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1.
Carbohydr Polym ; 331: 121842, 2024 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-38388050

RESUMO

Chitosan has been extensively explored in food coatings. Still, its practical application is largely hampered by its conventional wet processing in acetic acid, whose residuals negatively impact food quality and safety. Here, we propose a new method to formulate chitosan coatings for food applications by avoiding organic acid processing and validate them on a cheese model. The procedure entails modifying a previously reported process based on HCl chitosan treatment and neutralising the resulting gel. The obtained chitosan is solubilised in water using carbonic acid that forms in situ by dissolving carbon dioxide gas. The reversibility of water carbonation allows for easy removal of carbonic acid residues, resulting in acid-free chitosan films and coatings. The performance of the coating was tested against state-of-the-art chitosan-based and polymeric coatings. We preliminarily characterised the films' properties (water stability, barrier, and optical properties). Then, we assessed the performance of the coating on Provolone cheese as a food model (mass transfer and texture profiles over 14 days). The work demonstrated the advantage of the proposed approach in solving some main issues of food quality and safety, paving the way for an effective application of chitosan in future food contact applications.


Assuntos
Queijo , Quitosana , Quitosana/química , Conservação de Alimentos/métodos , Ácido Carbônico , Água , Embalagem de Alimentos/métodos
2.
Mar Environ Res ; 192: 106219, 2023 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-37848362

RESUMO

Based on observations in China's east coastal oceans, we conducted a preliminary assessment of 16 sets of carbonic acid dissociation constants (K1* and K2*) by comparing spectrophotometrically measured pH values at 25 °C with those calculated from total alkalinity and dissolved inorganic carbon. We obtained that K1* and K2* often performed differently within different salinity ranges, and that the constants of Millero et al. (2002) (M02) demonstrated the best performance for the salinity range of 24-35. In contrast, the often recommended constants of Mehrbach et al. (1973) refit by Dickson and Millero (1987) (DM87-M) and Lucker et al. (2000) (L00) would underestimate pH at salinities of 24-30. This was mainly associated with the higher product of K1* and K2* by DM87-M and L00 than by M02 at this salinity range. Also, we found almost no differences between pH values calculated with DM87-M and L00.


Assuntos
Carbono , Ácido Carbônico , Oceanos e Mares , Carbono/análise , Salinidade , China
3.
Food Microbiol ; 115: 104324, 2023 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-37567633

RESUMO

In dairy industry, filamentous fungi are used as adjunct cultures in fermented products for their technological properties but they could also be responsible for food spoilage and mycotoxin production. The consumer demands about free-preservative products has increased in recent years and lead to develop alternative methods for food preservation. Modified Atmosphere Packaging (MAP) can inhibit fungal growth and therefore increase the food product shelf-life. This study aimed to evaluate radial growth as a function of CO2 and more particularly carbonic acid for fourteen adjuncts and/or fungal spoiler isolated from dairy products or dairy environment by using predictive mycology tools. The impact of the different chemical species linked to CO2 (notably carbonic acid) were study because it was reported previously that undissociated carbonic acid impacted bacterial growth and bicarbonates ions were involved in modifications of physiological process of fungal cells. A significant diversity in the responses of selected strains was observed. Mucor circinelloides had the fastest growth rates (µ > 11 mm. day-1) while Bisifusarium domesticum, Cladosporium herbarum and Penicillium bialowiezense had the slowest growth rates (µ < 1 mm. day-1). Independently of the medium pH, the majority of strains were sensitive to total carbonic acid. In this case, it was not possible to conclude if CO2 active form was gaseous or aqueous so modeling were performed as a function of CO2 percentage. Only Geotrichum candidum and M. circinelloides strains were sensitive to undissociated carbonic acid. Among the fourteen strains, P. bialowiezense was the less sensitive strain to CO2, no growth was observed at 50% of CO2 only for this strain. M. lanceolatus was the less sensitive strain to CO2, the CO250 which reduce the growth rates by 50% was estimated at 138% of CO2. Low CO2 percentage improved the growth of Penicillium expansum, Penicillium roqueforti and Paecilomyces niveus. Mathematical models (without and with optimum) were suggested to describe the impact of CO2 percentage or undissociated carbonic acid concentration on fungal growth rate.


