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This paper describes the development of a simple voltammetric biosensor for the stereoselective discrimination of myo-inositol (myo-Ins) and D-chiro-inositol (D-chiro-Ins) by means of bovine serum albumin (BSA) adsorption onto a multi-walled carbon nanotube (MWCNT) graphite screen-printed electrode (MWCNT-GSPE), previously functionalized by the electropolymerization of methylene blue (MB). After a morphological characterization, the enantioselective biosensor platform was electrochemically characterized after each modification step by differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). The results show that the binding affinity between myo-Ins and BSA was higher than that between D-chiro-Ins and BSA, confirming the different interactions exhibited by the novel BSA/MB/MWCNT/GSPE platform towards the two diastereoisomers. The biosensor showed a linear response towards both stereoisomers in the range of 2-100 µM, with LODs of 0.5 and 1 µM for myo-Ins and D-chiro-Ins, respectively. Moreover, a stereoselectivity coefficient α of 1.6 was found, with association constants of 0.90 and 0.79, for the two stereoisomers, respectively. Lastly, the proposed biosensor allowed for the determination of the stereoisomeric composition of myo-/D-chiro-Ins mixtures in commercial pharmaceutical preparations, and thus, it is expected to be successfully applied in the chiral analysis of pharmaceuticals and illicit drugs of forensic interest.
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Inositol , Azul de Metileno , EstereoisomerismoRESUMEN
The overproduction of eumelanin leads to a panel of unaesthetic hyper-pigmented skin diseases, including melasma and age spots. The treatment of these diseases often requires the use of tyrosinase inhibitors, which act as skin whitening agents by inhibiting the synthesis of eumelanin, with harmful side effects. We report here that laccase from Trametes versicolor in association with a cocktail of natural phenol redox mediators efficiently degraded eumelanin from Sepia officinalis, offering an alternative procedure to traditional whitening agents. Redox mediators showed a synergistic effect with respect to their single-mediator counterpart, highlighting the beneficial role of the cocktail system. The pro-oxidant DHICA sub-units of eumelanin were degraded better than the DHI counterpart, as monitored by the formation of pyrrole-2,3,5-tricarboxylic acid (PTCA) and pyrrole-2,3-dicarboxylic acid (PDCA) degradation products. The most effective laccase-mediated cocktail system was successively applied in a two-component prototype of a topical whitening cream, showing high degradative efficacy against eumelanin.
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Lacasa , Preparaciones para Aclaramiento de la Piel , Lacasa/metabolismo , Melaninas/metabolismo , Preparaciones para Aclaramiento de la Piel/farmacología , Trametes/metabolismoRESUMEN
This work describes the development of a novel voltammetric immunosensor for the detection of salivary MMP-8 at the point-of-care. The electrochemical platform was based on a graphene (GPH) screen-printed electrode (SPE) functionalized by gold-nanospheres (AuNSs) and antibodies against MMP-8 protein (anti-MMP-8). The functionalization with anti-MMP-8 was realized by using 11-mercaptoundecanoic acid (11-MUA), thanks to its ability to give strong sulfur bonds with its -SH end, and to cross-link the -NH2 groups of the antibody molecule with the other -COOH end, using the traditional EDC-NHS method. The voltammetric sensor showed good performances with a linear range of 2.5-300 ng mL-1, a LOD value of 1.0 ± 0.1 ng mL-1 and a sensitivity of 0.05 µA mL cm-2 ng-1. Moreover, the proposed immunosensor was tested in real saliva samples, showing comparable results to those obtained with the conventional ELISA method. The biosensor was single-use and cost-effective and required a small quantity of test medium and a short preparation time, representing a very attractive biosensor for MMP-8 detection in human saliva.
