Chiral analysis of pesticides and drugs of environmental concern: biodegradation and enantiomeric fraction

The importance of stereochemistry for medicinal chemistry and pharmacology is well recognized and the dissimilar behavior of enantiomers is fully documented. Regarding the environment, the significance is equivalent since enantiomers of chiral organic pollutants can also differ in biodegradation processes and fate, as well as in ecotoxicity. This review comprises designed biodegradation studies of several chiral drugs and pesticides followed by enantioselective analytical methodologies to accurately measure the enantiomeric fraction (EF). The enantioselective monitoring of microcosms and laboratory-scale experiments with different environmental matrices is herein reported. Thus, this review focuses on the importance of evaluating the EF variation during biodegradation studies of chiral pharmaceuticals, drugs of abuse, and agrochemicals and has implications for the understanding of the environmental fate of chiral pollutants.info:eu-repo/semantics/publishedVersio

Solid Phase Extraction of Fluoroquinolone Antibiotics from Wastewaters – Assessment of Different Commercial Sorbents

Microbial degradation of fluorinated pharmaceuticals during wastewater treatment processes remains inadequate in most situations. Due to incomplete elimination, these residues are continually being introduced into the aquatic environments in which they settle throughout time since many of them are resistant to degradation. Fluoroquinolone antibiotics due to its persistence and implication on resistant-bacteria development, pose special interest in environmental analysis. Due to their zwitterionic characteristics, the extraction/pre-concentration process of fluoroquinolones prior analyses is an unquestionable challenge. This work compares the solid phase extraction efficiency of four fluoroquinolones (Ofloxacin, Norfloxacin, Ciprofloxacin and Moxifloxacin) from wastewater effluents by different commercial sorbents. Prior to wastewater analysis, preliminary tests were conducted in distilled water with a larger number of sorbents. Different experimental protocols and sorbents, namely OASIS® HLB, OASIS® WAX, OASIS® WCX (500 mg) and the molecularly imprinted polymer SupelMIP TM were applied to wastewater samples collected from a municipal wastewater treatment plant from the north of Portugal. The extracts were analyzed by a HPLC withFluorescence Detection validated method using a Luna PFP (2) 3µm column. Despite good results obtained with the molecularly imprinted polymer in distilled water, these cartridges did not perform efficiently when applied to wastewater effluents, probably due to the sample high complexity especially since their specific design for biological samples. Regarding OASIS® considered sorbents; HLB 500mg and WAX 500mg presented the best recovery rates of the fourstudied antibiotics, between 84-75% and 64-94%, respectively. Although the recoveries achievedwere not that dissimilar between the two mentioned sorbents, chromatograms of WAX extracts appear much cleaner in the antibiotics retention times while chromatograms of HLB extractsclearly show the presence of strong polar substances, probably matrix humic and fulvic acids,that behave as resilient interferences in the analysis, disturbing a proper identification of target compounds and reducing chromatographic resolution

Embedding Multi-Wall Carbon Nanotubes as Conductive Nanofiller onto Bi2Te3 Thermoelectric Matrix

Thermoelectric Generators (TEGs) are devices that have the ability to directly convert heat into electrical power, or vice-versa, and are being envisaged as one off-the-grid power source. Furthermore, carbon-based materials have been used as a conducting filler to improve several properties in thermoelectric materials. The present work studied the influence on the thermoelectric performance of Bi2Te3 bulk materials by incorporating different concentrations of Multi-Walled Carbon Nanotubes (MWCNT). In order to control and understand the influence of MWCNT dispersion in the nanocomposite, two different production methods (manual grinding and ultrasonication) were carried out and compared. It was verified that a larger dispersion leads to a better outcome for thermoelectric performance. The achieved Seebeck coefficient was up to -162 μV K-1 with a Power Factor of 0.50 μW K-2m-1, for the nanocomposite produced with 11.8 %V of MWCNT. This result demonstrates the ability to increase the thermoelectric performance of Bi2Te3 throughout the addition of MWCNT

Assessment of habitat suitability for common cockles in the Ria the Aveiro Lagoon under average and projected environmental conditions