Assuntos
Dióxido de Carbono , Ácido Carbônico , Dióxido de Carbono/farmacologia , Fungos , Laticínios/microbiologia , Conservação de Alimentos/métodos
4.
J Phys Chem A ; 127(2): 489-494, 2023 Jan 19.
Artigo em Inglês | MEDLINE | ID: mdl-36622286

RESUMO

Nonminimum carbonic acid clusters provide excitation energies and oscillator strengths in line with observed ice-phase UV absorptions better than traditional optimized minima. This equation-of-motion coupled cluster quantum chemical analysis on carbonic acid monomers and dimers shows that shifts to the dihedral angle for the internal heavy atoms in the monomer produce UV electronic excitations close to 200 nm with oscillator strengths that would produce observable features. This τ(OCOO) dihedral is actually a relatively floppy motion unlike what is often expected for sp2 carbons and can be distorted by 30° away from equilibrium for an energy cost of only 11 kcal/mol. As this dihedral decreases beyond 30°, the excitation energies decrease further. The oscillator strengths do, as well, but only to a point. Hence, the lower-energy distortions of τ(OCOO) are sufficient to produce structures that exhibit excitation energies and oscillator strengths that would red-shift observed spectra of carbonic acid ices away from the highest UV absorption feature at 139 nm. Such data imply that colder temperatures (20 K) in the experimental treatment of carbonic acid ices are freezing these structures out after annealing, whereas the warmer temperature experiments (80 K) are not.


Assuntos
Ácido Carbônico , Ácido Carbônico/química , Temperatura
5.
Int J Biol Macromol ; 222(Pt B): 2761-2774, 2022 Dec 01.
Artigo em Inglês | MEDLINE | ID: mdl-36252623

RESUMO

The tightly bonded shielding coating on biomatrix significantly enhances the functionality of medical devices, bioprostheses in particular. In our work we have obtained a polyelectrolyte coating on a biomatrix by sequentially depositing chitosan and hyaluronic acid (HA) from solutions in carbonic acid under pressure. This approach makes it possible to obtain hybrid biomatrix with a firmly bonded polymer screen due to the electrostatic bonding of polyions. High-precision analysis using a tritium label shows a 3-fold increase in quantity of HA in carbonic acid under pressure compared to the conventional method. The presence of the chitosan layer increases the HA adsorption by 15-20 % due to electrostatic interaction of differently charged polymers. Antimicrobial results show the possibility of implementing an induced antimicrobial response, due to the lysis of the upper layer of the coating (HA) and the release of antimicrobial agents in the case of growth of pathogens on the bioprosthesis.


Assuntos
Anti-Infecciosos , Quitosana , Ácido Hialurônico , Ácido Carbônico , Polieletrólitos , Anti-Infecciosos/farmacologia , Antibacterianos/farmacologia , Valvas Cardíacas , Carbono
6.
Toxicology ; 480: 153334, 2022 10.
Artigo em Inglês | MEDLINE | ID: mdl-36122607

