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To evaluate the effects in adults rats submitted of a low-protein, high-carbohydrate (LPHC; 6% protein, 74% carbohydrate) diet and reversion (R) to a balanced diet introduced after weaning. Research methods & procedures: Male rats weigting approximately 100g (30 to 32 d old) were treated with control (C; 17% protein, 63% carbohydrate) or LPHC diets for 120 days. The reverse group (R) was treated with the LPHC diet for 15 days, and changed to C diet for another 105 days. Results: The LPHC group showed an increase in serum fasting triglycerides (TAG). Serum adiponectin was increased only in the LPHC group. Lipoprotein lipase (LPL) activity was decreased in the extensor digitorum longus (EDL) and cardiac muscles. The adiponectin receptor 1 content is the same among groups in the cardiac muscle, but it is lower in the EDL muscle in the LPHC group. In animals from the R group, these parameters are the same as the LPHC group. Thus, the LPHC diet administered for a long period, it promotes an increase in TAG. It is possible that there is adiponectin resistance in the EDL muscle, due to the lower LPL activity. The reversal of the LPHC diet did not normalize these parameters.

The definition of the van der Waals crust as the spherical section between the atomic radius and the van der Waals radius of an element is discussed and a survey of the application of the penetration index between two interacting atoms in a wide variety of covalent, polar, coordinative or noncovalent bonding situations is presented. It is shown that this newly defined parameter permits the comparison of bonding between pairs of atoms in structural and computational studies independently of the atom sizes., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Copaifera langsdorffii Desf. is recognised as one of most famous medicinal and economic species of Copaiba, occurring in several distinct biomes. An untargeted metabolomic approach was used to evaluate the chemical variability of C. langsdorffii from contrasting climates biomes (Atlantic Rainflorest and the semiarid Cerrado). Metabolomic analysis enabled the identification of 11 compounds, including glycosylated flavonoids and galloylquinic acid derivatives. Multivariate analysis highlighted that Cerrado population had a significantly higher concentrations of galloylquinic acid derivatives in comparison to the rainforest biome. Meanwhile, Atlantic Rainforest populations presented higher content of flavonols. Semiarid biome, reduced the concentration of flavonoids, mainly concerning quercetin and kaempferol derivatives, however, in this biome flavonoids were more diverse. Both chemical classes presented relevance to be used as geographical origin chemical markers by qualitative and quantitative features.

The geometrical parameters and the bonding in [D···X···D] + halonium compounds, where D is a Lewis base with N as the donor atom and X is Cl, Br, or I, have been investigated through a combined structural and computational study. Cambridge Structural Database (CSD) searches have revealed linear and symmetrical [D···X···D] + frameworks with neutral donors. By means of density functional theory (DFT), molecular electrostatic potential (MEP), and energy decomposition analyses (EDA) calculations, we have studied the effect of various halogen atoms (X) on the [D···X···D] + framework, the effect of different nitrogen-donor groups (D) attached to an iodonium cation (X = I), and the influence of the electron density alteration on the [D···I···D] + halonium bond by variation of the R substituents at the N-donor upon the symmetry, strength, and nature of the interaction. The physical origin of the interaction arises from a subtle interplay between electrostatic and orbital contributions (σ-hole bond). Interaction energies as high as 45 kcal/mol suggest that halonium bonds can be exploited for the development of novel halonium transfer agents, in asymmetric halofunctionalization or as building blocks in supramolecular chemistry.

In this study, isolation and purification of lichen substances from Usnea cornuta were performed using conventional solvents, green solvents and green technologies. In addition, several lichen compounds were tentatively identified by UHPLC/ESI/MS/MS and usnic acid, diffractaic and galbinic acids were quantified as well. Limonene, ethyl lactate and methanol, were compared regarding their extraction properties and antioxidant capacities, determined by DPPH, ORAC, and FRAP assays. In the ethyl lactate, methanol and limonene extracts, 28 compounds in all, were detected for the first time by high resolution UHPLC-MS/MS fingerprinting. Untargeted metabolomics tentatively identified 14 compounds from the methanolic extract, 4 from limonene extract, and 20 metabolites from ethyl lactate extract. The green extract of ethyl lactate showed a similar antioxidant capacity to toxic methanol extract, except at ORAC assay where it was higher. Therefore, ethyl lactate can replace methanol, to provide more sustainable green chemistry methods.

Vanillin is the main component of natural vanilla extract and is responsible for its flavoring properties. Besides its well-known applications as an additive in food and cosmetics, it has also been reported that vanillin can inhibit fungi of clinical interest, such as Candida spp., Cryptococcus spp., Aspergillus spp., as well as dermatophytes. Thus, the present work approaches the synthesis of a series of vanillin derivatives with 1,2,3-triazole fragments and the evaluation of their antifungal activities against Candida albicans, Candida glabrata, Candida parapsilosis, Candida tropicalis, Cryptococcus neoformans, Cryptococcus gattii, Trichophyton rubrum, and Trichophyton interdigitale strains. Twenty-two vanillin derivatives were obtained, with yields in the range of 60%-91%, from copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) click reaction between two terminal alkynes prepared from vanillin and different benzyl azides. In general, the evaluated compounds showed moderate activity against the microorganisms tested, with minimum inhibitory concentration (MIC) values ranging from 32 to >512 µg mL -1 . Except for compound 3b against the C. gattii R265 strain, all vanillin derivatives showed fungicidal activity for the yeasts tested. The predicted physicochemical and ADMET (absorption, distribution, metabolism, excretion, and toxicity) properties for the compounds indicated favorable profiles for drug development. In addition, a four-dimensional structure-activity relationship (4D-SAR) analysis was carried out and provided useful insights concerning the structures of the compounds and their biological profile. Finally, molecular docking calculations showed that all compounds bind favorably at the lanosterol 14α-demethylase enzyme active site with binding energies ranging from -9.1 to -12.2 kcal/mol., (© 2023 Deutsche Pharmazeutische Gesellschaft.)

Bauhinia forficata Link. is a native South American plant, which possesses volatile compounds with pharmaceutical and medicinal properties such as antidiabetic and anti-inflammatory effects. However, the conservation and propagation of this plant are complicated by its recalcitrant seeds and delayed flowering transition. Hence, tissue culture is employed for the safe and efficient propagation of B. forficata . However, the optimal conditions for the in vitro cultivation of B. forficata remain unknown. Thus, this study aimed to characterize the volatile profile of adult B. forficata field plants and evaluate the effects of different light intensities (43 and 70 μmol m -2  s -1 ), gas exchange rates (14 and 25 µL L -1  s -1 ), and exogenous sucrose concentrations (0, 20, and 30 g L -1 ) on their in vitro development. The results showed that β-caryophyllene is the major volatile compound produced by B. forficata . Moreover, culturing in a medium containing 30 g L -1 of sucrose and flasks with membranes that allow CO 2 exchange at the rate of 25 µL L -1  s -1 produced vigorous and hardened plants with high survival rates independent of irradiance. This study is the first to report the optimal in vitro culture conditions for B. forficata as a reference for future studies on micropropagation and secondary metabolite production using this species., Supplementary Information: The online version contains supplementary material available at 10.1007/s13205-023-03634-8., Competing Interests: Conflict of interestThe authors have no competing interests to declare that are relevant to the content of this article., (© King Abdulaziz City for Science and Technology 2023, Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.)

