatment with nontargeted magnetic nanoparticles (MNPs) is used to boost the subsequent iron loading of cancer cells by the targeted immuno-modified MNPs. As a model example, LN229 cancer cells express specific cell-surface receptors (CXCR4) at levels sufficient for diagnostic identification but insufficient for achieving 100% effective monotherapeutic MHT based on CXCR4-targeted MNPs. The nontargeted boost of the iron content overcomes this limitation of the targeted loading and is positively correlated with the maximum temperature reached during MHT treatment of LN229 cells. The effectiveness of the dual-population MHT strategy is validated by achieving a 100% lethal outcome for LN229 cancer cells 72 h after the treatment, while its safety is confirmed by the minimal cytotoxicity observed in control experiments with normal HK-2 cells or with an isotype-control targeting antibody. Systematic in vitro measurements thus demonstrate that the magnetic loading by targeted MNPs can be significantly increased by the nontargeted boost, even to double the iron concentration, while improving the effectiveness and maintaining the safety of MHT. This validation of the dual-population MHT strategy opens a novel materials-based pathway, unassisted by highly and nonselectively cytotoxic chemotherapeutic agents, to overcome the limited effectiveness of MHT for treating cancer cells that express only moderate levels of cell-surface receptors.Begoña Espiña Laura Salonen M Soraia PS Fernandes Vanesa Romero
Tailoring Covalent Organic Frameworks to Capture Water Contaminants Journal Article
Chemistry: A European Journal, 2019.
@article{Fernandes2019,
title = {Tailoring Covalent Organic Frameworks to Capture Water Contaminants},
author = {Begoña Espiña Laura Salonen M Soraia PS Fernandes Vanesa Romero},
doi = {10.1002/chem.201806025},
year = {2019},
date = {2019-01-17},
journal = {Chemistry: A European Journal},
abstract = {Covalent organic frameworks (COFs) are attractive materials receiving increasing interest in the literature due to their crystallinity, large surface area, and pore uniformity. Their properties can be tailored towards specific applications by judicious design of COF building blocks, giving access to tailor-made pore sizes and surfaces. In this concept article, we discuss developments in the field of COFs that have allowed these materials to be explored for contaminant adsorption. Strategies to obtain water-stable materials with highly ordered structures and large surface areas are reviewed. Post-synthetic modification approaches, by which pore surfaces can be tuned to target specific contaminants, are described. Recent advances in COF formulations, crucial for future implementation in adsorption devices, are highlighted. At the end, we will discuss future challenges which need to be addressed to allow for the deployment of COFs for the capture of water contaminants.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Covalent organic frameworks (COFs) are attractive materials receiving increasing interest in the literature due to their crystallinity, large surface area, and pore uniformity. Their properties can be tailored towards specific applications by judicious design of COF building blocks, giving access to tailor-made pore sizes and surfaces. In this concept article, we discuss developments in the field of COFs that have allowed these materials to be explored for contaminant adsorption. Strategies to obtain water-stable materials with highly ordered structures and large surface areas are reviewed. Post-synthetic modification approaches, by which pore surfaces can be tuned to target specific contaminants, are described. Recent advances in COF formulations, crucial for future implementation in adsorption devices, are highlighted. At the end, we will discuss future challenges which need to be addressed to allow for the deployment of COFs for the capture of water contaminants.Ana Loureiro Pier Parpot Begoña Espiña Andreia Gomes Artur Cavaco-Paulo Artur Ribeiro C Ana Tinoco Marisa P. Sárria
BSA/ASN/Pol407 nanoparticles for acute lymphoblastic leukemia treatment Journal Article
Biochemical Engineering Journal, 141 , pp. 80-88, 2019.
@article{Tinoco2019,
title = {BSA/ASN/Pol407 nanoparticles for acute lymphoblastic leukemia treatment},
author = {Ana Loureiro Pier Parpot Begoña Espiña Andreia Gomes Artur Cavaco-Paulo Artur Ribeiro C Ana Tinoco Marisa P. Sárria},
doi = {10.1016/j.bej.2018.10.006},
year = {2019},
date = {2019-01-15},
journal = {Biochemical Engineering Journal},
volume = {141},
pages = {80-88},
abstract = {During the treatment of acute lymphoblastic leukemia (ALL) with asparaginase (ASN) there is an accumulation of ammonia in the body as result of asparagine hydrolysis. This accumulation known as hyperammonemia is one of the main side-effects of this therapy. To avoid hyperammonemia is urgent to develop new strategies for ammonia retention. Herein is presented the immobilization of ASN into bovine serum albumin/poloxamer 407 (BSA/Pol407) nanoparticles. The ability of the developed nanoparticles to hydrolyze asparagine while retaining the forming ammonia is also explored. Different percentages of ASN were entrapped into BSA nanoparticles coated with Poloxamer 407 and were prepared by high-pressure homogenization. The nanoparticles were characterized regarding their physico-chemical properties, stability, capacity to retain ammonia and safety using zebrafish embryos as an in vivo model of toxicity. The BSA/ASN25%/Pol407 nanoparticles were selected as the best formulation to hydrolyze asparagine using the lowest nanoparticle concentration. These nanoparticles presented physical characteristics suitable for an intravenous application and were capable to retain the forming ammonia decreasing the negative effect of free ASN on zebrafish survival. These nanoparticles could potentially be used to prevent hyperammonemia during ALL treatment with ASN.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}During the treatment of acute lymphoblastic leukemia (ALL) with asparaginase (ASN) there is an accumulation of ammonia in the body as result of asparagine hydrolysis. This accumulation known as hyperammonemia is one of the main side-effects of this therapy. To avoid hyperammonemia is urgent to develop new strategies for ammonia retention. Herein is presented the immobilization of ASN into bovine serum albumin/poloxamer 407 (BSA/Pol407) nanoparticles. The ability of the developed nanoparticles to hydrolyze asparagine while retaining the forming ammonia is also explored. Different percentages of ASN were entrapped into BSA nanoparticles coated with Poloxamer 407 and were prepared by high-pressure homogenization. The nanoparticles were characterized regarding their physico-chemical properties, stability, capacity to retain ammonia and safety using zebrafish embryos as an in vivo model of toxicity. The BSA/ASN25%/Pol407 nanoparticles were selected as the best formulation to hydrolyze asparagine using the lowest nanoparticle concentration. These nanoparticles presented physical characteristics suitable for an intravenous application and were capable to retain the forming ammonia decreasing the negative effect of free ASN on zebrafish survival. These nanoparticles could potentially be used to prevent hyperammonemia during ALL treatment with ASN. -
2018
Nuno Azoia Egipto Antunes Ana Loureiro Diana Guimaraẽs Jennifer Noro Alexandra Rollett Georg Guebitz Artur Cavaco-Paulo G Eugenia Nogueira Marisa P. Sarria
Internalization of Methotrexate Conjugates by Folate Receptor-alpha Journal Article
Biochemistry, 57 (49), pp. 6780-6786, 2018.