RESUMO

Placenta contains 3ß-hydroxysteroid dehydrogenase/steroid Δ5,4-isomerase (HSD3B), which catalyzes pregnenolone to progesterone for maintaining pregnancy. Perfluoroalkyl carbonic acids (PFC) are subclass of perfluoroalkyl substances containing 4-14 carbons (C4-C14) in the carbon backbone and are potential endocrine disruptors. Whether PFC inhibit HSD3B and structure-activity relationship (SAR) remains unclear. Herein, we screened 11 PFC for inhibiting human type I HSD3B (HSD3B1) and rat type IV HSD3B (HSD3B4) activities and determined SAR and mode of inhibition. HSD3B was measured by converting pregnenolone to progesterone assisted by NAD+ in placental microsomes. Of the 11 PFC, C9-C14 significantly inhibited human HSD3B1 activity at 100 µM. Half-maximal inhibitory concentration (IC50) values of C9-C14 compounds were 363.56 ± 12.14, 12.78 ± 0.69, 6.54 ± 0.65, 20.88 ± 0.41, 118.35 ± 0.16, and 149.26 ± 21.67 µM, respectively. We determined Ki values and mode of inhibition of three most potent PFC (C10-C12), and found that they were mixed inhibitors against pregnenolone, with Ki values of 5.57 ± 4.37, 2.04 ± 2.26, and 9.93 ± 7.71, respectively. Docking analysis showed that they bound steroid-binding site. Effects of PFC on rat placental HSD3B4 were performed. Of the 11 PFC, C10-C12 significantly inhibited rat HSD3B4 activity at 100 µM. IC50 values of C10-C12 compounds were 45.85 ± 1.49, 36.08 ± 1.50, and 88.74 ± 1.99 µM, respectively. Ki values and inhibition modes of the three most potent PFC (C10-C12) were studied. It was found that they were mixed inhibitors against pregnenolone, with Ki values of 48.16 ± 20.44, 36.28 ± 53.07, and 91.79 ± 21.75 µM, respectively. Docking analysis showed that they bound steroid-binding site of rat HSD3B4. In conclusion, PFC showed significant SAR differences. The potency of inhibiting HSD3B activity increased from C9 to C11, and then declined. Human HSD3B1 was more sensitive to the inhibition of rat HSD3B4.


Assuntos
Disruptores Endócrinos , Fluorocarbonos , 3-Hidroxiesteroide Desidrogenases/metabolismo , Animais , Carbono/metabolismo , Ácido Carbônico , Disruptores Endócrinos/metabolismo , Feminino , Fluorocarbonos/metabolismo , Fluorocarbonos/toxicidade , Humanos , Isomerases/metabolismo , Isomerases/farmacologia , Complexos Multienzimáticos , NAD/metabolismo , Placenta/metabolismo , Gravidez , Pregnenolona/metabolismo , Pregnenolona/farmacologia , Progesterona , Ratos , Relação Estrutura-Atividade
7.
Bioorg Med Chem ; 72: 117000, 2022 10 15.
Artigo em Inglês | MEDLINE | ID: mdl-36095944

RESUMO

Vanillic acid has always been in high-demand in pharmaceutical, cosmetic, food, flavor, alcohol and polymer industries. Present study achieved highly pure synthesis of vanillic acid from vanillin using whole cells of Ochrobactrum anthropi strain T5_1. The complete biotransformation of vanillin (2 g/L) in to vanillic acid (2.2 g/L) with 95 % yield was achieved in single step in 7 h, whereas 5 g/L vanillin was converted to vanillic acid in 31 h. The vanillic acid thus produced was validated using LC-MS, GC-MS, FTIR and NMR. Further, vanillic acid was evaluated for in vitro anti-tyrosinase and cytotoxic properties on B16F1 skin cell line in dose dependent manner with IC50 values of 15.84 mM and 9.24 mM respectively. The in silico Swiss target study predicted carbonic acid anhydrase IX and XII as key targets of vanillic acid inside the B16F1 skin cell line and revealed the possible mechanism underlying cell toxicity. Molecular docking indicated a strong linkage between vanillic acid and tyrosinase through four hydrogen and several hydrophobic bonds, with ΔG of -3.36 kJ/mol and Ki of 3.46 mM. The bioavailability of vanillic acid was confirmed by the Swiss ADME study with no violation of Lipinski's five rules.