Selective recognition and removal of sulfate and phosphates from aqueous media in the presence of highly competing anions is very demanding because of their biological and environmental implications. In this paper, we present the anion recognition approach for the selective and efficient extraction of sulfate by nitrophenyl-functionalized tris-urea receptors (L 1 -L 2 ) from highly competitive aqueous media with an equivalent concentration of nitrate and other anions. Tetrabutylammonium hydroxide has been used for the first time as a phase transfer anionic extractant for sulfate-exchange from the aqueous phase to the organic phase (dichloromethane) containing a tris-urea receptor (L 1 -L 3 ). The sulfate extraction efficacy of L 2 (≈84-90%) was observed to be higher than those of L 1 (≈76-82%) and L 3 (≈68-75%) in competitive extraction experiments. In contrast, an analogous nitrophenyl-functionalized tris-thiourea receptor (L 4 ) has been recognized for the selective and efficient extraction of phosphates from aqueous media in the presence of several competing anions including sulfate and nitrate, with ≈85-92% extraction efficiency. In this case, tetrabutylammonium acetate has been used as a phase transfer anionic extractant for phosphate exchange between the two immiscible phases. Due to the higher acidity of tris-thiourea -NH groups in comparison to the analogous tris-urea, tetrabutylammonium hydroxide could deprotonate a hydrogen bond donating -NH group of the thiourea receptor and phosphate extraction was observed to be inefficient in such a case. Several liquid-liquid extraction (LLE) experiments have been carried out to establish the selective removal of sulfate and phosphates by the tripodal receptors from competitive aqueous media having different combinations of two or more anions. The LLE products obtained from organic phases were characterized by NMR ( 1 H, 13 C, 31 P, and 19 F) spectroscopy to affirm the oxoanion selectivity of the receptors and purity of the complexes. The tripodal receptors can easily be recycled for successive extraction cycles by simply washing the LLE products (oxoanion complexes) with a methanol-water (1 : 1, v/v) solvent system followed by filtration., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Coenzyme A (CoA) is a key cellular metabolite which participates in diverse metabolic pathways, regulation of gene expression and the antioxidant defense mechanism. Human NME1 (hNME1), which is a moonlighting protein, was identified as a major CoA-binding protein. Biochemical studies showed that hNME1 is regulated by CoA through both covalent and non-covalent binding, which leads to a decrease in the hNME1 nucleoside diphosphate kinase (NDPK) activity. In this study, we expanded the knowledge on previous findings by focusing on the non-covalent mode of CoA binding to the hNME1. With X-ray crystallography, we solved the CoA bound structure of hNME1 (hNME1-CoA) and determined the stabilization interactions CoA forms within the nucleotide-binding site of hNME1. A hydrophobic patch stabilizing the CoA adenine ring, while salt bridges and hydrogen bonds stabilizing the phosphate groups of CoA were observed. With molecular dynamics studies, we extended our structural analysis by characterizing the hNME1-CoA structure and elucidating possible orientations of the pantetheine tail, which is absent in the X-ray structure due to its flexibility. Crystallographic studies suggested the involvement of arginine 58 and threonine 94 in mediating specific interactions with CoA. Site-directed mutagenesis and CoA-based affinity purifications showed that arginine 58 mutation to glutamate (R58E) and threonine 94 mutation to aspartate (T94D) prevent hNME1 from binding to CoA. Overall, our results reveal a unique mode by which hNME1 binds CoA, which differs significantly from that of ADP binding: the α- and β-phosphates of CoA are oriented away from the nucleotide-binding site, while 3'-phosphate faces catalytic histidine 118 (H118). The interactions formed by the CoA adenine ring and phosphate groups contribute to the specific mode of CoA binding to hNME1.

This work aimed to synthesize and characterize a nanocarrier that consisted of a ternary system, namely β-cyclodextrin-based nanosponge (NS) inclusion compounds (ICs) associated with silver nanoparticles (AgNPs) to increase the antimicrobial activity of quercetin (QRC). The nanosystem was developed to overcome the therapeutical limitations of QRC. The host-guest interaction between NSs and QRC was confirmed by field emission scanning electron microscopy (FE-SEM), X-ray powder diffraction (XRPD), thermogravimetric analysis (TGA), and proton nuclear magnetic resonance ( 1 H-NMR). Moreover, the association of AgNPs with the NS-QRC was characterized using FE-SEM, energy-dispersive spectroscopy (EDS), transmission electron microscopy (TEM), dynamic light scattering (DLS), ζ-potential, and UV-Vis. Finally, the antimicrobial activity of the novel formulations was tested, which depicted that the complexation of QRC inside the supramolecular interstices of NSs increases the inhibitory effects against Escherichia coli ATCC25922, as compared to that observed in the free QRC. In addition, at the same concentrations used to generate an antibacterial effect, the NS-QRC system with AgNPs does not affect the metabolic activity of GES-1 cells. Therefore, these results suggest that the use of NSs associated with AgNPs resulted in an efficient strategy to improve the physicochemical features of QRC.

Laccase enzyme can replace chemical additives to improve texture properties and the volume of bread. Laccase encoding gene from Phlebia brevispora, a native fungus from Misiones, Argentina, was expressed in the generally recognized as safe yeast Kluyveromyces lactis. To improve laccase activity, medium conditions were optimized. The use of iron sulfate at a concentration of 1 mM led to optimum laccase activity (1289 U·L -1 ) on the fourth day of incubation. SDS-PAGE analysis revealed that the molecular mass of purified laccase was about 180 kDa. Optimum pH for the enzyme was 4 and optimum temperature was 40°C. Laccase exhibited high stability at low pH and high temperature. The application of recombinant laccase to bread decreased hardness, gumminess, and chewiness and increased bread volume. Based on these results, recombinant laccase from P. brevispora with improved yield is a good option for application as an improver of the physicochemical quality of bread at the industrial level. Besides, it will allow us to advance toward our goal of developing healthy alternatives for the bakery industry. No previous work has been reported concerning the heterologous expression of the laccase gene native to the province of Misiones, Argentina, with an aim for application in baking. PRACTICAL APPLICATION: Healthy bakeries became a trend in recent years. The use of the laccase enzyme increases the specific volume and decreases the hardness of bread, being thus an alternative for the replacement of chemical additives in the bakery industry., (© 2023 Institute of Food Technologists.)