@article{Nogueira2018b,
title = {Internalization of Methotrexate Conjugates by Folate Receptor-alpha},
author = {Nuno Azoia Egipto Antunes Ana Loureiro Diana Guimaraẽs Jennifer Noro Alexandra Rollett Georg Guebitz Artur Cavaco-Paulo G Eugenia Nogueira Marisa P. Sarria},
doi = {10.1021/acs.biochem.8b00607},
year = {2018},
date = {2018-11-19},
journal = {Biochemistry},
volume = {57},
number = {49},
pages = {6780-6786},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Corine Reis Ana Milosevic Thomas Moore Sandor Balog Barbara Rothen-Rutishauser Curzio Ruegg Alke Petri-Fink L Laura Rodriguez-Lorenzo Sarah D. Rafiee
A rational and iterative process for targeted nanoparticle design and validation Journal Article
Colloids and Surfaces B: Biointerfaces, 171 , pp. 579-589, 2018.
@article{Rodriguez-Lorenzo2018b,
title = {A rational and iterative process for targeted nanoparticle design and validation},
author = {Corine Reis Ana Milosevic Thomas Moore Sandor Balog Barbara Rothen-Rutishauser Curzio Ruegg Alke Petri-Fink L Laura Rodriguez-Lorenzo Sarah D. Rafiee},
doi = {https://doi.org/10.1016/j.colsurfb.2018.07.066},
year = {2018},
date = {2018-11-01},
journal = {Colloids and Surfaces B: Biointerfaces},
volume = {171},
pages = {579-589},
abstract = {The lack of understanding of fundamental nano-bio interactions, and difficulties in designing particles stable in complex biological environments are major limitations to their translation into biomedical clinical applications. Here we present a multi-parametric approach to fully characterize targeted nanoparticles, and emphasizes the significant effect that each detail in the synthetic process can have on downstream in vitro results. Through an iterative process, particles were designed, synthesized and tested for physico-chemical and bio-interactive properties which allowed the optimization of nanoparticle functionality. Taken together all interative steps demonstrate that we have synthesized a multifunctional gold nanoparticles that can detect ERBB2-positive breast cancer cells while showing stealth-like behavior toward ERBB2-negative cells and excellent physicochemical stability.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}The lack of understanding of fundamental nano-bio interactions, and difficulties in designing particles stable in complex biological environments are major limitations to their translation into biomedical clinical applications. Here we present a multi-parametric approach to fully characterize targeted nanoparticles, and emphasizes the significant effect that each detail in the synthetic process can have on downstream in vitro results. Through an iterative process, particles were designed, synthesized and tested for physico-chemical and bio-interactive properties which allowed the optimization of nanoparticle functionality. Taken together all interative steps demonstrate that we have synthesized a multifunctional gold nanoparticles that can detect ERBB2-positive breast cancer cells while showing stealth-like behavior toward ERBB2-negative cells and excellent physicochemical stability.Barbara Drasler Laura Rodriguez-Lorenzo Dominic Urban Dimitri Vanhecke Dedy Septiadi Liliane Hirschi-Ackermann Alke Petri-Fink Barbara Rothen-Rutishauser A Estelle Durantie Hana Barosova
Carbon nanodots: Opportunities and limitations to study their biodistribution at the human lung epithelial tissue barrier Journal Article
Biointerphases, 13 (6), pp. 06D404, 2018.
@article{Durantie2018b,
title = {Carbon nanodots: Opportunities and limitations to study their biodistribution at the human lung epithelial tissue barrier},
author = {Barbara Drasler Laura Rodriguez-Lorenzo Dominic Urban Dimitri Vanhecke Dedy Septiadi Liliane Hirschi-Ackermann Alke Petri-Fink Barbara Rothen-Rutishauser A Estelle Durantie Hana Barosova},
doi = {10.1116/1.5043373},
year = {2018},
date = {2018-09-11},
journal = {Biointerphases},
volume = {13},
number = {6},
pages = {06D404},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Maria Blanco‐Formoso Leonardo Furini Laura Rodríguez‐Lorenzo Nicolas Pazos‐Perez Luca Guerrini Moises Pérez‐Lorenzo Miguel Correa‐Duarte Ramon Alvarez‐Puebla N A A Andrea Mariño‐Lopez Ana Sousa‐Castillo
Microporous Plasmonic Capsules as Stable Molecular Sieves for Direct SERS Quantification of Small Pollutants in Natural Waters Journal Article
CHEMNANOMAT, 5 (1), pp. 46-50, 2018.
@article{Mariño‐Lopez2018b,
title = {Microporous Plasmonic Capsules as Stable Molecular Sieves for Direct SERS Quantification of Small Pollutants in Natural Waters},
author = {Maria Blanco‐Formoso Leonardo Furini Laura Rodríguez‐Lorenzo Nicolas Pazos‐Perez Luca Guerrini Moises Pérez‐Lorenzo Miguel Correa‐Duarte Ramon Alvarez‐Puebla N A A Andrea Mariño‐Lopez Ana Sousa‐Castillo},
doi = {https://doi.org/10.1002/cnma.201800355},
year = {2018},
date = {2018-07-31},
journal = {CHEMNANOMAT},
volume = {5},
number = {1},
pages = {46-50},
abstract = {Fast and versatile optical SERS methods represent a major advance in chemical analysis of environmental samples such as water. To date, however, these ultrasensitive methods are hindered by two key drawbacks: (i) colloidal stability and (ii) chemical diversity, both arising from the compositional complexity of natural samples. Here, we present an engineered material that, due to its unique microporous structure, imparts colloidal stability and provides selectivity while confining a densely populated film of gold nanoparticles optimized for the generation of large electromagnetic fields. The material is tested against natural water for the ultraquantification of dichlorodiphenyl-trichloroethane (DDT), a ubiquitous environmental pollutant.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Fast and versatile optical SERS methods represent a major advance in chemical analysis of environmental samples such as water. To date, however, these ultrasensitive methods are hindered by two key drawbacks: (i) colloidal stability and (ii) chemical diversity, both arising from the compositional complexity of natural samples. Here, we present an engineered material that, due to its unique microporous structure, imparts colloidal stability and provides selectivity while confining a densely populated film of gold nanoparticles optimized for the generation of large electromagnetic fields. The material is tested against natural water for the ultraquantification of dichlorodiphenyl-trichloroethane (DDT), a ubiquitous environmental pollutant.Lester Barnsley Amal Taouallah João Fernandes Bruno Silva Susana Cardoso Lorena Diéguez Begoña Espiña Paulo Freitas C F B P Alexandre Chícharo Marco Martins
Enhanced magnetic microcytometer with 3D flow focusing for cell enumeration Journal Article
Lab on a chip, 18 , pp. 2593, 2018.