Assuntos
Ochrobactrum anthropi , Ácido Vanílico , Benzaldeídos/metabolismo , Benzaldeídos/farmacologia , Ácido Carbônico , Hidrogênio , Simulação de Acoplamento Molecular , Ochrobactrum anthropi/metabolismo , Preparações Farmacêuticas , Polímeros , Ácido Vanílico/metabolismo , Ácido Vanílico/farmacologia
8.
J Phys Chem A ; 126(23): 3739-3744, 2022 Jun 16.
Artigo em Inglês | MEDLINE | ID: mdl-35671440

RESUMO

Two theoretical structural motifs are proposed to match two experimental solid carbonic acid UV spectra from previous literature ( Astron. Astrophys. 2021, 646, A172): a linear ribbon structure as a single octamer and nonplanar orientations of carbonic acid clusters. The latter have some contribution from approximated amorphous solid carbonic acid in the form of 40 different clusters of 8 carbonic acid molecules ensemble-averaged together, but unoptimized pairs of optimized dimers oriented perpendicular to one another give the strongest intensities of lower energy UV transitions. The linear ribbon structure's predicted spectrum computed with CAM-B3LYP/6-311G(d,p) agrees well with Experimental Solid B─the ß-carbonic acid experimental data in the UV region. Meanwhile, the 40 amorphous clusters are built with a randomization script, and the electronically excited states are calculated with both CAM-B3LYP/6-311G(d,p) and ωB97XD/6-311G(d,p). The resulting theoretical spectrum is constructed by employing a Boltzmann distribution of the intensities and artificially broadening the simulated spectra. The nonplanar dimer pairs are computed with CAM-B3LYP and B3LYP with the 6-311G(d,p) basis set. The results of the amorphous simulation weakly correspond with the Experimental Solid A spectrum, but the fully nonplanar motif matches the experiment much more convincingly. As a result, the previous work appears to have observed the traditional crystalline phase of solid carbonic acid in Experimental Solid B, whereas the nonplanar orientations of the carbonic acids in the clusters appear to correlate with Experimental Solid A. This spectral classification will aid in future laboratory work exploring the role that carbonic acid can play in low temperature, low pressure desorbed environments with potential application to astrochemistry.


Assuntos
Ácido Carbônico , Análise Espectral Raman , Simulação por Computador , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Análise Espectral Raman/métodos , Temperatura
9.
Int J Biol Macromol ; 209(Pt B): 1629-1637, 2022 Jun 01.
Artigo em Inglês | MEDLINE | ID: mdl-35447270

RESUMO

Effective degradation of chitosan to D-glucosamine is considered to make a great contribution for the development of the medical industry. To address this issue, a porous carbon-based solid acid catalyst (PCSA) functionalized with -OH, -COOH and -SO3H groups was successfully prepared. Typically, the physicochemical properties of PCSA were deeply determined by a series of characterization technique including FT-IR, TGA, RM, NH3-TPD, SEM and Element Analysis. Moreover, the catalytic performances of PCSA towards to D-glucosamine production from chitosan were evaluated. In particular, the effects of catalyst acid density, ratio of acidic groups, chitosan concentration, reaction temperature, reaction time and catalyst dosage on the yield of D-glucosamine were investigated in detail. Interestingly, the experimental results indicated that a yield of D-glucosamine as high as 90.5% was achieved, and no obvious deactivation occurred even after six consecutive cycles. In light of the advantages of superior activity/recyclability and low cost, the starch-derived solid acid developed in this work might possess the broad industrial application prospects.


Assuntos
Quitosana , Carbono/química , Ácido Carbônico , Quitosana/química , Glucosamina/química , Porosidade , Espectroscopia de Infravermelho com Transformada de Fourier , Amido
10.
Water Res ; 210: 117988, 2022 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-34959066