A novel polymer bio-composite based on nano-hydroxyapatite (n-Hap) and chitosan (CS) (CS/n-Hap) was synthesized to effectively address toxic cadmium ions removal from water. The composition and structure of CS/n-Hap bio-composite were analyzed through different characterization techniques. XRD patterns affirmed that the crystalline structure of n-Hap remained unaltered during CS/n-Hap synthesis, while FT-IR spectrum sustained all the characteristic peaks of both CS and n-Hap, affirming the successful synthesis of CS/n-Hap. Adsorption studies, including pH, adsorbent dosage, contact time, initial Cd(II) concentration, and temperature, were carried out to explain and understand the adsorption mechanism. Comparatively, CS/n-Hap bio-composite exhibited better Cd(II) adsorption capacity than pristine CS, with an experimental maximum uptake of 126.65 mg/g under optimized conditions. In addition, the kinetic data were well fitted to the pseudo-second-order model, indicating the formation of chemical bonds between Cd(II) and CS/n-Hap during adsorption. Furthermore, the thermodynamic study suggested that Cd(II) adsorption onto CS/n-Hap was endothermic and spontaneous. The regeneration study showed only about a 3% loss in Cd(II) uptake by CS/n-Hap after five consecutive cycles. Thus, a simple and facile approach was here developed to synthesize an eco-friendly and cost-effective material that can be successfully employed for the removal of toxic heavy metal ions from water.

The prophylactic and therapeutic overuse of antimicrobials on the farm has contributed to the emergence of hard-to-fight bacterial strains causing bovine mastitis. Aiming at alternative therapies, this study evaluated the antimicrobial activity of 20 essential oils against clinical Staphylococcus aureus strains. Of them, five with strong activities were selected and evaluated for their minimum inhibitory concentrations (MIC) in culture medium and milk, cytotoxicity against bovine mammary cells (MAC-T), antiadhesive properties, and interactions among themselves and with cefoperazone. The oils remained active on milk, were not cytotoxic, and some concentrations stimulated MAC-T cells growth, suggesting healing potential. Subinhibitory concentrations of Coriandrum sativum, Origanum vulgare, Syzygium aromaticum, and Thymus vulgaris reduced biofilm formation by at least 80%. Several oil and cefoperazone combinations displayed additive interaction, with O. vulgare and C. sativum showing the most promising results. We developed formulations for being used as prophylactic postdipping solutions in the field, containing different concentrations (1% or 3%) of the active oils, alone or in combination, with 3% glycerin, 1% Tween 80, and water. The formulations showed strong antimicrobial activity in milk and enhanced antiadhesive properties, specially when two oils were combined in the formula, indicating promising biotechnological and therapeutical applications., (© The Author(s) 2023. Published by Oxford University Press on behalf of Applied Microbiology International.)

Opioid receptors mediate antinociceptive effects. Methanolic fractions from sugarcane varieties (MFSCf) were evaluated in classic nociception models. Interactions between bioactive compounds and the µ-opioid receptor (µOR) through docking analysis were also studied. Five methanolic fractions of sugarcane juice were obtained and analysed by LC-ESI-MS/MS. The fractions and standards of phenolic compounds were evaluated in a nociception model using the formalin test. All MFSCfs exhibited antinociceptive activity in the first phase of the formalin test. Docking analyses corroborates with the in vivo test results, suggesting that the phenolic substances are able to activate µOR. These results, for the first time, implicate phenolic constituents from sugarcane juice and other phenolic compounds in the activation of µOR. The antinociceptive activity of fractions from sugarcane juice suggests the potential pharmacological use of this species, widely cultivated in Brazil.

Previous studies focused on investigating particulate matter with aerodynamic diameter ≤ 2.5 µm (PM 2.5 ) have shown the risk of disease development, and association with increased morbidity and mortality rates. The current review investigate epidemiological and experimental findings from 2016 to 2021, which enabled the systemic overview of PM 2.5 's toxic impacts on human health. The Web of Science database search used descriptive terms to investigate the interaction among PM 2.5 exposure, systemic effects, and COVID-19 disease. Analyzed studies have indicated that cardiovascular and respiratory systems have been extensively investigated and indicated as the main air pollution targets. Nevertheless, PM 2.5 reaches other organic systems and harms the renal, neurological, gastrointestinal, and reproductive systems. Pathologies onset and/or get worse due to toxicological effects associated with the exposure to this particle type, since it can trigger several reactions, such as inflammatory responses, oxidative stress generation and genotoxicity. These cellular dysfunctions lead to organ malfunctions, as shown in the current review. In addition, the correlation between COVID-19/Sars-CoV-2 and PM 2.5 exposure was also assessed to help better understand the role of atmospheric pollution in the pathophysiology of this disease. Despite the significant number of studies about PM 2.5 's effects on organic functions, available in the literature, there are still gaps in knowledge about how this particulate matter can hinder human health. The current review aimed to approach the main findings about the effect of PM 2.5 exposure on different systems, and demonstrate the likely interaction of COVID-19/Sars-CoV-2 and PM 2.5 ., Competing Interests: Conflict of InterestThe authors declare no competing interests., (© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2023, Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.)

In this work, a cost-effective chitin-based magnesium oxide (CHt@MgO) biocomposite with excellent anionic methyl orange (MO) dye removal efficiency from water was developed. The CHt@MgO biocomposite was characterized by FT-IR, XRD, SEM-EDX, and TGA/DTG. Results proved the successful synthesis of CHt@MgO biocomposite. Adsorption of MO on the CHt@MgO biocomposite was optimized by varying experimental conditions such as pH, amount of adsorbent (m), contact time (t), temperature (T), and initial MO concentration ( C o ). The optimized parameters for MO removal by CHt@MgO biocomposite were as follows: pH, 6; m, 2 g/L; t, 120 min. Two common isotherm models (Langmuir and Freundlich) and three kinetic models (pseudo-first-order (PFO), pseudo-second-order (PSO), and intraparticle diffusion (IPD)) were tested for experimental data fitting. Results showed that Langmuir and PFO were the most suitable to respectively describe equilibrium and kinetic results on the adsorption of MO adsorption on CHt@MgO biocomposite. The maximum Langmuir monolayer adsorption capacity ( q m ) on CHt@MgO biocomposite toward MO dye was 252 mg/g at 60 °C. The reusability tests revealed that CHt@MgO biocomposite possessed high (90.7%) removal efficiency after the fifth regeneration cycle.

For the first time, we report a green extraction of lichen substances assisted by high power ultrasounds from Hypotrachyna cirrhata using ethyl lactate. This sustainable alternative was comparable, both in isolation and detection of lichen substances, to methanol. In the metabolomic analysis, a total of 77 lichen substances were detected comprising depsides, depsidones, dibenzofurans, organic acids, and lipids. Although the UHPLC/ESI/MS profiles were similar, the antioxidant activity was higher for the ethyl lactate extract. Ethyl lactate can replace toxic organic solvents, such as methanol, in order to provide more sustainable green chemistry methods.

Catasetum is a speciose Neotropical orchid genus of which male and female flowers emit scents acting both as attractant and reward for their exclusive pollinators, male orchid bees (Euglossini: Apidae). In Catasetum , it is well known that flowers display a remarkably morphological sexual dimorphism. However, it remains poorly investigated whether this is also true for floral scents. Here, we investigated the pollination ecology and floral scent traits (chemistry and total emission) of C. maranhense , a species endemic to the Brazilian N/NE region. Males of Euglossa securigera are the only pollinators of C. maranhense . The floral scent of C. maranhense is composed of 29 volatile compounds, with eucalyptol, indole, ( E )-Methyl p-methoxycinnamate, and ( Z )-Methyl p-methoxycinnamate accounting for more than 80% of the scent bouquet. No sexual dimorphism was detected in any of the traits investigated. We discuss the ecological and evolutionary significance of our findings to Catasetum species and other unisexual perfume plants.