@article{Chícharo2018b,
title = {Enhanced magnetic microcytometer with 3D flow focusing for cell enumeration},
author = {Lester Barnsley Amal Taouallah João Fernandes Bruno Silva Susana Cardoso Lorena Diéguez Begoña Espiña Paulo Freitas C F B P Alexandre Chícharo Marco Martins},
doi = {10.1039/c8lc00486b},
year = {2018},
date = {2018-07-05},
journal = {Lab on a chip},
volume = {18},
pages = {2593},
abstract = {We report the design and characterization of a lateral and vertical hydrodynamic focusing feature for whole cell detection on a miniaturized flow cytometer. The developed system, based on magnetic sensing, incor- porates spin valve sensors on the bottom of the microfluidic channels that detect cells labeled with mag- netic beads. An adaptable 3D hydrodynamic focusing system was developed that pushes labeled cells to- wards the bottom of the microchannel, closer to the sensors, allowing increased signal amplitude for cells labeled with magnetic beads and enhanced discrimination of labeled cells. Fluorescence microscopy indicates that the lateral and vertical hydrodynamic focusing effect was adequately implemented, consistent with simu- lation predictions. The sensitivity of the system to detect labeled cells was improved by at least two-fold. By estimating the coverage of magnetic beads on cells, the signal from labeled cells could be predicted using a mathematical model, which also demonstrated the sensitivity of the signal to the height of the cells relative to the sensor. The system is versatile allowing interchangeable flow rates for cells with different diameters.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}We report the design and characterization of a lateral and vertical hydrodynamic focusing feature for whole cell detection on a miniaturized flow cytometer. The developed system, based on magnetic sensing, incor- porates spin valve sensors on the bottom of the microfluidic channels that detect cells labeled with mag- netic beads. An adaptable 3D hydrodynamic focusing system was developed that pushes labeled cells to- wards the bottom of the microchannel, closer to the sensors, allowing increased signal amplitude for cells labeled with magnetic beads and enhanced discrimination of labeled cells. Fluorescence microscopy indicates that the lateral and vertical hydrodynamic focusing effect was adequately implemented, consistent with simu- lation predictions. The sensitivity of the system to detect labeled cells was improved by at least two-fold. By estimating the coverage of magnetic beads on cells, the signal from labeled cells could be predicted using a mathematical model, which also demonstrated the sensitivity of the signal to the height of the cells relative to the sensor. The system is versatile allowing interchangeable flow rates for cells with different diameters.Abdelkarim Mellah; Soraia Fernandes; Ramón Rodríguez; José Otero; Jairo Paz; Jacobo Cruces; Dana Medina; Harik Djamila; Begoña Espiña; Laura P S D M Salonen
Adsorption of Pharmaceutical Pollutants from Water Using Covalent Organic Frameworks Journal Article
Chemical European Journal, 2018.
@article{Salonen2018b,
title = {Adsorption of Pharmaceutical Pollutants from Water Using Covalent Organic Frameworks},
author = {Abdelkarim Mellah; Soraia Fernandes; Ramón Rodríguez; José Otero; Jairo Paz; Jacobo Cruces; Dana Medina; Harik Djamila; Begoña Espiña; Laura P S D M Salonen},
url = {https://doi.org/10.1002/chem.201801649},
doi = {10.1002/chem.201801649},
year = {2018},
date = {2018-06-12},
journal = {Chemical European Journal},
abstract = {Capture of pharmaceutical pollutants from water was studied using a novel fluorine‐bearing covalent organic framework TpBD‐(CF3)2, which showed ibuprofen adsorption capacity of 119 mg g‐1 at neutral pH. This value is further enhanced at pH 2, highlighting the potential of this class of materials to serve as adsorbents even under harsh conditions. The adsorbed pharmaceutical can be recovered from TpBD‐(CF3)2 in high yield, offering the option of recycling both the adsorbent and the pharmaceutical. The high efficiency of ibuprofen capture as compared to other less lipophilic pharmaceuticals suggests that COFs can be pre‐designed for selective capture of contaminants.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Capture of pharmaceutical pollutants from water was studied using a novel fluorine‐bearing covalent organic framework TpBD‐(CF3)2, which showed ibuprofen adsorption capacity of 119 mg g‐1 at neutral pH. This value is further enhanced at pH 2, highlighting the potential of this class of materials to serve as adsorbents even under harsh conditions. The adsorbed pharmaceutical can be recovered from TpBD‐(CF3)2 in high yield, offering the option of recycling both the adsorbent and the pharmaceutical. The high efficiency of ibuprofen capture as compared to other less lipophilic pharmaceuticals suggests that COFs can be pre‐designed for selective capture of contaminants.Marco Martins Susana Cardoso Lorena Diéguez Begoña Espiña Paulo Freitas P Alexandre Chicharo Lester C. Barnsley
Custom Magnet Design for a Multi-Channel Magnetic Microcytometer Journal Article
IEEE Transactions on Magnetics, 54 (11), 2018, ISSN: 1941-0069.
@article{Freitas2018,
title = {Custom Magnet Design for a Multi-Channel Magnetic Microcytometer},
author = {Marco Martins Susana Cardoso Lorena Diéguez Begoña Espiña Paulo Freitas P Alexandre Chicharo Lester C. Barnsley},
url = {https://ieeexplore.ieee.org/document/8379352/},
doi = {10.1109/TMAG.2018.2835369},
issn = {1941-0069},
year = {2018},
date = {2018-06-11},
journal = {IEEE Transactions on Magnetics},
volume = {54},
number = {11},
abstract = {Magnetic microflow cytometers integrate magnetic field sensors and microfluidic channels to detect cell suspensions labeled with magnetic beads. As the magnetic beads are superparamagnetic, commercial permanent magnets (PMs) are typiacally positioned bellow the microchip for an out-of-plane magnetization. Though, they require careful alignment as their magnetic field can impact the sensors sensitivity. In this paper, we overcome this drawback by presenting an innovative custom-made PM that notably combines high out-of-plane magnetic field (>100 mT) and low in-plane magnetic field (<1 mT) over a large area (30.2 mm²). This configuration qualifies the setup for simultaneous detection in multiple microfluidic channels within the same microchip, allowing parallel analysis of different cell samples or faster analysis of larger volumes of cell suspension.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Magnetic microflow cytometers integrate magnetic field sensors and microfluidic channels to detect cell suspensions labeled with magnetic beads. As the magnetic beads are superparamagnetic, commercial permanent magnets (PMs) are typiacally positioned bellow the microchip for an out-of-plane magnetization. Though, they require careful alignment as their magnetic field can impact the sensors sensitivity. In this paper, we overcome this drawback by presenting an innovative custom-made PM that notably combines high out-of-plane magnetic field (>100 mT) and low in-plane magnetic field (<1 mT) over a large area (30.2 mm²). This configuration qualifies the setup for simultaneous detection in multiple microfluidic channels within the same microchip, allowing parallel analysis of different cell samples or faster analysis of larger volumes of cell suspension.Nagamalai Vasimalai and Vânia Vilas-Boas and Juan Gallo and María Fátima de Cerqueira and Mario Menéndez-Miranda and José Manuel Costa-Fernández and Lorena Diéguez and Begoña Espiña and María Teresa Fernández-Argüelles.
Green synthesis of fluorescent carbon dots from spices for in vitro imaging and tumour cell growth inhibition Journal Article
BEILSTEIN JOURNAL OF NANOTECHNOLOGY, 9 , pp. 530-544, 2018.
