TY - JOUR A1 - Scala-Benuzzi, M. L. A1 - Takara, E. A. A1 - Alderete, M. A1 - Soler-Illia, G. J. A. A. A1 - Schneider, Rudolf A1 - Raba, J. A1 - Messina, G. A. T1 - Ethinylestradiol quantification in drinking water sources using a fluorescent paper based immunosensor N2 - In this work we report a novel paper-based analytical device read-out via LED-induced fluorescence detection (FPAD) for the quantification of the emerging pollutant ethinylestradiol (EE2) in river water samples. The PAD was used as a reaction platform for a competitive enzyme immunoassay. For the PAD development, microzones of filter paper, printed by a wax printing method, were modified with amino-functionalized SBA-15 and subsequently, anti-EE2 specific antibodies were covalently immobilized. The determination of EE2 in water was carried out by adding a fixed concentration of EE2 conjugated with the enzyme horseradish peroxidase (HRP) to samples and standards. Then, the FPAD were added and incubated for 10 min. Finally, the detection was performed by the reaction of 10-acetyl-3,7-dihydroxyphenoxazine (ADHP) whose oxidation is catalyzed by HRP in the presence of H2O2, obtaining the highly fluorescent resorufin (R). Resorufin was detected by LED excitation at 550 nm, observing emission at 585 nm. The EE2 concentration in the samples was inversely proportional to the relative fluorescence obtained from the enzymatic reaction products. The FPAD assay showed a detection Limit (LOD) of 0.05 ng L−1 and coefficients of variation (CV) below 4.5% within-assay and below 6.5% between-assay, respectively. The results obtained show the potential suitability of our FPAD for the selective and sensitive quantification of EE2 in river water samples. In addition, it has the PADs advantages of being disposable, easy to apply and inexpensive. KW - Immunoassay KW - Arzneimittel KW - Antikörper KW - LED-induzierte Fluoreszenz KW - Paper based devices KW - Mesoporöses Silica KW - Partikel PY - 2018 DO - https://doi.org/10.1016/j.microc.2018.05.038 SN - 0026-265X VL - 141 SP - 287 EP - 293 PB - Elsevier B.V. CY - Amsterdam, NL AN - OPUS4-45269 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Raysyan, Anna A1 - Galvidis, I. A. A1 - Schneider, Rudolf A1 - Eremin, S. A. A1 - Burkin, M. A. T1 - Development of a latex particles-based lateral flow immunoassay for group determination of macrolide antibiotics in breast milk N2 - A lateral flow immunoassay (LFIA) using latex particles labeled with antibody to BSAclarithromycin (CLA) was developed for the rapid simultaneous group determination of six macrolide antibiotics. Optimization of antigen spotting on the membrane and latex probe loading allowed improving visual detectability (vLOD) 100 times, which was 1, 1, 10, 10, 50, and 1000 ng/mL for CLA, roxithromycin, erythromycin, dirithromycin, azithromycin, and oleandomycin in buffer, respectively. The calculated limits of instrumental detection (cLOD) were respectively 0.12, 0.15, 1.4, 2.1, 2.4, and 3.3 ng/mL. To avoid a strong influence of breast milk of a very diverse and variable composition, a sample pretreatment is proposed. The six macrolides mentioned can be visually detected in breast milk after 20 minutes pretreatment at concentrations of 10-1000 ng / ml or instrumentally with cLOD of 4.0, 2.5, 30, 42, 42 and 180 ng/mL. The recovery rate from the spiked samples carried out using a strip scanner device ranged from 71% to 110%, and precision expressed as relative standard deviation was between 3-14%. The described rapid on-site diagnostic assay format can be useful for monitoring the content of antibiotics in breast milk during macrolide treatment to ensure safe breastfeeding of infants. KW - Clarithromycin KW - Roxithromycin KW - Erythromycin KW - Dirithromycin KW - Azithromycin KW - Oleandomycin KW - Macrolide antibiotics KW - Makrolide KW - Antibiotika PY - 2020 DO - https://doi.org/10.1016/j.jpba.2020.113450 SN - 0731-7085 VL - 189 IS - 113450 SP - 1 EP - 9 PB - Elsevier CY - Amsterdam, NL AN - OPUS4-51343 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Scala-Benuzzi, M. L. A1 - Soler-Illia, G. J. A. A. A1 - Rabia, J. A1 - Battaglini, F. A1 - Schneider, Rudolf A1 - Pereira, S. V. A1 - Messina, G. A. T1 - Immunosensor based on porous gold and reduced graphene platform for the determination of EE2 by electrochemical impedance spectroscopy N2 - In this work, we report an electrochemical immunosensor to detect ethinylestradiol in water samples, using electrochemical impedance spectroscopy (EIS) as a detection technique. For the development of this immunosensor, the direct modification of the working electrode of a screen-printed carbon electrode was carried out. First, to reduce the resistance of the electrode, electroreduced graphene was incorporated on the surface. Second, a porous gold structure was electrodeposited on reduced graphene by electrodeposition and the dynamic hydrogen bubble template assisted method. Thus, a marked increase in surface area was obtained for anti-EE2 antibodies immobilization. Subsequently, the specific anti-EE2 antibodies were covalently immobilized using α-lipoic acid for attaching them to the gold surface. The electrode modified with the antibodies was incubated for 30 min in the samples containing EE2, producing the specific Antigen antibody binding. As the charge transfer resistance of a redox probe in the electrode surface is governed by the surface blocking effects, the charge transfer resistance was related to the amount of EE2 captured to realize a quantitative determination. For this, the EIS measurements were performed in a 4 mM [Fe(CN)6]4−/3− solution in 0.1 M KCl. The obtained Nyquist diagrams were adjusted using the Randles circuit as an equivalent circuit to obtain the corresponding resistances. The developed methodology showed good selectivity, precision, and sensitivity; although the LOD obtained was higher than those presented in other published articles, it turned out to be an alternative that allows the determination of ethinylestradiol using a simple disposable electrode. KW - Ethinylestradiol KW - Biosensor KW - Elektrochemisch KW - Impedanz PY - 2021 DO - https://doi.org/10.1016/j.jelechem.2021.115604 SN - 1572-6657 VL - 897 SP - 115604 EP - 115611 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-54048 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schneider, Rudolf A1 - Carvalho, A. M. A1 - Manicardi, A. A1 - Montes, C. V. A1 - Gunnoo, S. B. A1 - Madder, A. T1 - Decoration of trastuzumab with short oligonucleotides: synthesis and detailed characterization N2 - Trastuzumab (Herceptin) is an FDA-approved therapeutic antibody currently employed in the treatment of metastatic stages of breast cancer. Herein, we propose a simple, fast and cost-effective methodology to conjugate trastuzumab with 22-mer 5' thiol-modified oligonucleotides using a bifunctional crosslinker. The conjugates were successfully characterized by MALDI-ToF MS and SDS-PAGE, obviating the need for enzymatic digestion and difficult chromatographic separations. Furthermore, ELISA was performed to ensure that trastuzumab activity is not affected by oligonucleotide conjugation. KW - MALDI-ToF KW - ELISA PY - 2017 DO - https://doi.org/10.1039/c7ob02216f SN - 1477-0539 VL - 15 IS - 42 SP - 8923 EP - 8928 AN - OPUS4-43328 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Scala-Benuzzi, M. L. A1 - Raba, J. A1 - Soler-Illia, G. J. A. A. A1 - Schneider, Rudolf A1 - Messina, G. A. T1 - Novel electrochemical paper-based immunocapture assay for the quantitative determination of ethinylestradiol in water samples N2 - We report a novel and innovative electrochemical paper-based immunocapture assay (EPIA) to address the need for ultrasensitive detection of emerging pollutants without regulatory status and whose effects on environment and human health are not completely yet understood. In particular, we present the application of this system toward highly sensitive detection of the emerging pollutant ethinyl estradiol (EE2). The EPIA approach is based on the use of paper microzones modified with silica nanoparticles (SNs) and anti-EE2 specific antibodies for capture and preconcentration of EE2 from river water samples. After