Inflammatory bowel diseases are a group of inflammatory disorders of the gastrointestinal tract. Their prevalence is still low in Brazil, but the incidence is increasing annually. A variety of compounds present in Curcuma longa L., particularly curcumin, have been shown to reduce oxidative stress and aid in the prevention of associated diseases. This study aimed to assess the effect of curcumin transdermal gel on oxidative stress and intestinal inflammation in IL-10 knockout mice. Female mice were divided into four groups: a control group (C0) treated with vehicle and three experimental groups treated with transdermal gel containing 50 (C50), 75 (C75), and 100 (C100) mg curcumin kg-1 body weight. Colon malondialdehyde concentrations were lower in C50 and C75 groups. C100 treatment led to reduced catalase activity in the small intestine, whereas C50, C75, and C100 treatments resulted in decreased catalase activity in the colon. In contrast, superoxide dismutase activity increased in the small intestine of C50 and C75 mice and decreased in the colon of C50, C75, and C100 mice. Glutathione S-transferase activity increased in the small intestine and decreased in the colon of C75 animals. These findings suggest that curcumin transdermal gel exerts a protective effect against oxidative stress.

Antibiotics, such as oxolinic acid (OXA), in aquaculture effluents contribute to the dissemination of antimicrobial resistance, which makes it urgent to develop efficient and sustainable processes for their removal. Aiming a photocatalytic degradation under solar radiation, different carbon quantum dots (CQDs) were produced in this work through a bottom-up hydrothermal methodology and incorporated into TiO 2 by a simple calcination method. A total of thirteen materials were synthesized and tested for OXA photocatalytic removal from synthetic and real matrices. Among them, CQDs produced with citric acid and incorporated into TiO 2 at 4% (w/w) (TiO 2 /CQDs-CA 4% (w/w)) were the most efficient photocatalysts, providing an OXA half-life time (t 1/2 ) decrease of 91%, 79% and 85% in phosphate buffer solution (PBS), synthetic sea salts (SSS) and brackish aquaculture effluent (BAE), respectively. Therefore, the herein synthesized TiO 2 /CQDs-CA 4% (w/w) composites have shown to be promising materials for a sustainable solar-driven removal of antibiotics from aquaculture effluents., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The species Myrsine umbellata is a native plant of Brazil, whose barks are traditionally used in herbal medicine to treat liver disorders and combat leprosy. Therefore, the aim of the study was to identify the phytochemical prospection of ethanolic (EE) and acetonic (EA) extracts by colorimetric tests and by gas chromatography coupled to mass spectrometry (GC-MS) of the essential oil (EO) of M. umbellata leaves; evaluate the antimicrobial activity in front of standard ATCC strains by the broth microdilution technique; the antioxidant potential by DPPH reduction method and antibiofilm action by crystal violet assay and cell viability was determined using 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) based on optical density. Phytochemical prospection of EE and EA detected the presence of free steroids, alkaloids, flavonoids (flavones, flavononoids, flavonols and xanthons) and tannins in both extracts (EE and EA) and saponins only in EE. In EO, the majority compounds identified were elixene, caryophyllene (E), spatulenol, d-Cadinene and aromadendrene. EA showed antimicrobial activity with MIC and MBC/MFC values ranging from 3.12 to 100 mg.mL-1, highlighting its efficiency on the Gram-positive strain S. epidermidis. EE showed antimicrobial potential in the range of 3.12 to 200 mg.mL-1, and the Gram-negative E. coli strain was the most susceptible. However, OE showed bacteriostatic potential against S. Typhimurium, S. Abaetetuba, P. aeruginosa, and S. epidermidis strains. The ability to sequester free radicals was evident in EA extract with antioxidant activity of 89.55% and in EE with 63.05%. The antibiofilm potential was observed in EE extract which eradicated the mature biofilm biomass of all tested bacteria with high activity (50% to 84.28%) and EO also showed antibiofilm effect on mature biofilm of UEL enteroaggregative E. coli, S. aureus and S. Enteritidis strains with biomass reduction percentage of 63.74%, 68.04% and 86.19%, respectively. These results indicate the potential of M. umbellata extracts and as a source of plant bioactivity for the development of new alternative strategies for the control of planktonic or biofilm-resistant microorganisms.

Within the 2,5-dioxopiperazine-containing natural products generated by "head-to-tail" cyclization of peptides, those derived from tryptophan allow further structural diversification due to the rich chemical reactivity of the indole heterocycle, which can generate tetracyclic fragments of hexahydropyrrolo[2,3- b ]indole or pyrrolidinoindoline skeleton fused to the 2,5-dioxopiperazine. Even more complex are the dimeric bispyrrolidinoindoline epi(poly)thiodioxopiperazines (BPI-ETPs), since they feature transannular (poly)sulfide bridges connecting C3 and C6 of their 2,5-dioxopiperazine rings. Homo- and heterodimers composed of diastereomeric epi(poly)thiodioxopiperazines increase the complexity of the family. Furthermore, putative biogenetically generated downstream metabolites with C11 and C11'-hydroxylated cores, as well as deoxygenated and/or oxidized side chain counterparts, have also been described. The isolation of these complex polycyclic tryptophan-derived alkaloids from the classical sources, their structural characterization, the description of the relevant biological activities and putative biogenetic routes, and the synthetic efforts to generate and confirm their structures and also to prepare and further evaluate structurally simple analogs will be reported.

A second-generation hydrogen bond donor (HBD) anion receptor with an inner amide cavity and an outer urea cavity can selectively and efficiently extract arsenate (AsO 4 3- ) from water in the presence of competitive oxoanions and halides. The X-ray structure showed encapsulation of AsO 4 3- in a π-stacked dimeric capsular assembly of the receptor, the first crystallography-based example of pentavalent AsO 4 3- trianion recognition by a HBD receptor.

Electronic absorption and emission spectra of [M 25 (MPA) 18 ] - (M = Au, Ag; MPA = SCH 2 CH 2 COOH) clusters have been recorded for energies below 5 eV at the time-dependent density functional theory (TDDFT) level using B3LYP and TPSSh functionals and compared to the calculated ones using the computationally inexpensive simplified TDDFT (sTDDFT) approach. The results show a qualitative agreement between the TDDFT and sTDDFT approaches used here, which were also in line with the experimental and theoretical spectra previously reported. However, the sTDDFT calculations were several orders of magnitude faster than those obtained by TDDFT. Our results support that sTDDFT provides an excellent balance between accuracy and low computational cost, becoming a suitable approach for studying the absorption and emission spectra of noble-metal clusters of sizes that would be unaffordable by the traditional TDDFT methods. The main peaks of the experimental absorption spectrum of [Au 25 (MPA) 18 ] - have been previously assigned, whereas [Ag 25 (MPA) 18 ] - has not been synthesised. However, its absorption spectrum resulted in having similar features to the experimental spectrum of [Ag 25 (GSH) 18 ] - (GSH = glutathione), used to validate our results. The emission spectra, which to date have not been reported either from experimental or theoretical means, were simulated by using the molecular structure of the first excited triplet state (T 1 ). The emission spectra were obtained by comparing them to those of [M 25 (GSH) 18 ] - since no experimental luminescence spectra have been reported for [M 25 (MPA) 18 ] - . The calculations suggest that [Ag 25 (SR) 18 ] - (SR = thiolate) clusters have a weak luminescence band in the NIR region. Finally, solvent shifts were found to be minor, whereas the absorption bands seem to be significantly redshifted in solid-state materials.