@article{Vasimalai2018,
title = {Green synthesis of fluorescent carbon dots from spices for in vitro imaging and tumour cell growth inhibition},
author = {Nagamalai Vasimalai and Vânia Vilas-Boas and Juan Gallo and María Fátima de Cerqueira and Mario Menéndez-Miranda and José Manuel Costa-Fernández and Lorena Diéguez and Begoña Espiña and María Teresa Fernández-Argüelles.},
url = {https://www.beilstein-journals.org/bjnano/articles/9/51},
doi = {doi:10.3762/bjnano.9.51},
year = {2018},
date = {2018-02-13},
journal = {BEILSTEIN JOURNAL OF NANOTECHNOLOGY},
volume = {9},
pages = {530-544},
abstract = {Carbon dots have demonstrated great potential as luminescent nanoparticles in bioapplications. Although such nanoparticles appear to exhibit low toxicity compared to other metal luminescent nanomaterials, today we know that the toxicity of carbon dots (C-dots) strongly depends on the protocol of fabrication. In this work, aqueous fluorescent C-dots have been synthesized from cinnamon, red chilli, turmeric and black pepper, by a one-pot green hydrothermal method. The synthesized C-dots were firstly characterized by means of UV–vis, fluorescence, Fourier transform infrared and Raman spectroscopy, dynamic light scattering and transmission electron microscopy. The optical performance showed an outstanding ability for imaging purposes, with quantum yields up to 43.6%. Thus, the cytotoxicity of the above mentioned spice-derived C-dots was evaluated in vitro in human glioblastoma cells (LN-229 cancer cell line) and in human kidney cells (HK-2 non-cancerous cell line). Bioimaging and viability studies were performed with different C-dot concentrations from 0.1 to 2 mg·mL−1, exhibiting a higher uptake of C-dots in the cancer cultures compared to the non-cancerous cells. Results showed that the spice-derived C-dots inhibited cell viability dose-dependently after a 24 h incubation period, displaying a higher toxicity in LN-229, than in HK-2 cells. As a control, C-dots synthesized from citric acid did not show any significant toxicity in either cancerous or non-cancerous cells, implying that the tumour cell growth inhibition properties observed in the spice-derived C-dots can be attributed to the starting material employed for their fabrication. These results evidence that functional groups in the surface of the C-dots might be responsible for the selective cytotoxicity, as suggested by the presence of piperine in the surface of black pepper C-dots analysed by ESI-QTOF-MS.Keywords: bioimaging; carbon quantum dots; fluorescence; spices},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Carbon dots have demonstrated great potential as luminescent nanoparticles in bioapplications. Although such nanoparticles appear to exhibit low toxicity compared to other metal luminescent nanomaterials, today we know that the toxicity of carbon dots (C-dots) strongly depends on the protocol of fabrication. In this work, aqueous fluorescent C-dots have been synthesized from cinnamon, red chilli, turmeric and black pepper, by a one-pot green hydrothermal method. The synthesized C-dots were firstly characterized by means of UV–vis, fluorescence, Fourier transform infrared and Raman spectroscopy, dynamic light scattering and transmission electron microscopy. The optical performance showed an outstanding ability for imaging purposes, with quantum yields up to 43.6%. Thus, the cytotoxicity of the above mentioned spice-derived C-dots was evaluated in vitro in human glioblastoma cells (LN-229 cancer cell line) and in human kidney cells (HK-2 non-cancerous cell line). Bioimaging and viability studies were performed with different C-dot concentrations from 0.1 to 2 mg·mL−1, exhibiting a higher uptake of C-dots in the cancer cultures compared to the non-cancerous cells. Results showed that the spice-derived C-dots inhibited cell viability dose-dependently after a 24 h incubation period, displaying a higher toxicity in LN-229, than in HK-2 cells. As a control, C-dots synthesized from citric acid did not show any significant toxicity in either cancerous or non-cancerous cells, implying that the tumour cell growth inhibition properties observed in the spice-derived C-dots can be attributed to the starting material employed for their fabrication. These results evidence that functional groups in the surface of the C-dots might be responsible for the selective cytotoxicity, as suggested by the presence of piperine in the surface of black pepper C-dots analysed by ESI-QTOF-MS.Keywords: bioimaging; carbon quantum dots; fluorescence; spices
Vânia Vilas-Boas and Begoña Espiña and Yury V Kolen'ko and Manuel Bañobre-Lopez and José A Duarte and Verónica C Martins and Dmitri Y Petrovykh and Paulo P Freitas and Felix D Carvalho
Combining CXCR4-targeted and nontargeted nanoparticles for effective unassisted in vitro magnetic hyperthermia Journal Article
Biointerphases, 13 (1), 2018.
@article{Vilas-Boas2018,
title = {Combining CXCR4-targeted and nontargeted nanoparticles for effective unassisted in vitro magnetic hyperthermia},
author = {Vânia Vilas-Boas and Begoña Espiña and Yury V Kolen'ko and Manuel Bañobre-Lopez and José A Duarte and Verónica C Martins and Dmitri Y Petrovykh and Paulo P Freitas and Felix D Carvalho},
url = {https://avs.scitation.org/doi/10.1116/1.5009989},
doi = {10.1116/1.5009989},
year = {2018},
date = {2018-01-15},
journal = {Biointerphases},
volume = {13},
number = {1},
abstract = {The use of targeted nanoparticles for magnetic hyperthermia (MHT) increases MHT selectivity, but often at the expense of its effectiveness. Consequently, targeted MHT is typically used in combination with other treatment modalities. This work describes an implementation of a highly effective monotherapeutic in vitro MHT treatment based on two populations of magnetic particles. Cells were sequentially incubated with two populations of magnetic particles: nonfunctionalized superparamagnetic nanoparticles and anti-CXCR4-functionalized particles. After removing the excess of free particles, an alternating magnetic field (AMF) was applied to produce MHT. The induced cytotoxicity was assessed at different time-points after AMF application. Complete loss of cell viability was observed 72 h after MHT when the iron loading of the anti-CXCR4-functionalized particles was boosted by that of a nontargeted population. Additionally, induction of necrosis resulted in more efficient cell death than did induction of apoptosis. Achieving a uniquely high effectiveness in monotherapeutic MHT demonstrates the potential of this approach to achieve complete loss of viability of cancer cells while avoiding the side effects of dual-treatment strategies that use MHT only as a sensitizing therapy.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}The use of targeted nanoparticles for magnetic hyperthermia (MHT) increases MHT selectivity, but often at the expense of its effectiveness. Consequently, targeted MHT is typically used in combination with other treatment modalities. This work describes an implementation of a highly effective monotherapeutic in vitro MHT treatment based on two populations of magnetic particles. Cells were sequentially incubated with two populations of magnetic particles: nonfunctionalized superparamagnetic nanoparticles and anti-CXCR4-functionalized particles. After removing the excess of free particles, an alternating magnetic field (AMF) was applied to produce MHT. The induced cytotoxicity was assessed at different time-points after AMF application. Complete loss of cell viability was observed 72 h after MHT when the iron loading of the anti-CXCR4-functionalized particles was boosted by that of a nontargeted population. Additionally, induction of necrosis resulted in more efficient cell death than did induction of apoptosis. Achieving a uniquely high effectiveness in monotherapeutic MHT demonstrates the potential of this approach to achieve complete loss of viability of cancer cells while avoiding the side effects of dual-treatment strategies that use MHT only as a sensitizing therapy. -
2017
Espiña B Vasimalai N Fernández-Argüelles MT
ACS Appl Mater Interfaces, 2017.