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Técnicas Biosensibles , Periodontitis , Humanos , Metaloproteinasa 8 de la Matriz , Inmunoensayo , Técnicas Biosensibles/métodos , Técnicas Electroquímicas/métodos , Límite de Detección , Biomarcadores , Periodontitis/diagnóstico , Electrodos , OroRESUMEN
Stressors can initiate a cascade of central and peripheral changes that modulate mesocorticolimbic dopaminergic circuits and, ultimately, behavioral response to rewards. Driven by the absence of conclusive evidence on this topic and the Research Domain Criteria framework, random-effects meta-analyses were adopted to quantify the effects of acute stressors on reward responsiveness, valuation, and learning in rodent and human subjects. In rodents, acute stress reduced reward responsiveness (g = -1.43) and valuation (g = -0.32), while amplifying reward learning (g = 1.17). In humans, acute stress had marginal effects on valuation (g = 0.25), without affecting responsiveness and learning. Moderation analyses suggest that acute stress neither has unitary effects on reward processing in rodents nor in humans and that the duration of the stressor and specificity of reward experience (i.e., food vs drugs) may produce qualitatively and quantitatively different behavioral endpoints. Subgroup analyses failed to reduce heterogeneity, which, together with the presence of publication bias, pose caution on the conclusions that can be drawn and point to the need of guidelines for the conduction of future studies in the field.
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Chitosan and lignin mixed nanoparticles were prepared by layer-by-layer and nanoprecipitation methodologies as responsive platforms for sustainable biosensors. The novel nanoparticles showed effective chemophysical and electrochemical properties dependent on the preparation methodology, molecular weight of chitosan, and type of lignin. HOMO-LUMO energy gap calculations suggested the presence of structure-activity relationships between the electrochemical responsiveness and the order and orientation of lignin aromatic subunits and chitosan chains in the nanodevices.
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Quitosano , Nanopartículas , Lignina/química , Nanopartículas/química , Relación Estructura-ActividadRESUMEN
Deficits in motivational functioning including impairments in reward learning or reward sensitivity are common in psychiatric disorders characterized by anhedonia. Recently, anhedonic symptoms have been exacerbated by the pandemic caused by the Coronavirus disease 2019 (COVID-19) in the general population. The present study examined the putative associations between loss of smell (anosmia) and taste (ageusia) sensitivity, irrespective of COVID-19 infection, and anhedonia, measured by a signal-detection task probing the ability to modify behavior as a function of rewards (Probabilistic Reward Task; PRT). Tonic heart rate variability (HRV) was included in the model, due to its association with both smell and taste sensitivity as well as motivational functioning. The sample included 114 healthy individuals (81 females; mean age 22.2 years), who underwent a laboratory session in which dispositional traits, resting HRV and PRT performance were assessed, followed by a 4-days ecological momentary assessment to obtain daily measures of anosmia and ageusia. Lower levels of tonic HRV and lower momentary levels of smell and taste sensitivity were associated with impaired reward responsiveness and ability to shape future behavioral choices based on prior reinforcement experiences. Overall, the current results provide initial correlational evidence that could be fruitfully used to inform future experimental investigations aimed at elucidating the disruptive worldwide mental health consequences triggered by the pandemic.