An Ag@Au bimetallic nanoparticle (BNP) formulation was developed in this work. The proposed formulation was developed using photochemical and chemical methods and non-toxic reagents, showing high reproducibility and homogeneity. The synthesized BNPs have an average size of 7 nm, a core-shell-like structure (silver core and gold shell), high colloidal and long-term stability, and superior catalytic activity under darkness and white light irradiation conditions when evaluating the reduction of 4-nitrophenol to 4-aminophenolate, with respect to the monometallic Ag and Au counterparts. Furthermore, BNP concentrations as low as 2 nM were required to reach 100% conversions in less than 30 minutes. Therefore, considering future applications, the high surface-to-volume ratio of the prepared BNPs coupled with their well-defined optical properties makes them a great candidate for developing heterogeneous catalyzer materials to be applicable under sunlight as an environmentally friendly catalytic system., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

The high reactivity of gold-vinylidene complexes, generated in situ by [1,2]-bromine shift from the corresponding 1-bromoalkynes, allows the activation of one of the strongest bonds in organic chemistry (Si-O), strategically placed at the ortho -position. In this way, the synthesis of 3-bromo-2-silylbenzofuranes is achieved in good yields. Several substituents with different electronic properties and substitution patterns are well tolerated on the tethering aromatic ring as well as a number of silyl groups on the O-atom. A preliminary mechanistic study is compatible with the participation of gold vinylidene intermediate species. The synthetic applicability of the obtained scaffolds was preliminarily showcased by orthogonal C-C bond forming transformations.

Four difluorenoheteroles having a central quinoidal core with the heteroring varying as furan, thiophene, its dioxide derivative and pyrrole have shown to be medium character diradicals. Solid-state structures, optical, photophysical, magnetic, and electrochemical properties have been discussed in terms of diradical character, variation of aromatic character and captodative effects (electron affinity). Organic field-effect transistors (OFETs) have been prepared, showing balanced hole and electron mobilities of the order of 10 -3  cm 2  V -1  s -1 or ambipolar charge transport which is first inferred from their redox amphoterism. Quantum chemical calculations show that the electrical behavior is originated from the medium diradical character which produces similar reorganization energies for hole and electron transports. The vision of a diradical as simultaneously bearing pseudo-hole and pseudo-electron defects might justify the reduced values of reorganization energies for both regimes. Structure-function relationships between diradical and ambipolar electrical behavior are revealed., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Coenzyme A (CoA) is a key cellular metabolite known for its diverse functions in metabolism and regulation of gene expression. CoA was recently shown to play an important antioxidant role under various cellular stress conditions by forming a disulfide bond with proteins, termed CoAlation. Using anti-CoA antibodies and liquid chromatography tandem mass spectrometry (LC-MS/MS) methodologies, CoAlated proteins were identified from various organisms/tissues/cell-lines under stress conditions. In this study, we integrated currently known CoAlated proteins into mammalian and bacterial datasets (CoAlomes), resulting in a total of 2093 CoAlated proteins (2862 CoAlation sites). Functional classification of these proteins showed that CoAlation is widespread among proteins involved in cellular metabolism, stress response and protein synthesis. Using 35 published CoAlated protein structures, we studied the stabilization interactions of each CoA segment (adenosine diphosphate (ADP) moiety and pantetheine tail) within the microenvironment of the modified cysteines. Alternating polar-non-polar residues, positively charged residues and hydrophobic interactions mainly stabilize the pantetheine tail, phosphate groups and the ADP moiety, respectively. A flexible nature of CoA is observed in examined structures, allowing it to adapt its conformation through interactions with residues surrounding the CoAlation site. Based on these findings, we propose three modes of CoA binding to proteins. Overall, this study summarizes currently available knowledge on CoAlated proteins, their functional distribution and CoA-protein stabilization interactions.

Herein, we describe the design and synthesis of a new variety of bio-based hydrogel films using a Cu(I)-catalyzed photo-click reaction. These films exhibited thermal-triggered swelling-deswelling and were constructed by crosslinking a triazide derivative of glycerol ethoxylate and dialkyne structures derived from isosorbide, a well-known plant-based platform molecule. The success of the click reaction was corroborated through infrared spectroscopy (FTIR) and the smooth surface of the obtained films was confirmed by scanning electron microscopy (SEM). The thermal characterization was carried out in terms of thermogravimetry (TGA) and differential scanning calorimetry (DSC), from which the decomposition onset and glass transition temperatures were determined, respectively. Additionally, mechanical properties of the samples were estimated by stress-strain experiments. Then, their swelling and deswelling properties were systematically examined in PBS buffer, revealing a thermoresponsive behavior that was successfully tested in the release of the anticancer drug doxorubicin. We also confirmed the non-cytotoxicity of these materials, which is a fundamental aspect for their potential use as drug carriers or tissue engineering matrices.

Atmospheric particulate matter (APM) emitted by iron ore processing industries has a complex composition, including diverse metallic particles and nanoparticles. Settleable APM (SePM) causes air to water cross-contamination and has recently been demonstrated to have harmful sublethal impacts on fish, eliciting stress responses, affecting the immune system, and reducing blood oxygen-carrying capacity. These findings imply potential consequences for fish aerobic performance and energy allocation, particularly in their ability to tolerate respiratory challenges such as aquatic hypoxia. To assess that potential limitation, we analyzed metabolic, cardiorespiratory, and morphological alterations after exposing tilapia, Oreochromis niloticus, to an environmentally relevant concentration of SePM (96 h) and progressive hypoxia. The contamination initiated detectable gill damage, reducing respiratory efficiency, increasing ventilatory effort, and compromising fish capacity to deal with hypoxia. Even in normoxia, the resting respiratory frequency was elevated and limited respiratory adjustments during hypoxia. SePM increased O 2 crit from 26 to 34% of O 2 (1.84 to 2.76 mg O 2 ·L -1 ). Such ventilatory inefficacy implies higher ventilatory cost with relevant alterations in energy allocation. Progression in gill damage might be problematic and cause: infection, blood loss, ion imbalance, and limited cardiorespiratory performance. The contamination did not cause immediate lethality but may threaten fish populations due to limitations in physiological performance. This was the first investigation to evaluate the physiological responses of fish to hypoxia after SePM contamination. We suggest that the present level of environmental SePM deserves attention. The present results demonstrate the need for comprehensive studies on SePM effects in aquatic fauna., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Steel industry emissions of atmospheric particulate matter are responsible for air to water cross-contamination, which deposits metal/metalloid contaminants in aquatic ecosystems. This source of contamination has not been considered in most of the environmental monitoring protocols. Settleable atmospheric particulate matter (SePM) collected in an area of steel industry influence was used to analyze the sublethal effects on the hematological and innate immunological variables in Nile tilapia (Oreochromis niloticus) after short-term exposure (96 h). Blood samples were analyzed to evaluate the oxygen-carrying transport capacity, innate immune activity and stress biomarkers after exposure to ecologically relevant concentration of SePM. The exposure reduced blood oxygen-carrying capacity by lessening hematocrit, hemoglobin, erythrocyte, and mean corpuscular hemoglobin concentration. Compensatory increments in mean corpuscular volume and mean corpuscular hemoglobin have also been observed. The contaminant impacted the immune system by reducing the number of leukocytes, thrombocytes, and monocytes, total plasma protein, leukocyte respiratory activity, and by increasing lysozyme concentration. Furthermore, the contaminant caused endocrine stress response, raising plasma cortisol and glucose. Therefore, the alterations caused by SePM threatened the capacity of sustaining aerobic metabolism, impaired the immune system, and changed the energy allocation due to both stress response and immune effect. This may have important implications for the impact of SePM on aquatic ecosystems. Future investigations should assess SePM impact on general physiology and aerobic performance, especially to face common ecological challenges such as hypoxia and sustained swimming. These results point out the need to develop proper protocols to address the air-to-water cross-contamination risks by iron ore processing industries., (Copyright © 2022 Elsevier Inc. All rights reserved.)