the preconcentration procedure, the paper microzones are placed onto a screen-printed carbon electrode modified with electrochemically reduced graphene (RG). The bound EE2 is subsequently desorbed adding a diluted solution of sulfuric acid on the paper microzones. Finally, recovered EE2 is electrochemically detected by OSWV. The proposed novel methodology showed an appropriate LOD and linear range for the quantification of EE2 for water samples with different origins. The nonsophisticated equipment required, the adequate recovery values obtained (from 97% to 104%, with a RSD less than 4.9%), and the appropriate LOD and linear range value (0.1 ng L−1 and 0.5−120 ng L−1, respectively) achieved by our immunocapture sensor present significant analytical figures of merit, particularly when the routine quantification of EE2 is considered. In addition, our System was based on electrochemical paper-based technology, which allows obtainment of portable, easy-to-use, inexpensive, and disposable devices. The EPIA can also serve as a general-purpose immunoassay platform applicable to quantitation of other drugs and emerging pollutants in environmental samples. KW - Immunoassay KW - EE2 KW - Estrogens KW - Screen-printed electrode KW - Square-wave voltammetry PY - 2018 DO - https://doi.org/10.1021/acs.analchem.8b00028 SN - 0003-2700 SN - 1520-6882 VL - 90 IS - 6 SP - 4104 EP - 4111 PB - American Chemical Society CY - Washington, D.C., USA AN - OPUS4-44690 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Hickel, Tilmann A1 - Divinski, S. A1 - Starikov, S. A1 - Soisson, F. A1 - Mény, C. A1 - Hegde, O. A1 - Gerlitz, M. A1 - Magnifouet, G. A1 - Schneider, A. A1 - Barreteau, C. A1 - Mirebeau, I. A1 - Tran, V.T. A1 - Förster, G. A1 - Front, A. A1 - Egorov, A. A1 - Wilde, G. A1 - Amara, H. A1 - Hammerschmidt, T. A1 - Mrovec, M. A1 - Pierron-Bohnes, V. A1 - Drautz, R. A1 - Fu, C. T1 - Magnetism in iron alloys: methodological advances for thermodynamics, defects, and kinetics N2 - Steels are among the technologically and economically most relevant materials. Key innovations in important sectors of human society such as mobility, energy and safety, are currently based on alloying of Fe with other transition-metal elements such as Mn, Cr, or Co. Due to strong impacts and conceptual challenges related to magnetism, however, the fundamental understanding and the ability to computationally design these steels in high-throughput approaches lags behind other classes of alloys. In this article, we will provide a substantial review of the role of magnetism, magnetic excitations and transformations for alloy thermodynamics, point defects, interfaces and kinetics. This will be achieved by combining insights from different methods: Ab initio simulations have the advantage that the magnetic ground state is intrinsic part of the electronic minimization. Due to the coarsening of the many-electron structures and therewith magnetic interactions, tight-binding methods can handle larger system sizes. Effective interaction models provide the freedom to exploit more sophisticated magnetic interactions. The performance of these methods in terms of magnetic properties of Fe alloys will be evaluated by providing state-of-the-art results for their sensitivity to magnetism. Furthermore, dedicated experiments will be discussed to complete the understanding of magnetic effects in Fe alloys and to validate the modeling strategy. KW - Magnetic excitations KW - Defects KW - Diffusion KW - Density functional theory KW - Tight-binding KW - Effective interaction models PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-634530 DO - https://doi.org/10.1515/ijmr-2023-0225 SN - 1862-5282 VL - 60 IS - 99 SP - 1 EP - 14761 PB - Walter de Gruyter GmbH AN - OPUS4-63453 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Almeida, Â. A1 - Calisto, V. A1 - Esteves, V. A1 - Schneider, Rudolf A1 - Figueira, E. A1 - Soares, A. A1 - Freitas, R. T1 - Can ocean warming alter sub-lethal effects of antiepileptic and antihistaminic pharmaceuticals in marine bivalves? N2 - The negative effects induced in marine