@article{Vasimalai2017,
title = {Detection of sulfide using mercapto tetrazine protected fluorescent gold nanodots: The preparation of paper based testing kit for on-site monitoring},
author = {Espiña B Vasimalai N Fernández-Argüelles MT},
url = {https://www.ncbi.nlm.nih.gov/pubmed/29271189},
doi = {10.1021/acsami.7b11769},
year = {2017},
date = {2017-12-22},
journal = {ACS Appl Mater Interfaces},
abstract = {This work demonstrates the development of a highly sensitive method to detect and quantify the sulfide ions (S2-) in water samples. First, we synthesized 6-mercapto-s-triazolo(4,3-b)-s-tetrazine (MTT) by the reaction between formaldehyde and 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole at room temperature. The synthetic MTT was used as a capping ligand for the synthesis of gold nanodots (AuNDs) via one-pot green method at room temperature with only a 10 min reaction time. TEM images exhibited that the MTT-AuNDs has an average particle size of 1.9 nm and an emission maximum at 672 nm upon excitation at 360 nm. The synthesized highly red emissive MTT-AuNDs are used as specific fluorescent probes for the detection of S2-. The fluorescence of MTT-AuNDs was significantly and dose-dependently quenched from the addition of S2-. The observed fluorescence quenching was ascribed to the formation of an Au2S complex, which was determined by Raman and mass spectroscopy. A good linearity was achieved for the increasing concentration of S2- from 870 nM to 16 µM and the detection limit (LOD) was found to be 2 nM (S/N = 3). The S2- detection system that is described in this study was validated and agreed well with the standard methylene blue method. Furthermore, the present sensor was examined for the use in quantifying S2- in real water samples obtained from lake and river. In addition, the specificity was checked against the most likely ion interferences in real water. Moreover, a cost-effective and viable paper based S2- sensor was fabricated for environmental monitoring based on the use of MTT-AuNDs. The developed system would be an environmentally friendly and easy to use detection device for S2- in water.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}This work demonstrates the development of a highly sensitive method to detect and quantify the sulfide ions (S2-) in water samples. First, we synthesized 6-mercapto-s-triazolo(4,3-b)-s-tetrazine (MTT) by the reaction between formaldehyde and 4-amino-3-hydrazino-5-mercapto-1,2,4-triazole at room temperature. The synthetic MTT was used as a capping ligand for the synthesis of gold nanodots (AuNDs) via one-pot green method at room temperature with only a 10 min reaction time. TEM images exhibited that the MTT-AuNDs has an average particle size of 1.9 nm and an emission maximum at 672 nm upon excitation at 360 nm. The synthesized highly red emissive MTT-AuNDs are used as specific fluorescent probes for the detection of S2-. The fluorescence of MTT-AuNDs was significantly and dose-dependently quenched from the addition of S2-. The observed fluorescence quenching was ascribed to the formation of an Au2S complex, which was determined by Raman and mass spectroscopy. A good linearity was achieved for the increasing concentration of S2- from 870 nM to 16 µM and the detection limit (LOD) was found to be 2 nM (S/N = 3). The S2- detection system that is described in this study was validated and agreed well with the standard methylene blue method. Furthermore, the present sensor was examined for the use in quantifying S2- in real water samples obtained from lake and river. In addition, the specificity was checked against the most likely ion interferences in real water. Moreover, a cost-effective and viable paper based S2- sensor was fabricated for environmental monitoring based on the use of MTT-AuNDs. The developed system would be an environmentally friendly and easy to use detection device for S2- in water.Fernandes Louçano Carbó-Argibay Sarria Rodríguez-Abreu Peixoto Espiña. S P S J E M P C J B L. M. Salonen S. R. Pinela
Adsorption of marine phycotoxin okadaic acid on a covalent organic framework Journal Article
J Chromatogr A., 1525:17-22 , 2017.
@article{Salonen2017,
title = {Adsorption of marine phycotoxin okadaic acid on a covalent organic framework},
author = {Fernandes Louçano Carbó-Argibay Sarria Rodríguez-Abreu Peixoto Espiña. S P S J E M P C J B L. M. Salonen S. R. Pinela},
url = {https://www.ncbi.nlm.nih.gov/pubmed/29037592},
doi = {10.1016/j.chroma.2017.10.017},
year = {2017},
date = {2017-11-24},
journal = {J Chromatogr A.},
volume = {1525:17-22},
abstract = {Phycotoxins, compounds produced by some marine microalgal species, can reach high concentrations in the sea when a massive proliferation occurs, the so-called harmful algal bloom. These compounds are especially dangerous to human health when concentrated in the digestive glands of seafood. In order to generate an early warning system to alert for approaching toxic outbreaks, it is very important to improve monitoring methods of phycotoxins in aquatic ecosystems. Solid-phase adsorption toxin tracking devices reported thus far based on polymeric resins have not been able to provide an efficient harmful algal bloom prediction system due to their low adsorption capabilities. In this work, a water-stable covalent organic framework (COF) was evaluated as adsorbent for the hydrophobic toxin okadaic acid, one of the most relevant marine toxins and the parental compound of the most common group of toxins responsible for the diarrhetic shellfish poisoning. Adsorption kinetics of okadaic acid onto the COF in seawater showed that equilibrium concentration was reached in only 60min, with a maximum experimental adsorption of 61mgg-1. Desorption of okadaic acid from the COF was successful with both 70% ethanol and acetonitrile as solvent, and the COF material could be reused with minor losses in adsorption capacity for three cycles. The results demonstrate that COF materials are promising candidates for solid-phase adsorption in water monitoring devices.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Phycotoxins, compounds produced by some marine microalgal species, can reach high concentrations in the sea when a massive proliferation occurs, the so-called harmful algal bloom. These compounds are especially dangerous to human health when concentrated in the digestive glands of seafood. In order to generate an early warning system to alert for approaching toxic outbreaks, it is very important to improve monitoring methods of phycotoxins in aquatic ecosystems. Solid-phase adsorption toxin tracking devices reported thus far based on polymeric resins have not been able to provide an efficient harmful algal bloom prediction system due to their low adsorption capabilities. In this work, a water-stable covalent organic framework (COF) was evaluated as adsorbent for the hydrophobic toxin okadaic acid, one of the most relevant marine toxins and the parental compound of the most common group of toxins responsible for the diarrhetic shellfish poisoning. Adsorption kinetics of okadaic acid onto the COF in seawater showed that equilibrium concentration was reached in only 60min, with a maximum experimental adsorption of 61mgg-1. Desorption of okadaic acid from the COF was successful with both 70% ethanol and acetonitrile as solvent, and the COF material could be reused with minor losses in adsorption capacity for three cycles. The results demonstrate that COF materials are promising candidates for solid-phase adsorption in water monitoring devices.D Viegas, E Fernandes, R Queirós, DY Petrovykh and PAA De Beule
Adapting Bobbert-Vlieger model to spectroscopic ellipsometry of gold nanoparticles with bio-organic shells Journal Article
Biomed Opt Express, 8 , pp. 3538–3550, 2017.