Probabilities of the outcomes of consecutive quantum measurements can be obtained by construction probability amplitudes, thus implying the unitary evolution of the measured system, broken each time a measurement is made. In practice, the experimenter needs to know all past outcomes at the end of the experiment, and that requires the presence of probes carrying the corresponding records. With this in mind, we consider two different ways to extend the description of a quantum system beyond what is actually measured and recorded. One is to look for quantities whose values can be ascertained without altering the existing probabilities. Such "elements of reality" can be found, yet they suffer from the same drawback as their EPR counterparts. The probes designed to measure non-commuting operators frustrate each other if set up to work jointly, so no simultaneous values of such quantities can be established consistently. The other possibility is to investigate the system's response to weekly coupled probes. Such weak probes are shown either to reduce to a small fraction the number of cases where the corresponding values are still accurately measured, or lead only to the evaluation of the system's probability amplitudes, or their combinations. It is difficult, we conclude, to see in quantum mechanics anything other than a formalism for predicting the likelihoods of the recorded outcomes of actually performed observations.

Despite the increasing progress achieved in the last 20 years in both the fabrication of porous dental implants and the development of new biopolymers for targeting drug therapy, there are important issues such as bone resorption, poor osseointegration, and bacterial infections that remain as critical challenges to avoid clinical failure problems. In this work, we present a novel microtechnology based on polycaprolactone microspheres that can adhere to porous titanium implant models obtained by the spacer holder technique to allow a custom biomechanical and biofunctional balance. For this purpose, a double emulsion solvent evaporation technique was successfully employed for the fabrication of the microparticles properly loaded with the antibacterial therapeutic agent, rose bengal. The resulting microspheres were infiltrated into porous titanium substrate and sintered at 60 °C for 1 h, obtaining a convenient prophylactic network. In fact, the sintered polymeric microparticles were demonstrated to be key to controlling the drug dissolution rate and favoring the early healing process as consequence of a better wettability of the porous titanium substrate to promote calcium phosphate nucleation. Thus, this joint technology proposes a suitable prophylactic tool to prevent both early-stage infection and late-stage osseointegration problems.

The effects of particle interactions on the size segregation and assembly of colloidal mixtures during drying were investigated. A cationic surfactant was added to a binary latex/silica colloidal dispersion that has been shown to self-stratify upon drying at room temperature. Atomic force microscopy was used to show that the change in particle interactions due to the presence of surfactants reduced the degree of stratification and, in some cases, suppressed the effect altogether. Colloidal dispersions containing higher surfactant concentrations can undergo a complete morphology change, resulting instead in the formation of armored particles consisting of latex particles coated with smaller silica nanoparticles. To further prove that armored particles are produced and that stratification is suppressed, cross-sectional images were produced with energy-dispersive X-ray spectroscopy and confocal fluorescence microscopy. The growth of armored particles was also measured using dynamic light scattering. To complement this research, Brownian dynamics simulations were used to model the drying. By tuning the particle interactions to make them more attractive, the simulations showed the presence of armored particles, and the size segregation process was hindered. The prevention of segregation also results in enhanced transparency of the colloidal films. Overall, this research proves that there is a link between particle interactions and size segregation in drying colloidal blends and provides a valuable tool to control the assembly of different film architectures using an extremely simple method.

The extraction and characterization of the essential oils (EO) from Satureja montana L., Myristica fragrans H. and Cymbopogon flexuosus and the determination of their antibacterial and antioxidant activities were achieved. The EO were identified by gas chromatography/mass spectrometry and quantified by gas chromatography using a flame ionization detector. The antibacterial potential against Escherichia coli and Staphylococcus aureus was evaluated by cell susceptibility assays and by scanning electron microscopy. The antioxidant activity was evaluated by the 2,2-diphenyl-1-picrylhydrazyl assay, by β-carotene bleaching and by determining the reducing power. Borneol (36·18%), γ-terpineol (12·66%) and carvacrol (11·07%) were the principal components in the EO from S. montana, and sabinene (49·23%) and α-pinene (13·81%) were found in the EO from M. fragrans. Geranial (59·66%) and neral (38·98%) isomers were the only major components in the EO from C. flexuosus. The EO from S. montana was effective against E. coli, with minimum inhibitory and bactericidal concentrations (MIC and MBC) of 6·25 µl ml -1 , whereas bactericidal potential against both was observed for the EO from M. fragrans; MIC = 6·25 µl ml -1 for S. aureus and MBC = 12·5 µl ml -1 for E. coli. A significant protective role on lipid substrates in the β-carotene bleaching assay was seen for the EO from S. montana and M. fragrans. Overall, such EO can be promising agents against pathogenic bacteria and for protecting biomolecules during oxidative stress., (© 2022 The Society for Applied Microbiology.)

A new macrolide, enigmazole C ( 1 ), and two additional analogues, enigmazoles E ( 2 ) and D ( 3 ), were obtained from a new species of the Homophymia genus as part of an ongoing discovery program at PharmaMar to study cytotoxic substances from marine sources. The structures were fully characterized by cumulative analyses of NMR, IR, and MS spectra, along with density functional theory computational calculations. All three of the new compounds feature an unusual 2,3-dihydro-4 H -pyran-4-one moiety, but only enigmazoles C ( 1 ) and D ( 3 ) showed cytotoxic activity in the micromolar range against A-549 (lung), HT-29 (colon), MDA-MB-231 (breast), and PSN-1 (pancreas) tumor cells.

The synthesis, characterization, crystal structure and detailed magnetic properties of a pyrazine (pyz) and azido (N 3 ) bridged cobalt(II) compound of formula [Co(N 3 ) 2 (pyz)] (1) are reported. Compound 1 shows a layered structure formed by Co(II) chains with double μ-N 3 (κN 1 ,N 1 ) bridges that are further connected by μ-(pyrazine-κN 1 ,N 4 ) bridges. The layers present weak van der Waals interactions between azido terminal groups. The magnetic properties show the presence of a metamagnetic behaviour in 1 with two critical fields of 200 and 400 mT at low temperatures. AC magnetic measurements show the presence of a long-range 2D ferromagnetic order at T c ≈ 8.0-7.0 K for dc fields above 200 mT and a long-range 3D ferromagnetic order at T c ≈ 4.5 K for dc fields above 400 mT.