organisms by Climate Change related abiotic factors consequences, namely ocean warming, are well-known. However, few works studied the combined impacts of ocean warming and contaminants, as pharmaceutical drugs. Carbamazepine (CBZ) and cetirizine (CTZ) occur in the marine environment, showing negative effects in marine organisms. This study aimed to evaluate the impacts of Ocean warming on the effects of CBZ and CTZ, when acting individually and combined (drug vs drug), in the edible clam Ruditapes philippinarum. For that, drugs concentration, bioconcentration factors and biochemical parameters, related with clam’s metabolic capacity and oxidative stress, were evaluated after 28 days exposure to environmentally relevant scenarios of these stressors. The results showed limited impacts of the drugs (single and combined) at control and warming condition. Indeed, it appeared that warming improved the oxidative status of contaminated clams (higher reduced to oxidized glutathione ratio, lower lipid peroxidation and Protein carbonylation levels), especially when both drugs were combined. This may result from clam’s defence mechanisms activation and reduced metabolic capacity that, respectively, increased elimination and limited production of reactive oxygen species. At low stress levels, defence mechanisms were not activated which resulted into oxidative stress. The present findings highlighted that under higher stress levels clams may be able to activate defence strategies that were sufficient to avoid cellular damages and loss of redox homeostasis. Nevertheless, low concentrations were tested in the present study and the observed responses may greatly Change under increased pollution levels or temperatures. Further research on this topic is needed since marine heat waves are increasing in frequency and intensity and pollution levels of some pharmaceuticals are also increasing in coastal systems. KW - Klimaerwärmung KW - Meer KW - Antiepileptika KW - Antihistaminika KW - Muscheln KW - Immunoassay KW - ELISA KW - Carbamazepine KW - Cetirizine PY - 2021 DO - https://doi.org/10.1016/j.aquatox.2020.105673 SN - 0166-445X VL - 230 SP - 105673 PB - Elsevier B.V. AN - OPUS4-51840 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schneider, Rudolf A1 - Almeida, Â. A1 - Calisto, V. A1 - Esteves, V. I. A1 - Soares, A. M. V. M. A1 - Freitas, R. T1 - Salinity-dependent impacts on the effects of antiepileptic and antihistaminic drugs in Ruditapes philippinarum N2 - In Coastal Systems, pollutants as pharmaceutical drugs exert changes from the molecular to the organism level in marine bivalves. Besides pollutants, Coastal Systems are prone to changes in environmental Parameters, as the alteration of salinity values because of Climate Change. Together, these Stressors (pharmaceutical drugs and salinity changes) can exert different threats than each Stressor acting individually; for example, salinity can change the physical-chemical properties of the drugs and/or the sensitivity of the organisms to them. However, limited Information is available on this subject, with variable results, and for this reason, this study aimed to evaluate the impacts of salinity changes (15,25 and 35) on the effects of the antiepileptic carbamazepine (CBZ, 1 (ig/L) and the antihistamine cetirizine (CTZ, 0.6 pg/L), when acting individually and combined (CBZ + CTZ), in the edible clam Ruditapes philippinarum. After 28 days ofexposure, drugs concentrations, bioconcentration factors and biochemical parameters, related to clam's metabolic caparity and oxidative stress were evaluated. The results showed that dams under low salinity suffered more changes in metabolic, antioxidant and biotransformation activities, in comparison with the remaining salinities under study. However, limited impacts were observed when comparing drug effects at low salinity. Indeed, it seemed that CTZ and CBZ + CTZ, under high salinity (salinity 35) were the worst exposure conditions for the dams, since they caused higher leveis of cellular damage. It Stands out that salinity changes altered the impact of pharmaceutical drugs