The common cockle Cerastoderma edule is a widespread bivalve species inhabiting estuarine systems across the North East Atlantic, where it provides several ecosystem services, and represents a valuable fishery resource for local economies. However, anthropogenic pressure and more frequent extreme weather events threaten the resilience of the species. Spatially explicit information on species distribution is critical for the implementation of management and conservation practices. This study assessed the potential distribution of C. edule in the Ria de Aveiro by estimating the habitat suitability using an ensemble approach based on ecological niche modeling and recently developed hydrodynamic and water quality models to forecast both average and projected estuarine conditions. The models were developed for the summer of 2013 and spring of 2019 and potential range shifts in the species distribution were forecasted under projected environmental conditions: high and low estimates of freshwater discharge, a 2 °C increase in water temperature, and the combined effect of low freshwater discharge and increased water temperature. The results suggest that salinity, time of submersion, and current velocity play an important role in the distribution of cockles, and large areas were consistently classified with high habitat suitability. Increased freshwater discharge (both seasons) and low discharge coupled to increased temperature (spring) resulted in large decreases in suitable habitat. Conversely, low freshwater discharges and average (unchanged) temperatures increased the suitable habitat in the outermost regions of the Ria. The spatially explicit information provided contributes to a better understanding of the vulnerability of C. edule in the Ria de Aveiro to extreme weather events (e.g., droughts, river floods) and may support adaptive management strategies of the cockle fishery during these conditions. Moreover, this approach can be transferred to other estuarine ecosystems for which data describing the environmental conditions (e.g., derived from numerical models), and information about species presence are available (including data-poor species).publishe

Selective albumin-binding surfaces modified with a thrombin-inhibiting peptide

Blood-contacting medical devices have been associated with severe clinical complications, such as thrombus formation, triggered by the activation of the coagulation cascade due to the adsorption of certain plasma proteins on the surface of biomaterials. Hence, the coating of such surfaces with antithrombotic agents has been used to increase biomaterial haemocompatibility. Biomaterial-induced clotting may also be decreased by albumin adsorption from blood plasma in a selective and reversible way, since this protein is not involved in the coagulation cascade. In this context, this paper reports that the immobilization of the thrombin inhibitor D-Phe-Pro-D-Arg-D-Thr-CONH2 (fPrt) onto nanostructured surfaces induces selective and reversible adsorption of albumin, delaying the clotting time when compared to peptide-free surfaces. fPrt, synthesized with two glycine residues attached to the N-terminus (GGfPrt), was covalently immobilized onto self-assembled monolayers (SAMs) having different ratios of carboxylate-hexa(ethylene glycol)- and tri(ethylene glycol)-terminated thiols (EG6-COOH/EG3) that were specifically designed to control GGfPrt orientation, exposure and density at the molecular level. In solution, GGfPrt was able to inactivate the enzymatic activity of thrombin and to delay plasma clotting time in a concentration-dependent way. After surface immobilization, and independently of its concentration, GGfPrt lost its selectivity to thrombin and its capacity to inhibit thrombin enzymatic activity against the chromogenic substrate n-p-tosyl-Gly-Pro-Arg-p-nitroanilide. Nevertheless, surfaces with low concentrations of GGfPrt could delay the capacity of adsorbed thrombin to cleave fibrinogen. In contrast, GGfPrt immobilized in high concentrations was found to induce the procoagulant activity of the adsorbed thrombin. However, all surfaces containing GGfPrt have a plasma clotting time similar to the negative control (empty polystyrene wells), showing resistance to coagulation, which is explained by its capacity to adsorb albumin in a selective and reversible way. This work opens new perspectives to the improvement of the haemocompatibility of blood-contacting medical devices

Degradation of Fluoroquinolone Antibiotics and Identification of Metabolites/Transformation Products by LC-MS/MS

Antibiotics are a therapeutic class widely found inenvironmental matrices and extensively studied due to its persistence and implications for multi-resistant bacteria development. Degradation of four fluoroquinolone antibiotics, namely Ofloxacin (OFL), Norfloxacin (NOR), Ciprofloxacin (CPF) and Moxifloxacin (MOX), at 10 mg L-1 using a mixed bacterial culture, was assessed for 60 days. The assays were followed by a developed and validated analytical method of HPLC with Fluorescence Detection using a Luna PFP (2) 3µm column. The optimized conditions allowed picturing metabolites/transformation products formation and accumulation during the process, stating an incomplete mineralization, also shown byfluoride release. OFL and MOX presented the highest (98.3%) and the lowest (80.5%) extent of degradation after 19 days of assay, respectively. Some of these intermediate compounds were identified by LCMS/MS in selected degradation samples. Most of the intermediates were already described as biodegradation and/or photodegradationproducts in different conditions, but new and/or unknown metabolites were also present

Enhanced sweet taste perception in obesity: joint analysis of gustatory data from multiple studies