A wide range of protein acyl modifications has been identified on enzymes across various metabolic processes; however, the impact of these modifications remains poorly understood. Protein glutarylation is a recently identified modification that can be nonenzymatically driven by glutaryl-CoA. In mammalian systems, this unique metabolite is only produced in the lysine and tryptophan oxidative pathways. To better understand the biology of protein glutarylation, we studied the relationship between enzymes within the lysine/tryptophan catabolic pathways, protein glutarylation, and regulation by the deglutarylating enzyme sirtuin 5 (SIRT5). Here, we identify glutarylation on the lysine oxidation pathway enzyme glutaryl-CoA dehydrogenase (GCDH) and show increased GCDH glutarylation when glutaryl-CoA production is stimulated by lysine catabolism. Our data reveal that glutarylation of GCDH impacts its function, ultimately decreasing lysine oxidation. We also demonstrate the ability of SIRT5 to deglutarylate GCDH, restoring its enzymatic activity. Finally, metabolomic and bioinformatic analyses indicate an expanded role for SIRT5 in regulating amino acid metabolism. Together, these data support a feedback loop model within the lysine/tryptophan oxidation pathway in which glutaryl-CoA is produced, in turn inhibiting GCDH function via glutaryl modification of GCDH lysine residues and can be relieved by SIRT5 deacylation activity., Competing Interests: Conflict of interest The authors declare that they have no conflicts of interest with the contents of this article., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

The level of detail attained in the computational description of reaction mechanisms can be vastly improved through tools for automated chemical space exploration, particularly for systems of small to medium size. Under this approach, the unimolecular decomposition landscape for indole was explored through the automated reaction mechanism discovery program AutoMeKin. Nevertheless, the sheer complexity of the obtained mechanisms might be a hindrance regarding their chemical interpretation. In this spirit, the new Python library amk-tools has been designed to read and manipulate complex reaction networks, greatly simplifying their overall analysis. The package provides interactive dashboards featuring visualizations of the network, the three-dimensional (3D) molecular structures and vibrational normal modes of all chemical species, and the corresponding energy profiles for selected pathways. The combination of the joined mechanism generation and postprocessing workflow with the rich chemistry of indole decomposition enabled us to find new details of the reaction (obtained at the CCSD(T)/aug-cc-pVTZ//M06-2X/MG3S level of theory) that were not reported before: (i) 16 pathways leading to the formation of HCN and NH 3 (via amino radical); (ii) a barrierless reaction between methylene radical and phenyl isocyanide, which might be an operative mechanism under the conditions of the interstellar medium; and (iii) reaction channels leading to both hydrogen cyanide and hydrogen isocyanide, of potential astrochemical interest as the computed HNC/HCN ratios greatly exceed the calculated equilibrium value at very low temperatures. The reported reaction networks can be very valuable to supplement databases of kinetic data, which is of remarkable interest for pyrolysis and astrochemical studies., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The reactions of N-sulfonylhydrazones derived from cyclic ketones with γ-azidopropylboronic acid and 2-(azidomethyl)phenylboronic acid give rise to spirocyclic pyrrolidines and spiroisoindolines, respectively. The reactions proceed without the need of any transition-metal catalyst through a domino process that comprises the formation of a Csp 3 -C and a Csp 3 -N bond of the former hydrazonic carbon. The scope of the reaction has been explored by the preparation of over 50 examples of NH-unprotected spirocyclic derivatives. Importantly, this methodology could be applied for the preparation of alkaloid steroids from steroid N-tosylhydrazones., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

This study aimed to encapsulate and characterise a potential anti-tuberculosis copper complex (CuCl 2 (INH) 2 .H 2 O: I1 ) into polymeric nanoparticles (PNs) of polymethacrylate copolymers (Eudragit®, Eu) developed by nanoprecipitation method. NE30D, S100 and, E100 polymers were tested. The physicochemical characterisations were performed by DLS, TEM, FTIR, encapsulation efficiency and, in vitro release studies. Encapsulation of I1 in PN-NE30D, PN-E100, and PN-S100 was 26.3%, 94.5%, 22.6%, respectively. The particle size and zeta potentials were 82.3 nm and -24.5 mV for PNs-NE30D, 304.4 nm and +18.7 mV for PNs-E100, and 517.9 nm and -6.9 mV for PNs-S100, respectively. All PDIs were under 0.5. The formulations showed an I1 controlled release at alkaline pH with 29.7% from PNs-NE30D, 7.9% from PNs-E100 and, 28.1% from PNs-S100 at 1 h incubation. PNs were stable for at least 3 months. Particularly, PNs-NE30D demonstrated moderate inhibition of M. tuberculosis and low cytotoxic activity. None of the PNs induced mutagenicity.

Type 2 diabetes mellitus (T2DM) is one of the most prevalent chronic metabolic diseases of the 21st century. Nevertheless, its prevalence might be attenuated by taking advantage of bioactive compounds commonly found in fruits and vegetables. This work is focused on the recovery of polyphenols and polysaccharide-polyphenol conjugates from grape pomace for T2DM management and prevention. Bioactives were extracted by solid-liquid extraction and by pressurized hot water extraction (PHWE). Polyphenolic fraction recovered by PHWE showed the highest value for total phenolic content (427 μg GAE.mg -1 ), mainly anthocyanins and proanthocyanidins, and higher antioxidant activity compared to the fraction recovered by solid-liquid extraction. Polysaccharide-polyphenol conjugates comprehended pectic polysaccharides to which approximately 108 μg GAE of phenolic compounds (per mg fraction) were estimated to be bound. Polyphenols and polysaccharide-polyphenol conjugates exhibited distinct antidiabetic effects, depending on the extraction methodologies employed. Extracts were particularly relevant in the inhibition of a-glucosidase activity, with free polyphenols showing an IC 50 of 0.47 μg.mL -1 while conjugates showed an IC 50 of 2.7, 4.0 and 5.2 μg.mL -1 (solid-liquid extraction, PHWE at 95 and 120 °C, respectively). Antiglycation effect was more pronounced for free polyphenols recovered by PHWE, while the attenuation of glucose uptake by Caco-2 monolayers was more efficient for conjugates obtained by PHWE. The antidiabetic effect of grape pomace bioactives opens new opportunities for the exploitation of these agri-food wastes in food nutrition, the next step towards reaching a circular economy in grape products.

The enhancement of catalysts efficiency of bimetallic nanoparticles depends on the ability to exert control over surface composition. However, results relating surface composition and feeding solution of bimetallic nanoparticles synthesized in microemulsions are controversial and apparently contradictory. In order to comprehend how the resulting surface can be modified under different synthesis conditions and for different pairs of metals, a computer simulation study was carried out. The resulting surface compositions are explained based on the relative rates of deposition of the two metals, which depend on the particular metal pair, the concentration of reactants and the microemulsion composition. This study provides a satisfactory understanding of experimental results and allows us to identify the main factors affecting the nanoparticle's surface composition. Consequently, concrete and practical guidelines can be established to facilitate the experimental synthesis of bimetallic nanoparticles with tailored surfaces., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier Inc. All rights reserved.)