RESUMO

Drinking water disinfection by chlorination or chloramination can result in the formation of disinfection byproducts (DBPs) such as haloacetic acids (HAAs) and trihalomethanes (THMs). Pyrogenic carbonaceous matter (PCM), such as activated carbon (AC), is commonly used as an ostensibly inert adsorbent to remove HAAs from water. HAA degradation has been mainly attributed to biological factors. This study, for the first time, revealed that abiotic HAA degradation in the presence of PCM could be important under water treatment conditions. Specifically, we observed complete destruction of Br3AA, a model HAA, in the presence of powder AC at pH 7 within 30 min. To understand the role of PCM and the reaction mechanism, we performed a systematic study using a suite of HAAs and various PCM types. We found that PCM significantly accelerated the transformation of three HAAs (Br3AA, BrCl2AA, Br2ClAA) at pH 7. Product characterization indicated an approximately 1:1 HAA molar transformation into their respective THMs following a decarboxylation pathway with PCM. The Br3AA activation energy (Ea) was measured by kinetic experiments at 15-45 °C with and without a model PCM, wherein a significant decrease in Ea from 25.7 ± 3.2 to 13.6 ± 2.2 kcal•mol-1 was observed. We further demonstrated that oxygenated functional groups on PCM (e.g., -COOH) can accelerate HAA decarboxylation using synthesized polymers to resemble PCM. Density functional theory simulations were performed to determine the enthalpy of activation (ΔH‡) for Br3AA decarboxylation with H3O+ and formic acid (HCOOH). The presence of HCOOH significantly lowered the overall ΔH‡ value for Br3AA decarboxylation, supporting the hypothesis that -COOH catalyzes the C-C bond breaking in Br3AA. Overall, our study demonstrated the importance of a previously overlooked abiotic reaction pathway, where HAAs can be quickly converted to THMs with PCM under water treatment relevant conditions. These findings have substantial implications for DBP mitigation in water quality control, particularly for potable water reuse or pre-chlorinated water that allow direct contact between HAAs and AC during filtration as well as PAC fines traveling with finished water in water distribution systems. As such, the volatilization and relative low toxicity of volatile THMs may be considered as a detoxification process to mitigate adverse DBP effects in drinking water, thereby lowering potential health risks to consumers.


Assuntos
Água Potável , Poluentes Químicos da Água , Ácido Carbônico , Descarboxilação , Trialometanos/análise , Poluentes Químicos da Água/análise
11.
J Phys Chem B ; 125(41): 11473-11490, 2021 10 21.
Artigo em Inglês | MEDLINE | ID: mdl-34623157

RESUMO

Protonation of the strong base methylamine CH3NH2 by carbonic acid H2CO3 in aqueous solution, HOCOOH···NH2CH3 → HOCOO-···+HNH2CH3, has been previously studied ( J. Phys. Chem. B 2016, 109, 2271-2280; J. Phys. Chem. B 2016, 109, 2281-2290) via Car-Parinnello molecular dynamics. This proton transfer (PT) reaction within a hydrogen (H)-bonded complex was found to be barrierless and very rapid, with key reaction coordinates comprising the proton coordinate, the H-bond separation RON, and a solvent coordinate, reflecting the water solvent rearrangement involved in the neutral to ion pair conversion. In the present work, the reaction's charge flow aspects are analyzed in detail, especially a description via Mulliken charge transfer for PT (MCTPT). A natural bond orbital analysis and some extensions of them are employed for the complex's electronic structure during the reaction trajectories. Results demonstrate that consistent with the MCTPT picture, the charge transfer (CT) occurs from a methylamine base nonbonding orbital to a carbonic acid antibonding orbital. A complementary MCTPT reaction product perspective of CT from the antibonding orbital of the HN+ moiety to the nonbonding orbital of the oxygen in the H-bond complex is also presented. σOH and σHN+ bond order expressions show this CT to occur within the H-bond OHN triad, an aspect key for simultaneous bond-breaking and -forming in the PT reaction.


Assuntos
Ácido Carbônico , Prótons , Elétrons , Solventes , Água
12.
Chemistry ; 27(65): 16112-16116, 2021 Nov 22.
Artigo em Inglês | MEDLINE | ID: mdl-34542205

RESUMO

The carboarylation reaction of biphenyl-alkynes was successfully triggered by electrophilic attack of 1,1-bis(triflyl)ethylene on the alkyne moiety to give polycyclic aromatic hydrocarbons (PAHs) decorated by superacidic carbon acid functionality. Neutralisation of thus obtained acids with NaHCO3 yielded the corresponding sodium salts, which showed improved solubility in both aqueous and organic solvents.