@article{Viegas2017,
title = {Adapting Bobbert-Vlieger model to spectroscopic ellipsometry of gold nanoparticles with bio-organic shells},
author = {D Viegas, E Fernandes, R Queirós, DY Petrovykh and PAA De Beule},
url = {https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5560823/},
doi = {10.1364/BOE.8.003538},
year = {2017},
date = {2017-08-01},
journal = {Biomed Opt Express},
volume = {8},
pages = {3538–3550},
abstract = {We investigate spectroscopic imaging ellipsometry for monitoring biomolecules at surfaces of nanoparticles. For the modeling of polarimetric light scattering off surface-adsorbed core-shell nanoparticles, we employ an extension of the exact solution for the scattering by particles near a substrate presented by Bobbert and Vlieger, which offers insight beyond that of the Maxwell-Garnett effective medium approximation. Varying thickness and refractive index of a model bio-organic shell results in systematic and characteristic changes in spectroscopic parameters Ψ and Δ. The salient features and trends in modeled spectra are in qualitative agreement with experimental data for antibody immobilization and fibronectin biorecognition at surfaces of gold nanoparticles on a silicon substrate, but achieving a full quantitative agreement will require including additional effects, such as nanoparticle-substrate interactions, into the model.
OCIS codes: (120.2130) Ellipsometry and polarimetry, (240.6680) Surface plasmons, (280.1415) Biological sensing and sensors, (280.4788) Optical sensing and sensors},
keywords = {},
pubstate = {published},
tppubtype = {article}
}We investigate spectroscopic imaging ellipsometry for monitoring biomolecules at surfaces of nanoparticles. For the modeling of polarimetric light scattering off surface-adsorbed core-shell nanoparticles, we employ an extension of the exact solution for the scattering by particles near a substrate presented by Bobbert and Vlieger, which offers insight beyond that of the Maxwell-Garnett effective medium approximation. Varying thickness and refractive index of a model bio-organic shell results in systematic and characteristic changes in spectroscopic parameters Ψ and Δ. The salient features and trends in modeled spectra are in qualitative agreement with experimental data for antibody immobilization and fibronectin biorecognition at surfaces of gold nanoparticles on a silicon substrate, but achieving a full quantitative agreement will require including additional effects, such as nanoparticle-substrate interactions, into the model.
OCIS codes: (120.2130) Ellipsometry and polarimetry, (240.6680) Surface plasmons, (280.1415) Biological sensing and sensors, (280.4788) Optical sensing and sensors -
2016
Fernandez-Arguelles Diéguez Fuciños Vial Oliveira Reis Boehme B ; M T ; L ; P ; S ; J M ; R L ; K Prado M.; Espiña
Detection of Foodborne Pathogens Using Nanoparticles. Advantages and Trends Book Chapter
Antimicrobial Food Packaging, pp. pp.183-202, Jorge Barros-Velazquez, 1st Edition, 2016, ISBN: 978-0-12-800723-5.
@inbook{Prado2016bc,
title = {Detection of Foodborne Pathogens Using Nanoparticles. Advantages and Trends},
author = {Fernandez-Arguelles Diéguez Fuciños Vial Oliveira Reis Boehme B ; M T ; L ; P ; S ; J M ; R L ; K Prado M.; Espiña},
url = {https://www.sciencedirect.com/science/book/9780128007235},
isbn = {978-0-12-800723-5},
year = {2016},
date = {2016-12-01},
booktitle = {Antimicrobial Food Packaging},
journal = {Academic Press, London},
pages = {pp.183-202},
publisher = {Jorge Barros-Velazquez},
edition = {1st Edition},
abstract = {Due to their critical impact on public health, the detection of foodborne pathogens in food and water is an important issue for both, the food industry and control authorities. Fast and reliable analytical methods are needed in order to ensure the health of consumers, to easily determine whether a food product has been subjected to cross-contamination, and, simultaneously, to identify how and when this cross-contamination occurred in order to establish the proper corrective actions.Recent developments in nanotechnology are greatly impacting the advancement of some analytical techniques, including foodborne pathogen detection. Herein, the advantages and the recent applications of nanoparticles (NPs) in foodborne pathogen detection are reviewed. The most frequently used NPs in this context (gold nanoparticles, quantum dots, and magnetic nanoparticles) are described, and their applicability for food analysis is emphasized. Finally, this chapter provides an overview of the use of micro and nanofluidics, combined with nanoparticles, for food pathogen analysis, and the integration of nanomaterial-based sensors for pathogen detection in food packaging systems.},
keywords = {},
pubstate = {published},
tppubtype = {inbook}
}Due to their critical impact on public health, the detection of foodborne pathogens in food and water is an important issue for both, the food industry and control authorities. Fast and reliable analytical methods are needed in order to ensure the health of consumers, to easily determine whether a food product has been subjected to cross-contamination, and, simultaneously, to identify how and when this cross-contamination occurred in order to establish the proper corrective actions.Recent developments in nanotechnology are greatly impacting the advancement of some analytical techniques, including foodborne pathogen detection. Herein, the advantages and the recent applications of nanoparticles (NPs) in foodborne pathogen detection are reviewed. The most frequently used NPs in this context (gold nanoparticles, quantum dots, and magnetic nanoparticles) are described, and their applicability for food analysis is emphasized. Finally, this chapter provides an overview of the use of micro and nanofluidics, combined with nanoparticles, for food pathogen analysis, and the integration of nanomaterial-based sensors for pathogen detection in food packaging systems.Fernandez-Arguelles MT Bañobre-López M Gallo J Vasimalai N
Green synthesis of multimodal 'OFF-ON' activatable MRI/optical probes Journal Article
Dalton Trans., 45 , pp. 17672-17680, 2016.
@article{J2016b,
title = {Green synthesis of multimodal 'OFF-ON' activatable MRI/optical probes},
author = {Fernandez-Arguelles MT Bañobre-López M Gallo J Vasimalai N},
url = {https://www.ncbi.nlm.nih.gov/pubmed/27752669},
doi = {10.1039/c6dt02840c},
year = {2016},
date = {2016-11-28},
journal = {Dalton Trans.},
volume = {45},
pages = {17672-17680},
abstract = {Diagnosis by MRI is frequently non-trivial due to the low sensitivity of the technique. Signal enhancing contrast agents (CAs) are used to aid in the analysis of MR images. We present here a simple protocol for the preparation of responsive CAs based on Mn nanosheets. Mn nanostructures presented here undergo a chemical and structural change in the presence of altered physiological conditions that activate their signal. This strategy allows for a reduction of background, increasing the sensitivity of the technique. The simple synthetic protocol followed allows for the combination of the nanosheets with reporter molecules for other imaging techniques, like carbon quantum dots for optical imaging.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Diagnosis by MRI is frequently non-trivial due to the low sensitivity of the technique. Signal enhancing contrast agents (CAs) are used to aid in the analysis of MR images. We present here a simple protocol for the preparation of responsive CAs based on Mn nanosheets. Mn nanostructures presented here undergo a chemical and structural change in the presence of altered physiological conditions that activate their signal. This strategy allows for a reduction of background, increasing the sensitivity of the technique. The simple synthetic protocol followed allows for the combination of the nanosheets with reporter molecules for other imaging techniques, like carbon quantum dots for optical imaging.N Vasimalai and Maria T Fernández-Argüelles*.