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Ageusia , COVID-19 , Trastornos del Olfato , Femenino , Humanos , Adulto Joven , Adulto , COVID-19/complicaciones , Olfato , Ageusia/epidemiología , Ageusia/etiología , Frecuencia Cardíaca , SARS-CoV-2 , Anhedonia , Anosmia/complicacionesRESUMEN
The regulation of nervous and cardiovascular systems and some brain-related behaviors, such as stress, panic, anxiety, and depression, are strictly dependent on the levels of the main catecholamines of clinical interest, dopamine (DA), epinephrine (EP), and norepinephrine (NEP). Therefore, there is an urgent need for a reliable sensing device able to accurately monitor them in biological fluids for early diagnosis of the diseases related to their abnormal levels. In this paper, we present the first tyrosinase (Tyr)-based biosensor based on chitosan nanoparticles (ChitNPs) for total catecholamine (CA) detection in human urine samples. ChitNPs were synthetized according to an ionic gelation process and successively characterized by SEM and EDX techniques. The screen-printed graphene electrode was prepared by a two-step drop-casting method of: (i) ChitNPS; and (ii) Tyr enzyme. Optimization of the electrochemical platform was performed in terms of the loading method of Tyr on ChitNPs (nanoprecipitation and layer-by-layer), enzyme concentration, and enzyme immobilization with and without 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) and N-hydroxysuccinimide (NHS) as cross-linking agents. The Tyr/EDC-NHS/ChitNPs nanocomposite showed good conductivity and biocompatibility with Tyr enzyme, as evidenced by its high biocatalytic activity toward the oxidation of DA, EP, and NEP to the relative o-quinone derivatives electrochemically reduced at the modified electrode. The resulting Tyr/EDC-NHS/ChitNPs-based biosensor performs interference-free total catecholamine detection, expressed as a DA concentration, with a very low LOD of 0.17 µM, an excellent sensitivity of 0.583 µA µM-1 cm-2, good stability, and a fast response time (3 s). The performance of the biosensor was successively assessed in human urine samples, showing satisfactory results and, thus, demonstrating the feasibility of the proposed biosensor for analyzing total CA in physiological samples.
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Técnicas Biosensibles , Quitosano , Nanopartículas , Técnicas Biosensibles/métodos , Catecolaminas , Quitosano/química , Técnicas Electroquímicas/métodos , Electrodos , Humanos , Monofenol Monooxigenasa , Nanopartículas/químicaRESUMEN
In this work, we report on the development of a simple electrochemical immunosensor for the detection of D-dimer protein in human plasma samples. The immunosensor is built by a simple drop-casting procedure of chitosan nanoparticles (CSNPs) as biocompatible support, Protein A (PrA), to facilitate the proper orientation of the antibody sites to epitopes as a capture biomolecule, and the D-dimer antibody onto a carboxyl functionalized multi-walled carbon nanotubes screen printed electrode (MWCNTs-SPE). The CSNPs have been morphologically characterized by Scanning Electron Microscopy (SEM) and Dynamic Light Scattering (DLS) techniques. Successively, the electrochemical properties of the screen-printed working electrode after each modification step have been characterized by differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy (EIS). The resulting MWCNTs-CSNPs-PrA-D-dimer Ab immunosensor displays an optimal and promising platform for antibody immobilization and specific D-dimer detection. DPV has been used to investigate the antigen/antibody interaction at different D-dimer concentrations. The proposed voltammetric immunosensor allowed a linear range from 2 to 500 µg L-1 with a LOD of 0.6 µg L-1 and a sensitivity of 1.3 µA L µg-1 cm-2. Good stability and a fast response time (5 s) have been reported. Lastly, the performance of the voltammetric immunosensor has been tested in human plasma samples, showing satisfactory results, thus attesting to the promising feasibility of the proposed platform for detecting D-dimer in physiological samples.
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Técnicas Biosensibles , COVID-19 , Quitosano , Nanopartículas del Metal , Nanotubos de Carbono , Humanos , Técnicas Biosensibles/métodos , Nanotubos de Carbono/química , Inmunoensayo , COVID-19/diagnóstico , Biomarcadores , Pronóstico , Anticuerpos , Nanopartículas del Metal/química , Electrodos , Quitosano/química , Técnicas Electroquímicas , Límite de Detección , Oro/químicaRESUMEN
Green, biocompatible, and biodegradable antioxidants represent a milestone in cosmetic and cosmeceutical applications. Lignin is the most abundant polyphenol in nature, recovered as a low-cost waste from the pulp and paper industry and biorefinery. This polymer is characterized by beneficial physical and chemical properties which are improved at the nanoscale level due to the emergence of antioxidant and UV shielding activities. Here we review the use of lignin nanoparticles in cosmetic and cosmeceutical applications, focusing on sunscreen and antiaging formulations. Advances in the technology for the preparation of lignin nanoparticles are described highlighting structure activity relationships.