Assuntos
Hidrocarbonetos Policíclicos Aromáticos , Alcinos , Carbono , Ácido Carbônico , Ciclização
13.
Chemistry ; 27(45): 11618-11626, 2021 Aug 11.
Artigo em Inglês | MEDLINE | ID: mdl-34076322

RESUMO

The heterolytic decomposition of tert-butyl peroxyformate to tert-butanol and carbon dioxide, catalyzed by pyridine, is a long-known example of a reaction whose kinetics are strongly affected by solvent polarity. From DFT and ab initio methods together with the SMD implicit solvation model, an extension on the formerly accepted mechanism is proposed. This novel proposal involves the formation of a carbonic acid ester intermediate and its further decomposition, through an unreported pyridine-mediated stepwise route. Computed barriers for this mechanism at DLPNO/CCSD(T)-def2-TZVP are in excellent agreement with experimental kinetic data across different solvents. Furthermore, the strong relationships between activation energies, geometric parameters in the transition state and the characteristics of the different solvents are also analyzed in depth.


Assuntos
Ácido Carbônico , Cinética , Solventes
14.
Eur Phys J E Soft Matter ; 44(3): 41, 2021 Mar 23.
Artigo em Inglês | MEDLINE | ID: mdl-33759011

RESUMO

pH gradient-driven modular micro-swimmers are investigated as a model for a large variety of quasi-two-dimensional chemi-phoretic self-propelled entities. Using three-channel micro-photometry, we obtain a precise large field mapping of pH at a spatial resolution of a few microns and a pH resolution of [Formula: see text] units for swimmers of different velocities propelling on two differently charged substrates. We model our results in terms of solutions of the three-dimensional advection-diffusion equation for a 1:1 electrolyte, i.e. carbonic acid, which is produced by ion exchange and consumed by equilibration with dissolved [Formula: see text]. We demonstrate the dependence of gradient shape and steepness on swimmer speed, diffusivity of chemicals, as well as the fuel budget. Moreover, we experimentally observe a subtle, but significant feedback of the swimmer's immediate environment in terms of a substrate charge-mediated solvent convection. We discuss our findings in view of different recent results from other micro-fluidic or active matter investigations. We anticipate that they are relevant for quantitative modelling and targeted applications of diffusio-phoretic flows in general and artificial micro-swimmers in particular.


Assuntos
Ácido Carbônico/farmacologia , Meio Ambiente , Movimento/efeitos dos fármacos , Concentração de Íons de Hidrogênio , Natação
15.
Carbohydr Polym ; 258: 117614, 2021 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-33593532

RESUMO

The functionalization of the bacterial cellulose (BC) surface with a chitosan biopolymer to expand the areas of possible applications of the modified BC is an important scientific task. The creation of such composites in the carbonic acid solutions that were performed in this work has several advantages in terms of being biocompatible and eco-friendly. Quantitative analysis of chitosan content in the composite was conducted by tritium-labeled chitosan radioactivity detection method and this showed three times increased chitosan loading. Different physicochemical methods showed successful incorporation of chitosan into the BC matrix and interaction with it through hydrogen bonds. Microscopy results showed that the chitosan coating with a thickness of around 10 nm was formed in the bulk of BC, covering each microfibril. It was found that the inner specific surface area increased 1.5 times on deposition of chitosan from the solutions in carbonic acid.