Nanotechnology, Volume 27 (Issue 47), pp. article id. 475505, 2016.
@article{Vasimalai2016,
title = {Novel one-pot and facile room temperature synthesis of gold nanodots and application as highly sensitive and selective probes for cyanide detection},
author = {N Vasimalai and Maria T Fernández-Argüelles*.},
url = {https://www.ncbi.nlm.nih.gov/pubmed/27779114},
doi = {10.1088/0957-4484/27/47/475505},
year = {2016},
date = {2016-11-01},
journal = {Nanotechnology},
volume = {Volume 27},
number = {Issue 47},
pages = {article id. 475505},
abstract = {Highly fluorescent gold nanodots have been synthesized through a novel rapid, facile and one-pot room temperature route using trithiocyanuric acid as mild reducing agent and surface ligand. The proposed synthesis overcomes limitations of other synthetic routes in terms of cost, time, complexity and environmental risks, and gives rise to highly fluorescent gold nanodots within 10 min at room temperature, with a maximum emission wavelength at 623 nm and a large Stokes shift (213 nm). Moreover, the synthesized gold nanodots showed a large emission QY (9.62 × 10-2) and excellent photostability and colloidal properties during long periods. Increasing concentrations of CN- in aqueous solution progressively quenched the fluorescence emission and produced a slight blue shift of the synthesized gold nanodots. A good linear relationship was observed for CN- concentrations between 0.29 and 8.87 μM, obtaining a detection limit estimated according to the 3s IUPAC criteria of 150 nM. Besides, the influence on the fluorescence signal of potential interferents at high concentrations (1000 μM) was studied, including I-, F-, citrate, PO43-, NO3-, SO42-, CH3COO-, EDTA, Br-, CO32-, Cl- and S2- K+, Na+, Li+, Mg2+, Ca2+, Ba2+, Cu2+, Zn2+, Ni2+, Al3+, Fe2+, Fe3+, Pb2+, Cd2+, Hg2+ and Co2+. Results showed a high selectivity towards all the investigated ions, except for Pb2+, Cd2+ and Hg2+, although the use of glutathione and BSA as masking agents drastically minimized the effect of such cations at high concentrations. The synthesized gold nanodots were successfully evaluated as highly sensitive and selective probes for cyanide determination in environmental water samples, including tap, river, lake and sea water, indicating the validity of TCA-AuNDs for analytical CN- contamination control.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Highly fluorescent gold nanodots have been synthesized through a novel rapid, facile and one-pot room temperature route using trithiocyanuric acid as mild reducing agent and surface ligand. The proposed synthesis overcomes limitations of other synthetic routes in terms of cost, time, complexity and environmental risks, and gives rise to highly fluorescent gold nanodots within 10 min at room temperature, with a maximum emission wavelength at 623 nm and a large Stokes shift (213 nm). Moreover, the synthesized gold nanodots showed a large emission QY (9.62 × 10-2) and excellent photostability and colloidal properties during long periods. Increasing concentrations of CN- in aqueous solution progressively quenched the fluorescence emission and produced a slight blue shift of the synthesized gold nanodots. A good linear relationship was observed for CN- concentrations between 0.29 and 8.87 μM, obtaining a detection limit estimated according to the 3s IUPAC criteria of 150 nM. Besides, the influence on the fluorescence signal of potential interferents at high concentrations (1000 μM) was studied, including I-, F-, citrate, PO43-, NO3-, SO42-, CH3COO-, EDTA, Br-, CO32-, Cl- and S2- K+, Na+, Li+, Mg2+, Ca2+, Ba2+, Cu2+, Zn2+, Ni2+, Al3+, Fe2+, Fe3+, Pb2+, Cd2+, Hg2+ and Co2+. Results showed a high selectivity towards all the investigated ions, except for Pb2+, Cd2+ and Hg2+, although the use of glutathione and BSA as masking agents drastically minimized the effect of such cations at high concentrations. The synthesized gold nanodots were successfully evaluated as highly sensitive and selective probes for cyanide determination in environmental water samples, including tap, river, lake and sea water, indicating the validity of TCA-AuNDs for analytical CN- contamination control.Moreira Fernandes Castro Lopes Corte-Real Cavaco-Paulo Real Oliveira Gomes P J L I M A M E C D A C C.N. Oliveira M.P. Sarria
Counter ions and constituents combination affect DODAX:MO nanocarriers toxicity in vitro and in vivo Journal Article
Toxicology Research, 5 (Issue 4), pp. 1244-1255, 2016.
@article{Oliveira2016,
title = {Counter ions and constituents combination affect DODAX:MO nanocarriers toxicity in vitro and in vivo},
author = {Moreira Fernandes Castro Lopes Corte-Real Cavaco-Paulo Real Oliveira Gomes P J L I M A M E C D A C C.N. Oliveira M.P. Sarria},
url = {http://pubs.rsc.org/-/content/articlelanding/2016/tx/c6tx00074f/unauth#!divAbstract},
doi = {10.1039/C6TX00074F},
year = {2016},
date = {2016-06-13},
journal = {Toxicology Research},
volume = {5},
number = {Issue 4},
pages = {1244-1255},
abstract = {Liposomes have received extensive attention as nanocarriers for bioactive compounds due to their good biocompatibility, possibility of targeting and incorporation of hydrophilic and hydrophobic compounds. Although generally considered as safe, detailed knowledge of the effects induced in cells and tissues with which they interact is still underexplored. The aim of this study is to gain insight into the toxicity profile of dioctadecyldimethylammonium (DODAX) : monoolein(MO) liposomes (X is bromide or chloride), previously validated for gene therapy, by evaluating the effect of the counter ions Br− or Cl−, and of the cationic : neutral lipid molar fraction, both in vitro and in vivo. Effects on cellular metabolism and proliferation, plasma membrane integrity, oxidative stress, mitochondrial membrane potential dysfunction and ability to trigger apoptosis and necrosis were evaluated in a dose-/time-dependent manner in normal human skin fibroblasts. Also, newly fertilized zebrafish zygotes were exposed to liposomes, permitting a fast-track evaluation of the morphophysiological modifications. In vitro data showed that only very high doses of DODAX : MO induce apoptosis and necrosis, inhibit cell proliferation, and affect the metabolism and plasma membrane integrity of fibroblasts in a dose-/time-dependent manner. Furthermore, liposomes affected mitochondrial function, increasing ROS accumulation and disturbing mitochondrial membrane potential. DODAC-based liposomes were consistently more toxic when compared to DODAB-based formulations; furthermore, the inclusion of MO was found to reduce toxicity, in contrast to liposomes with cationic DODAX only, especially in DODAB : MO (1 : 2) nanocarriers. These results were corroborated, in a holistic approach, by cytotoxicity profiling in five additional human cell lines, and also with the zebrafish embryotoxicity testing, which constitutes a sensitive and informative tool and accurately extends cell-based assays.},
keywords = {},
pubstate = {published},
tppubtype = {article}
}Liposomes have received extensive attention as nanocarriers for bioactive compounds due to their good biocompatibility, possibility of targeting and incorporation of hydrophilic and hydrophobic compounds. Although generally considered as safe, detailed knowledge of the effects induced in cells and tissues with which they interact is still underexplored. The aim of this study is to gain insight into the toxicity profile of dioctadecyldimethylammonium (DODAX) : monoolein(MO) liposomes (X is bromide or chloride), previously validated for gene therapy, by evaluating the effect of the counter ions Br− or Cl−, and of the cationic : neutral lipid molar fraction, both in vitro and in vivo. Effects on cellular metabolism and proliferation, plasma membrane integrity, oxidative stress, mitochondrial membrane potential dysfunction and ability to trigger apoptosis and necrosis were evaluated in a dose-/time-dependent manner in normal human skin fibroblasts. Also, newly fertilized zebrafish zygotes were exposed to liposomes, permitting a fast-track evaluation of the morphophysiological modifications. In vitro data showed that only very high doses of DODAX : MO induce apoptosis and necrosis, inhibit cell proliferation, and affect the metabolism and plasma membrane integrity of fibroblasts in a dose-/time-dependent manner. Furthermore, liposomes affected mitochondrial function, increasing ROS accumulation and disturbing mitochondrial membrane potential. DODAC-based liposomes were consistently more toxic when compared to DODAB-based formulations; furthermore, the inclusion of MO was found to reduce toxicity, in contrast to liposomes with cationic DODAX only, especially in DODAB : MO (1 : 2) nanocarriers. These results were corroborated, in a holistic approach, by cytotoxicity profiling in five additional human cell lines, and also with the zebrafish embryotoxicity testing, which constitutes a sensitive and informative tool and accurately extends cell-based assays.