Chitosan has garnered much interest due to its properties and possible applications. Every year the number of publications and patents based on this polymer increase. Chitosan exhibits poor solubility in neutral and basic media, limiting its use in such conditions. Another serious obstacle is directly related to its natural origin. Chitosan is not a single polymer with a defined structure but a family of molecules with differences in their composition, size, and monomer distribution. These properties have a fundamental effect on the biological and technological performance of the polymer. Moreover, some of the biological properties claimed are discrete. In this review, we discuss how chitosan chemistry can solve the problems related to its poor solubility and can boost the polymer properties. We focus on some of the main biological properties of chitosan and the relationship with the physicochemical properties of the polymer. Then, we review two polymer applications related to green processes: the use of chitosan in the green synthesis of metallic nanoparticles and its use as support for biocatalysts. Finally, we briefly describe how making use of the technological properties of chitosan makes it possible to develop a variety of systems for drug delivery.

Phenolics are size products present in tons concentrations in industrial wastewater that can cause adverse health effects when released in the environment. As such, there is a growing interest in the development of efficient strategies for the removal of phenolic compounds from polluted water. Herein we describe the use of poly(3,4-ethylenedioxythiophene) (PEDOT)-Au/peroxidase micromotors as dynamic biocatalytic platforms for the removal of model phenolics (phenol, bisphenol A, guaiacol, pyrogallol and catechol). Micromotors are synthetized by using a simplified template electrodeposition protocol followed by covalent enzyme immobilization in the inner Au layer. Kinetic parameters revealed that enzyme immobilization in the inner micromotor layer increased over 2-fold the enzymatic activity, along with increasing operational pH and thermal stabilities. The micromotors can propel at speed of up to 60 µm/s, generating an enhanced fluid mixing that results in removal efficiencies of up to 60% as compared with the 27% removal when using free peroxidase under the same conditions. In addition, excellent activities of almost 100% were obtained within ten cycles of removal using the micromotors. This newly developed bioremediation strategy holds considerable promise in for its application in large scale water treatment systems and many relevant environmental processes., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Wigner's friend scenarios involve an Observer, or Observers, measuring a Friend, or Friends, who themselves make quantum measurements. In recent discussions, it has been suggested that quantum mechanics may not always be able to provide a consistent account of a situation involving two Observers and two Friends. We investigate this problem by invoking the basic rules of quantum mechanics as outlined by Feynman in the well-known " Feynman Lectures on Physics ". We show here that these "Feynman rules" constrain the a priori assumptions which can be made in generalised Wigner's friend scenarios, because the existence of the probabilities of interest ultimately depends on the availability of physical evidence (material records) of the system's past. With these constraints obeyed, a non-ambiguous and consistent account of all measurement outcomes is obtained for all agents, taking part in various Wigner's Friend scenarios.

A new series of 3-aryl-4-(N-aryl)aminocoumarins was synthesized in two steps starting from the natural product 4-hydroxycoumarin using the photoredox catalysis for the key step. These conditions reactions allowed to make CC bonds is up to 95% yields in mild conditions, easy operation, in an environmentally benign way, and are compatible with several patterns of substitution. The biological activity of the new compounds was tested in vitro against MCF-7, MDA-MB-231, and CCD-1072Sk cancer cell lines, as soon as to promastigotes and intracellular amastigotes of Leishmania amazonensis. Compounds 17d, 17s and 17x showed activity against promastigote forms (IC 50  = 5.96 ± 3.210, 9.05 ± 2.855 and 5.65 ± 2.078 μM respectively), and compound 17x presented the best activity against L. amazonensis amastigote intracellular form (IC 50  = 9.6 ± 1.148 μM), no BALB/c peritoneal macrophage cytotoxicity at assayed concentrations (CC 50  > 600 μM), and high selectivity to parasites over the mammalian cells (Selectivity Index > 62.2). There was no expressive activity for the cancer cell lines. Single crystal X-ray diffraction analysis was employed for structural elucidation of compounds 17a and 17s. In silico analyses of physicochemical, pharmacokinetic, and toxicological properties suggest that compound 17x is a potential candidate for anti-leishmaniasis drugs., (Copyright © 2021 Elsevier Inc. All rights reserved.)

The so far poorly understood factors controlling the complete meta-selectivity observed in the C-H activation reactions of alkylarenes promoted by aluminyl anions have been explored in detail by means of Density Functional Theory calculations. To this end, a combination of state-of-the-art computational methods, namely the activation strain model of reactivity and energy decomposition analysis, has been applied to quantitatively unveil the origin of the selectivity of the transformation as well as the influence of the associated potassium cation. It is found that the selectivity takes place during the initial nucleophilic addition step where the key LP(Al)→π*(C=C) molecular orbital interaction is more stabilizing for the meta-pathway, which results in a stronger interaction between the reactants along the entire transformation., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Detection and removal of metal ion contaminants have attracted great interest due to the health risks that they represent for humans and wildlife. Among the proposed compounds developed for these purposes, thiourea derivatives have been shown as quite efficient chelating agents of metal cations and have been proposed for heavy metal ion removal and for components of high-selectivity sensors. Understanding the nature of metal-ionophore activity for these compounds is thus of high relevance. We present a theoretical study on the interaction between substituted thioureas and metal cations, namely, Cd 2+ , Hg 2+ , and Pb 2+ . Two substituent groups have been chosen: 2-furoyl and m -trifluoromethylphenyl. Combining density functional theory simulations with wave function analysis techniques, we study the nature of the metal-thiourea interaction and characterize the bonding properties. Here, it is shown how the N , N '-disubstituted derivative has a strong affinity for Hg 2+ , through cation-hydrogen interactions, due to its greater oxidizing capacity.

Urease is an enzyme associated with the degradation of urea, an important nitrogen fertilizer in agriculture. Thus, this current report describes the use of a paper-based analytical device (UrePAD) designed to contain a microzone array for colorimetric determination of urease activity in soils in the absence/presence of potential enzyme inhibitors. The UrePAD can be used at the point-of-need (point-of-care), and it offers advantages such as low cost, simplicity in handling, low sample/reagent volumes, and no use of toxic reagents. The acid-base indicator phenol red was used to monitor the urea hydrolysis reaction catalyzed by urease in the evaluated systems. The images were digitalized in a bench scanner, and the analysis was performed using Corel Draw X8 software. The device offered a LOD of 0.10 U mL -1 with linearity between 0.25 and 4.0 U mL -1 and a relative standard deviation ≤ 1.38%. UrePAD was tested in four soil samples of different characteristics and with eight urease inhibitors of varied classes. The results obtained through the proposed device did not differ statistically (95% confidence interval) from those employing the classic method based on the Berthelot reaction, thus indicating that UrePAD was effective for determining urease activity and screening inhibitors, besides showing the capacity to simplify fieldwork involving the application of urea in the soil., (Copyright © 2021 Elsevier B.V. All rights reserved.)