Assuntos
Bactérias/metabolismo , Dióxido de Carbono/química , Ácido Carbônico/química , Celulose/química , Quitosana/química , Materiais Biocompatíveis/química , Biopolímeros/química , Química Verde , Microscopia Eletrônica de Varredura , Nanopartículas/química , Pressão , Espectroscopia de Infravermelho com Transformada de Fourier , Termogravimetria , Engenharia Tecidual/métodos , Trítio/química , Difração de Raios X
16.
Environ Sci Pollut Res Int ; 28(17): 21285-21302, 2021 May.
Artigo em Inglês | MEDLINE | ID: mdl-33411290

RESUMO

Residues of açaí seeds (Euterpe oleracea Mart.) were a novel source for the synthesis of the acid heterogeneous catalyst applied in the conversion of low free fatty acid waste cooking oil (WCO) to biodiesel. Yield of activated carbon (AC) and catalyst (CAT), as well as density of SO3H groups and total acidity, was analyzed in an entirely random designed experiment using multiple linear regression, one-way ANOVA, and Tukey's post hoc test. Time, temperature, dosage of KOH, and ratio of H2SO4/AC were the predictor variables with 3 levels each, at a significance level of α = .05. A significant yield variation portion of AC was explained by the experimental factors (R2 = .891, F (3, 23) = 62.9, p < .0001), as did the yield of CAT (R2 = .960, F (3, 23) = 185.7, p < .0001), density of SO3H (R2 = .969, F (3, 23) = 242.2, p < .0001), and total acidity (R2 = .973, F (3, 23) = 280.6, p < .0001). Levels of time (p = .001) and KOH dosage (p = .006) were significant to the yield of AC, and temperature levels were not influent on density of SO3H (p = .731) or total acidity (p = .762). CAT showed a SBET of 249 m2 g-1, Vpore of 0.104 cm3 g-1, low crystallinity, high thermal stability, and a mesoporous amorphous structure. Optimized catalytic tests resulted in 89% conversion of WCO and 11 cycles of reuse, better than pure H2SO4 or pure KOH (p < .0001) and also better than many biomass-derived catalysts reported in the literature.


Assuntos
Euterpe , Biocombustíveis/análise , Brasil , Ácido Carbônico , Catálise , Culinária , Esterificação , Ácidos Graxos não Esterificados , Óleos de Plantas
18.
Biochemistry ; 59(33): 3026-3037, 2020 08 25.
Artigo em Inglês | MEDLINE | ID: mdl-32786399

RESUMO

Boronic acids have been successfully employed as inhibitors of hydrolytic enzymes. Typically, an enzymatic nucleophile catalyzing hydrolysis adds to the electrophilic boron atom forming a tetrahedral species that mimics the intermediate(s)/transition state(s) for the hydrolysis reaction. We show that para-substituted phenylboronic acids (PBAs) are potent competitive inhibitors of mandelate racemase (MR), an enzyme that catalyzes a 1,1-proton transfer rather than a hydrolysis reaction. The Ki value for PBA was 1.8 ± 0.1 µM, and p-Cl-PBA exhibited the most potent inhibition (Ki = 81 ± 4 nM), exceeding the binding affinity of the substrate by ∼4 orders of magnitude. Isothermal titration calorimetric studies with the wild-type, K166M, and H297N MR variants indicated that, of the two Brønsted acid-base catalysts Lys 166 and His 297, the former made the greater contribution to inhibitor binding. The X-ray crystal structure of the MR·PBA complex revealed the presence of multiple H-bonds between the boronic acid hydroxyl groups and the side chains of active site residues, as well as formation of a His 297 Nε2-B dative bond. The dramatic upfield change in chemical shift of 27.2 ppm in the solution-phase 11B nuclear magnetic resonance spectrum accompanying binding of PBA by MR was consistent with an sp3-hybridized boron, which was also supported by density-functional theory calculations. These unprecedented findings suggest that, beyond substituting boron at carbon centers participating in hydrolysis reactions, substitution of boron at the acidic carbon center of a substrate furnishes a new approach for generating inhibitors of enzymes catalyzing the deprotonation of carbon acid substrates.