Copyright © 2022 Ribeiro, Torres, Fernandes, Camacho, Branco, Martins, Raimundo and Oliveira-Maia. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.Introduction: While sweet taste perception is a potential determinant of feeding behavior in obesity, the supporting evidence is inconsistent and is typically associated with methodological limitations. Notably, possible associations between sweet taste perception and measures of food reward remain undetermined. Materials and methods: We conducted a cross-sectional analysis comparing 246 individuals with severe obesity and 174 healthy volunteers using a validated method for taste perception assessment. We included gustatory variables, namely intensity and pleasantness ratings of sour, salt, sweet, and bitter tastants, and taste thresholds assessed by electrogustometry. Reward-related feeding behavior, including hedonic hunger, food addiction, feeding behavior traits, and acceptance of foods and alcohol, was evaluated using self-rated scales for comparison with gustatory measures. Result: In logistic regressions adjusted for age, gender, educational level, and research center, we found that a greater likelihood of belonging to the obesity group was associated with higher sweet intensity ratings (OR = 1.4, P = 0.01), hedonic hunger, food addiction symptoms, restrained and emotional eating (1.7 < OR ≤ 4.6, all P ≤ 0.001), and lower alcohol acceptance (OR = 0.6, P = 0.0002). Using principal component analysis, we found that while hedonic hunger, food addiction, and emotional eating were strongly interrelated, they were not associated with sweet intensity perception that, in turn, had a closer relationship with alcohol acceptance and restrained eating. Conclusion: We found that individuals with obesity report higher sweet taste intensity ratings than healthy controls. Furthermore, while psychological measures of reward-related feeding behavior assess a common construct, sweet intensity perception may represent a different obesity-related dimension.AJO-M was supported by grants from the BIAL Foundation (176/10), from Fundação para a Ciência e Tecnologia (FCT), through a Junior Research and Career Development Award from the Harvard Medical Portugal Program (HMSP/ICJ/0020/2011), and by a Starting Grant from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 950357). ST was funded by the Center for Psychology at the University of Porto (FCT UIDB/00050/2020). AF was funded by a postdoctoral fellowship from FCT (SFRH/BPD/880972/2012). GR was funded by doctoral fellowships from Universidade de Lisboa (BD/2015Call) and FCT (SFRH/BD/128783/2017).info:eu-repo/semantics/publishedVersio

Enhanced sweet taste perception in obesity: joint analysis of gustatory data from multiple studies

Copyright © 2022 Ribeiro, Torres, Fernandes, Camacho, Branco, Martins, Raimundo and Oliveira-Maia. This is an open-access article distributed under the terms of the Creative Commons Attribution License (CC BY). The use, distribution or reproduction in other forums is permitted, provided the original author(s) and the copyright owner(s) are credited and that the original publication in this journal is cited, in accordance with accepted academic practice. No use, distribution or reproduction is permitted which does not comply with these terms.Introduction: While sweet taste perception is a potential determinant of feeding behavior in obesity, the supporting evidence is inconsistent and is typically associated with methodological limitations. Notably, possible associations between sweet taste perception and measures of food reward remain undetermined. Materials and methods: We conducted a cross-sectional analysis comparing 246 individuals with severe obesity and 174 healthy volunteers using a validated method for taste perception assessment. We included gustatory variables, namely intensity and pleasantness ratings of sour, salt, sweet, and bitter tastants, and taste thresholds assessed by electrogustometry. Reward-related feeding behavior, including hedonic hunger, food addiction, feeding behavior traits, and acceptance of foods and alcohol, was evaluated using self-rated scales for comparison with gustatory measures. Result: In logistic regressions adjusted for age, gender, educational level, and research center, we found that a greater likelihood of belonging to the obesity group was associated with higher sweet intensity ratings (OR = 1.4, P = 0.01), hedonic hunger, food addiction symptoms, restrained and emotional eating (1.7 < OR ≤ 4.6, all P ≤ 0.001), and lower alcohol acceptance (OR = 0.6, P = 0.0002). Using principal component analysis, we found that while hedonic hunger, food addiction, and emotional eating were strongly interrelated, they were not associated with sweet intensity perception that, in turn, had a closer relationship with alcohol acceptance and restrained eating. Conclusion: We found that individuals with obesity report higher sweet taste intensity ratings than healthy controls. Furthermore, while psychological measures of reward-related feeding behavior assess a common construct, sweet intensity perception may represent a different obesity-related dimension.AJO-M was supported by grants from the BIAL Foundation (176/10), from Fundação para a Ciência e Tecnologia (FCT), through a Junior Research and Career Development Award from the Harvard Medical Portugal Program (HMSP/ICJ/0020/2011), and by a Starting Grant from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No. 950357). ST was funded by the Center for Psychology at the University of Porto (FCT UIDB/00050/2020). AF was funded by a postdoctoral fellowship from FCT (SFRH/BPD/880972/2012). GR was funded by doctoral fellowships from Universidade de Lisboa (BD/2015Call) and FCT (SFRH/BD/128783/2017).info:eu-repo/semantics/publishedVersio