on marine bivalves. KW - Muscheln KW - Salinität KW - Carbamazepin KW - Cetirizin KW - ELISA KW - Immunoassay KW - Antiepileptikum PY - 2022 DO - https://doi.org/10.1016/j.scitotenv.2021.150369 SN - 1879-1026 VL - 806 SP - 1 EP - 13 PB - Elsevier Science CY - Amsterdam AN - OPUS4-55561 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Almeida, Â. A1 - Calisto, V. A1 - Esteves, V. I. A1 - Schneider, Rudolf A1 - Soares, A. M. V. M. A1 - Freitas, R. T1 - Responses of Ruditapes philippinarum to contamination by pharmaceutical drugs under ocean acidification scenario N2 - In coastal systems, organisms are exposed to amultitude of stressors whose interactions and effects are poorly studied. Pharmaceutical drugs and Climate Change consequences, such as lowered pH, are examples of stressors affecting marine organisms, as bivalves. Although a vast literature is available for the effects of these stressors when acting individually, very limited information exists on the impacts that the combination of both can have on marine bivalves. For this reason, this study aimed to evaluate the impacts of a simulated ocean acidification scenario (control pH, 8.0; lowered pH, pH 7.6) on the effects of the antiepileptic carbamazepine (CBZ, 1 μg/L) and the antihistamine cetirizine (CTZ, 0.6 μg/L), when acting individually and combined (CBZ + CTZ), on the edible clam Ruditapes philippinarum. After 28 days of exposure, drug concentrations, bioconcentration factors and biochemical parameters related to the clams' metabolic capacity and oxidative stress were evaluated. The results showed that R. philippinarum clams responded differently to pharmaceutical drugs depending on the pH tested, influencing both bioconcentration and biological responses. In general, drug combined treatments showed fewer impacts than drugs acting alone, and acidification seemed to activate at a higher extension the elimination processes that were not activated under control pH. Also, lowered pH per se exerted negative impacts (e.g., cellular damage) on R. philippinarum and the combination with pharmaceutical drugs did not enhance the toxicity. KW - Biosensoren KW - Immunoassay KW - ELISA KW - Vor-Ort-Analytik KW - Toxikologie KW - Pharmaceutical drugs KW - Bivalves KW - Ocean acidification KW - Biomarkers KW - Climate change PY - 2022 DO - https://doi.org/10.1016/j.scitotenv.2022.153591 SN - 1879-1026 VL - 824 SP - 1 EP - 11 PB - Elsevier Science CY - Amsterdam AN - OPUS4-55590 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pieres, A. A1 - Almeida, Ângela A1 - Correia, J. A1 - Calisto, V. A1 - Schneider, Rudolf A1 - Esteves, V. I. A1 - Soares, A. M. V. M. A1 - Figueira, E. A1 - Freitas, R. T1 - Long-term exposure to caffeine and carbamazepine: Impacts on the regenerative capacity of the polychaete Diopatra neapolitana N2 - The toxicity induced in non-target organisms by pharmaceutical drugs has been the focus of several studies. In the aquatic environment, most of the studies have been devoted to fish and bivalves, while little is known on the impacts induced in polychaetes. The present study evaluated the impacts of carbamazepine and caffeine on the regenerative capacity of Diopatra neapolitana, a polychaete species with high ecological and economic relevance. Under laboratory controlled conditions polychaetes were exposed, during 28 days, to carbamazepine (Ctl-0.0; 0.3; 3.0; 6.0; 9.0 mg/L) and caffeine (Ctl-0.0; 0.5; 3.0; 18.0 mg/L). During the experiment, at days 11, 18, 25, 32, 39 and 46 after amputation, for each specimen, the percentage of the body width regenerated was determined and the number of new segments was counted. The regenerative capacity was assessed considering the number of days needed to achieve full regeneration and the total number of new segments. The obtained results revealed that with the increase of drugs concentrations organisms regenerated less new segments and took longer to completely regenerate. KW - Diopatra neapolitana KW - Pollution KW - Pharmaceutical drugs KW - Regenerative capacity PY - 2016 DO - https://doi.org/10.1016/j.chemosphere.2015.12.035 SN - 