Assuntos
Boro/farmacologia , Ácidos Borônicos/farmacologia , Racemases e Epimerases/antagonistas & inibidores , Substituição de Aminoácidos , Sítios de Ligação/efeitos dos fármacos , Boro/química , Ácidos Borônicos/farmacocinética , Carbono/química , Carbono/farmacocinética , Carbono/farmacologia , Ácido Carbônico/química , Ácido Carbônico/farmacologia , Catálise/efeitos dos fármacos , Domínio Catalítico/efeitos dos fármacos , Cinética , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Mutagênese Sítio-Dirigida , Racemases e Epimerases/genética , Racemases e Epimerases/metabolismo , Estereoisomerismo , Relação Estrutura-Atividade , Especificidade por Substrato
19.
Molecules ; 25(14)2020 Jul 21.
Artigo em Inglês | MEDLINE | ID: mdl-32708283

RESUMO

This review gives an overview of current trends in the investigation of small guest molecules, confined in neat and functionalized mesoporous silica materials by a combination of solid-state NMR and relaxometry with other physico-chemical techniques. The reported guest molecules are water, small alcohols, and carbonic acids, small aromatic and heteroaromatic molecules, ionic liquids, and surfactants. They are taken as characteristic role-models, which are representatives for the typical classes of organic molecules. It is shown that this combination delivers unique insights into the structure, arrangement, dynamics, guest-host interactions, and the binding sites in these confined systems, and is probably the most powerful analytical technique to probe these systems.


Assuntos
Dióxido de Silício/química , Álcoois/química , Ácido Carbônico/química , Hidrocarbonetos Aromáticos/química , Líquidos Iônicos/química , Espectroscopia de Ressonância Magnética , Simulação de Dinâmica Molecular , Estrutura Molecular , Porosidade , Tensoativos/química , Água/química
20.
J Physiol Anthropol ; 39(1): 2, 2020 Feb 04.
Artigo em Inglês | MEDLINE | ID: mdl-32019602

RESUMO

BACKGROUND: This study examined the effects of immersion in stirred, high-concentration, artificial carbonic acid water on body cooling. METHODS: Seven healthy male students (23 ± 2 years old) participated in the experiment. Signed informed consent was obtained from all subjects before the experiment. The subjects changed into shorts and T-shirts and entered an experimental room (with room temperature controlled at 30 °C and relative humidity maintained at 70%) at least 30 min before starting the experiment. After starting the experiment, the subjects were asked to rest on an exercise bike for 5 min and then pedal for 20 min. The exercise load was set to reach 50% of each subject's presumed maximum oxygen intake at 5 min after starting exercise. Subjects then continued pedaling for 1 min to cool down. After this exercise, subjects sat on a chair and immersed forearms in tap water or artificial carbonic acid water (CO2 water) at 25 °C for 20 min. During immersion, tap water or CO2 water was stirred slowly with a pump. After immersion, subjects rested for 10 min. Skin temperature and skin blood flow (left forearm), as well as heart rate and ear canal temperature, were measured continuously. Thermal sensation and thermal comfort were measured intermittently. RESULTS: Skin blood flow of the immersed forearms was higher in CO2 water than in tap water during immersion. The blood flow in the last 5 min (average at rest was 100%) was significantly higher in CO2 water (290.85 ± 84.81%) than in tap water (104.80 ± 21.99%). Thermal sensation and thermal comfort were not different between conditions. Ear canal temperature significantly declined more in CO2 water (- 0.56 ± 0.31 °C) than in tap water (- 0.48 ± 0.30 °C) during immersion. CONCLUSIONS: Our study suggests that immersion of the forearms in slowly stirred CO2 water at 25 °C reduces core temperature elevated by heat stress or exercise more effectively than does tap water at the same temperature. Immersion of the forearms in stirred CO2 water at 25 °C could be useful as a preventive measure against heat stroke from summer work or exercise.


Assuntos
Temperatura Corporal/fisiologia , Ácido Carbônico , Temperatura Baixa , Antebraço/fisiologia , Adulto , Crioterapia , Golpe de Calor , Humanos , Masculino , Pele/irrigação sanguínea , Adulto Jovem
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