GROUP LEADER
THE TEAM
Raquel Queirós
Staff Researcher
Marília Santos
Staff Researcher
Laura Rodriguez-Lorenzo
Staff Researcher
Najib Ben Messaoud
Research Fellow
Patricia Taladriz
Research Fellow
Antonio Rubino
Research Fellow
Lurdes Gonçalves
Research Fellow
Renato Gil
Research Fellow
Bruna Alves
Research Fellow
Ana Vieira
Research Engineer
Monica Quarato
Junior Research fellow
Ivone Pinheiro
Junior Research Fellow
Ana Castanheira
Junior Research Fellow
Sofia Azevedo
Junior Research Fellow
Samuel Silva
Junior Research Fellow
Soraia P. Fernandes
PhD Student (FCT Grant)
Tianxing Wang
Scientific Associate (South China University of Technology, China)
Tânia Rebelo
Scientific Associate (DIN)
Juliana Dias
Scientific Associate (ICVS)
Sofia Neto
Scientific Associate (MSc student, UM)
Maria Catarino
Scientific Associate (MSc student, UM)
FORMER MEMBERS
Marisa P. Sárria
Research Fellow
Nagamalai Vasimalai
Research Fellow
Teodora Miclăuș
Research Fellow
Riya Gupta
Junior Research Fellow
Vânia Vilas-Boas
Research Laboratory Assistant
Vanesa Romero
Scientific Associate (UVigo, Spain)
Juan López
Scientific Associate (UVigo, Spain)
Juan Sanchéz
Scientific Associate (USantiago Compostela, Spain)
Blanca Astray
Scientific Associate (USantiago Compostela, Spain)
Catarina Ribeiro
Scientific Associate (FCT – NOVA , Portugal)
Beatriz Santamaria
Scientific Associate (Universidad Politécnica de Madrid, Spain)
Alexsandra Valerio
Scientific Associate (Federal University of Santa Catarina, Brazil)
Maria Rita Vega
Scientific Associate (Universidade Federal do Rio Grande do Sul, Brazil)
Cindy Dias
Master Student (UMinho, Portugal)
Sara Pinela
Master student (UMinho, Portugal)
Ana Castanheiro
Master student (UMinho, Portugal)
Filipe Ferreira
BSc Student (Instituto Superior de Engenharia do Porto, Portugal)
Rui Oliveira
BSc student (UMinho, Portugal)
Nanotechnology for a Safe and Sustainable use of Water Resources
We work on overcoming some of the most challenging issues in water environment making responsible use of the great opportunities that nanotechnology offers. The Water Quality research group focuses in three main activities:
- Nanotech-based sensors for water quality monitoring; we fully develop portable and/or remote biosensors for water biological and chemical contaminants.
- Nanomaterials for water contaminants capture; we design, fabricate and test nanomaterials for the selective capture of water chemical contaminants.
- (Eco) nanotoxicology; we develop and carry out methods for evaluating nanomaterials’ fate, bioaccumulation and toxicity. Special emphasis in implementing the safety-by-design concept to the in house produced nanomaterials.
RESEARCH PROJECTS
Industrial application of protocols for the mussel and pectinides detoxification using processing or depuration by microencapsulated agents. Nanotechnology enabled systems for aquacultured seafood contamination forecast.
Research on nanotechnologies applied to the environmental control in the water cycle.
Advanced web tools for enhancing the implementation of nanotechnology and the safe use of nanomaterials in the plastic industrial sector
New systems for water contaminants capture are being explored by means of novel tailored nanomaterials. On the other hand, biosensing devices are developed and/or tailored to detect and quantify the presence of water contaminants such as biotoxins, pathogens and invasive species.
Nanoporous COFs as modulable platforms for monitoring and analysis of pollutants in marine environment. The main objective of the COFsMEM project is the immobilization of highly accessible porous COFs onto solid substrates that can be implemented in Solid Phase Extraction modules for the selective adsorption of pollutants in the marine environment, such as biotoxins.
NANOEATERS is a network of Research Centers created with the objective of supporting Euroregional “early adopters” companies in the application of new nanotechnology-based solutions. Companies, Universities and Technology Centers will work together with INL in the definition of new nano-based commercially available products and /or services. The technologies targeted by the project will offer effective responses to the weaknesses detected in the cross border Smart Specialization Strategy (S3) Galicia – Northern Portugal, contributing to major social challenges as Health, Environmental Monitoring, Food Safety, Energy Efficiency or Industry 4.0
FOR MORE INFORMATION
GROUP LEADER
THE TEAM
Raquel Queirós
Staff Researcher
Marisa P. Sárria
Research Fellow
Marilia Santos
Research Fellow
Laura Rodriguez-Lorenzo
Research fellow
Ivone Pinheiro
Research Laboratory Assistant
Ana Castanheira
Research Laboratory Assistant
Vanesa Romero
Scientific Associate (UVigo, Spain)
Soraia P. Fernandes
PhD Student (FCT Grant)
FORMER MEMBERS
Nagamalai Vasimalai
Research Fellow
Vânia Vilas-Boas
Research Laboratory Assistant