0045-6535 VL - 146 SP - 565 EP - 573 PB - Elsevier AN - OPUS4-38497 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Freitas, R. A1 - Almeida, Ângela A1 - Calisto, V. A1 - Velez, C. A1 - Moreira, A. A1 - Schneider, Rudolf A1 - Esteves, V. I. A1 - Wrona, F. J. A1 - Figueira, E. A1 - Soares, A. M. V. M. T1 - The impacts of pharmaceutical drugs under ocean acidification: Newdata on single and combined long-term effects of carbamazepine on Scrobicularia plana N2 - Ocean acidification and increasing discharges of pharmaceutical contaminants into aquatic systems are among key and/or emerging drivers of environmental change affecting marine ecosystems. A growing body of evidence demonstrates that ocean acidification can have direct and indirect impacts on marine organisms although combined effects with other stressors, namely with pharmaceuticals, have received very little attention to date. The present study aimed to evaluate the impacts of the pharmaceutical drug Carbamazepine and pH 7.1, acting alone and in combination, on the clamScrobicularia plana. For this, a long-termexposure (28 days)was conducted and a set of oxidative stress markers was investigated. The results obtained showed that S. plana was able to develop mechanisms to prevent oxidative damage when under low pH for a long period, presenting higher survival when exposed to this stressor compared to CBZ or the combination of CBZ with pH 7.1. Furthermore, the toxicity of CBZ on S. plana was synergistically increased under ocean acidification conditions (CBZ + pH 7.1): specimens survival was reduced and oxidative stress was enhanced when compared to single exposures. These findings add to the growing body of evidence that ocean acidification will act to increase the toxicity of CBZ to marine organisms,which has clear implications for coastal benthic ecosystems suffering chronic pollution from pharmaceutical drugs. KW - Ocean acidification KW - Pharmaceuticals KW - Biomarkers KW - Oxidative stress KW - Clams KW - Long-term exposures PY - 2016 DO - https://doi.org/10.1016/j.scitotenv.2015.09.138 VL - 541 SP - 977 EP - 985 PB - Elsevier B.V. AN - OPUS4-38502 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Pires, A. A1 - Almeida, Ângela A1 - Calisto, V. A1 - Schneider, Rudolf A1 - Esteves, V. I. A1 - Wrona, F. J. A1 - Soares, A. M. V. M. A1 - Figueira, E. A1 - Freitas, R. T1 - Long-term exposure of polychaetes to caffeine: Biochemical alterations induced in Diopatra neapolitana and Arenicola marina N2 - In the last decade studies have reported the presence of several pharmaceutical drugs in aquatic environments worldwide and an increasing effort has been done to understand the impacts induced on wildlife. Among the most abundant drugs in the environment is caffeine, which has been reported as an effective chemical anthropogenic marker. However, as for the majority of pharmaceuticals, scarce information is available on the adverse effects of caffeine on marine benthic organisms, namely polychaetes which are the most abundant group of organisms in several aquatic ecossystems. Thus, the present study aimed to evaluate the biochemical alterations induced by environmentally relevant concentrations of caffeine on the polychaete species Diopatra neapolitana and Arenicola marina. The results obtained demonstrated that after 28 days exposure oxidative stress was induced in both species, especially noticed in A. marina, resulting from the incapacity of antioxidant and biotransformation enzymes to prevent cells from lipid peroxidation. The present study further revealed that D. neapolitana used glycogen and proteins as energy to develop defense mechanisms while in A. marina these reserves were maintained independently on the exposure concentration, reinforcing the low capacity of this species to fight against oxidative stress. KW - Invertebrates KW - Pharmaceuticals KW - Oxidative stress biomarkers KW - Energy reserves PY - 2016 DO - https://doi.org/10.1016/j.envpol.2016.04.031 VL - 2016 IS - 214 SP - 456 EP - 463 PB - Elsevier Ltd. AN - OPUS4-38505 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -