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121.
Vivian E. Cornelio Mariele M. Pedroso André S. Afonso João B. Fernandes M.Fátima G.F. da Silva Ronaldo C. Faria Paulo C. Vieira 《Analytica chimica acta》2015
The hemoglobin (Hb) released from erythrocytes is a primary nutritive component for many blood-feeding parasites. The aspartic protease cathepsin D is a hemoglobinase that is involved in the Hb degradation process and is considered an interesting target for chemotherapy intervention. However, traditional enzymatic assays for studying Hb degradation utilize spectrophotometric techniques, which do not allow real-time monitoring and can present serious interference problems. Herein, we describe a biosensor using simple approach for the real-time monitoring of Hb hydrolysis as well as an efficient screening method for natural products as enzymatic inhibitors using a quartz crystal microbalance (QCM) technique. Hemoglobin was anchored on the quartz crystal surface using mixed self-assembled monolayers. The addition of the enzyme caused a mass change (frequency shift) due to Hb hydrolysis, which was monitored in real time. From the frequency change patterns of the Hb-functionalized QCM, we evaluated the enzymatic reaction by determining the kinetic parameters of product formation (kcat). The QCM enzymatic assay using immobilized human Hb was shown to be an excellent approach for screening possible inhibitors in complex mixtures, opening up a new avenue for the discovery of novel inhibitors. 相似文献
122.
A Novel Alkaloid from Aspidosperma pyricollum (Apocynaceae) and Complete 1H and 13C Chemical Shift Assignments
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Hádria M. do Carmo Raimundo Braz‐Filho Ivo J. Curcino Vieira 《Helvetica chimica acta》2015,98(10):1381-1386
A novel natural product indole, alkaloid, named rel‐pyricolluminol ( 1 ), was isolated from Aspidosperma pyricollum Müll .Arg . together with six known metabolites sitsirikine ( 2 ), aparicin ( 3 ), ulein ( 4 ), stemmadenine ( 5 ), lupeol ( 6 ), and (3β)‐sitoster‐3‐yl β‐D ‐glucopyranoside ( 7 ). These compounds were characterized on the basis of their spectral data, mainly 1D‐ (1H,13C‐DEPTQ) and 2D‐NMR (1H,1H‐COSY, NOESY, HSQC, and HMBC), and mass spectra (EI‐MS and HR‐ES‐MS), involving also comparison with data from the literature. 相似文献
123.
João M. Leça Ana C. Pereira Ana C. Vieira Marco S. Reis José C. Marques 《Analytica chimica acta》2015
Vicinal diketones, namely diacetyl (DC) and pentanedione (PN), are compounds naturally found in beer that play a key role in the definition of its aroma. In lager beer, they are responsible for off-flavors (buttery flavor) and therefore their presence and quantification is of paramount importance to beer producers. Aiming at developing an accurate quantitative monitoring scheme to follow these off-flavor compounds during beer production and in the final product, the head space solid-phase microextraction (HS-SPME) analytical procedure was tuned through experiments planned in an optimal way and the final settings were fully validated. Optimal design of experiments (O-DOE) is a computational, statistically-oriented approach for designing experiences that are most informative according to a well-defined criterion. This methodology was applied for HS-SPME optimization, leading to the following optimal extraction conditions for the quantification of VDK: use a CAR/PDMS fiber, 5 ml of samples in 20 ml vial, 5 min of pre-incubation time followed by 25 min of extraction at 30 °C, with agitation. The validation of the final analytical methodology was performed using a matrix-matched calibration, in order to minimize matrix effects. The following key features were obtained: linearity (R2 > 0.999, both for diacetyl and 2,3-pentanedione), high sensitivity (LOD of 0.92 μg L−1 and 2.80 μg L−1, and LOQ of 3.30 μg L−1 and 10.01 μg L−1, for diacetyl and 2,3-pentanedione, respectively), recoveries of approximately 100% and suitable precision (repeatability and reproducibility lower than 3% and 7.5%, respectively). The applicability of the methodology was fully confirmed through an independent analysis of several beer samples, with analyte concentrations ranging from 4 to 200 g L−1. 相似文献
124.
Gabriela Furlan Giordano Luis Carlos Silveira Vieira Angelo Luiz Gobbi Renato Sousa Lima Lauro Tatsuo Kubota 《Analytica chimica acta》2015
An integrated platform was developed for point-of-use determination of ethanol in sugar cane fermentation broths. Such analysis is important because ethanol reduces its fuel production efficiency by altering the alcoholic fermentation step when in excess. The custom-designed platform integrates gas diffusion separation with voltammetric detection in a single analysis module. The detector relied on a Ni(OH)2-modified electrode. It was stabilized by uniformly depositing cobalt and cadmium hydroxides as shown by XPS measurements. Such tests were in accordance with the hypothesis related to stabilization of the Ni(OH)2 structure by insertion of Co2+ and Cd2+ ions in this structure. The separation step, in turn, was based on a hydrophobic PTFE membrane, which separates the sample from receptor solution (electrolyte) where the electrodes were placed. Parameters of limit of detection and analytical sensitivity were estimated to be 0.2% v/v and 2.90 μA % (v/v)−1, respectively. Samples of fermentation broth were analyzed by both standard addition method and direct interpolation in saline medium based-analytical curve. In this case, the saline solution exhibited ionic strength similar to those of the samples intended to surpass the tonometry colligative effect of the samples over analyte concentration data by attributing the reduction in quantity of diffused ethanol vapor majorly to the electrolyte. The approach of analytical curve provided rapid, simple and accurate analysis, thus contributing for deployment of point-of-use technologies. All of the results were accurate with respect to those obtained by FTIR method at 95% confidence level. 相似文献
125.
M. Ferreira M. M. Rodrigues N. Vieira 《Mathematical Methods in the Applied Sciences》2017,40(18):7033-7050
In this work, we obtain the fundamental solution (FS) of the multidimensional time‐fractional telegraph Dirac operator where the 2 time‐fractional derivatives of orders α∈]0,1] and β∈]1,2] are in the Caputo sense. Explicit integral and series representation of the FS are obtained for any dimension. We present and discuss some plots of the FS for some particular values of the dimension and of the fractional parameters α and β. Finally, using the FS, we study some Poisson and Cauchy problems. 相似文献
126.
The interaction of bovine serum albumin (BSA) with the ionic surfactants sodium dodecylsulfate (SDS, anionic), cetyltrimethylammonium chloride (CTAC, cationic) and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS, zwitterionic) was studied by electron paramagnetic resonance (EPR) spectroscopy of spin label covalently bound to the single free thiol group of the protein. EPR spectra simulation allows to monitor the protein dynamics at the labeling site and to estimate the changes in standard Gibbs free energy, enthalpy and entropy for transferring the nitroxide side chain from the more motionally restricted to the less restricted component. Whereas SDS and CTAC showed similar increases in the dynamics of the protein backbone for all measured concentrations, HPS presented a smaller effect at concentrations above 1.5mM. At 10mM of surfactants and 0.15 mM BSA, the standard Gibbs free energy change was consistent with protein backbone conformations more expanded and exposed to the solvent as compared to the native protein, but with a less pronounced effect for HPS. In the presence of the surfactants, the enthalpy change, related to the energy required to dissociate the nitroxide side chain from the protein, was greater, suggesting a lower water activity. The nitroxide side chain also detected a higher viscosity environment in the vicinity of the paramagnetic probe induced by the addition of the surfactants. The results suggest that the surfactant-BSA interaction, at higher surfactant concentration, is affected by the affinities of the surfactant to its own micelles and micelle-like aggregates. Complementary DLS data suggests that the temperature induced changes monitored by the nitroxide probe reflects local changes in the vicinity of the single thiol group of Cys-34 BSA residue. 相似文献
127.
Di?go P. Bezerra Ronan S. Oliveira Rodrigo S. Vieira Célio L. Cavalcante Diana C. S. Azevedo 《Adsorption》2011,17(1):235-246
Adsorption may be a potentially attractive alternative to capturing CO2 from stationary sources in the context of Carbon Capture and Sequestration (CCS) technologies. Activated carbon and zeolites
are state-of-art adsorbents which may be used for CO2 adsorption, however physisorption alone tends to be insignificant at high temperatures. In the present work, commercial adsorbents
have been impregnated with monoethanolamine (MEA) and triethanolamine (TEA) in order to investigate the effect of the modified
surface chemistry on CO2 adsorption, especially above room temperature. Adsorption isotherms for CO2, N2 and CH4 were measured in a gravimetrically system in the pressure range of UHV to 10 bar, at 298 and 348 K for activated carbon and
zeolite 13X supports. The adsorbed concentration of CO2 was significantly higher than those of CH4 and N2 for both adsorbents in the whole pressure range studied, zeolite 13X showing a remarkable affinity for CO2 at very low pressures. However, at 348 K, the adsorbed concentration of CO2 decreases significantly. The supports impregnated with concentrated amine solutions and dried in air suffered a detrimental
effect on the textural properties, although CO2 uptake became much less susceptible to temperature increase. Impregnations carried out with dilute solution followed by drying
in inert atmosphere yielded materials with very similar textural characteristics as compared to the parent support. CO2 isotherms in such materials showed a significant change with similar capacities at 348 K as compared to the original support
at 298 K in the case of activated carbons. The impregnated zeolite showed a decrease in adsorbed phase concentration in low
pressures for a given temperature, but the adsorbed amount also seemed to be less affected by temperature. These results are
promising and indicate that CO2 adsorption may be enhanced despite high process temperatures (e.g. 348 K), if convenient impregnation and drying methods
are applied. 相似文献
128.
Börner J Vieira Idos S Pawlis A Döring A Kuckling D Herres-Pawlis S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(16):4507-4512
Zinc bis(chelate) guanidine complexes promote living lactide polymerization at elevated temperatures. By means of kinetic and spectroscopic analyses the mechanism has been elucidated for these special initiators that make use of neutral N-donor ligands. The neutral guanidine function initiates the polymerization by a nucleophilic ring-opening attack on the lactide molecule. DFT calculations on the first ring-opening step show that the guanidine is able to act as a nucleophile. Three transition states were located for ligand rearrangement, nucleophilic attack, and ring-opening. The second ring-opening step was modeled as a representation for the chain growth because here, the lactate alcoholate opens the second lactide molecule via two transition states (nucleophilic attack and ring-opening). Additionally, the resulting reaction profile proceeds overall exothermically, which is the driving force for the reaction. The experimental and calculated data are in good agreement and the presented mechanism explains why the polymerization proceeds without co-initiators. 相似文献
129.
Heparin Binding by Murine Recombinant Prion Protein Leads to Transient Aggregation and Formation of RNA-Resistant Species 总被引:1,自引:0,他引:1
Vieira TC Reynaldo DP Gomes MP Almeida MS Cordeiro Y Silva JL 《Journal of the American Chemical Society》2011,133(2):334-344
The conversion of cellular prion protein (PrP(C)) into the pathological conformer PrP(Sc) requires contact between both isoforms and probably also requires a cellular factor, such as a nucleic acid or a glycosaminoglycan (GAG). Little is known about the structural features implicit in the GAG-PrP interaction. In the present work, light scattering, fluorescence, circular dichroism, and nuclear magnetic resonance (NMR) spectroscopy were used to describe the chemical and physical properties of the murine recombinant PrP 23-231 interaction with low molecular weight heparin (LMWHep) at pH 7.4 and 5.5. LMWHep interacts with rPrP 23-231, thereby inducing transient aggregation. The interaction between murine rPrP and heparin at pH 5.5 had a stoichiometry of 2:1 (LMWHep:rPrP 23-231), in contrast to a 1:1 binding ratio at pH 7.4. At binding equilibrium, NMR spectra showed that rPrP complexed with LMWHep had the same general fold as that of the free protein, even though the binding can be indicated by significant changes in few residues of the C-terminal domain, especially at pH 5.5. Notably, the soluble LMWHep:rPrP complex prevented RNA-induced aggregation. We also investigated the interaction between LMWHep and the deletion mutants rPrP Δ51-90 and Δ32-121. Heparin did not bind these constructs at pH 7.4 but was able to interact at pH 5.5, indicating that this glycosaminoglycan binds the octapeptide repeat region at pH 7.4 but can also bind other regions of the protein at pH 5.5. The interaction at pH 5.5 was dependent on histidine residues of the murine rPrP 23-231. Depending on the cellular milieu, the PrP may expose different regions that can bind GAG. These results shed light on the role of GAGs in PrP conversion. The transient aggregation of PrP may explain why some GAGs have been reported to induce the conversion into the misfolded, scrapie conformation, whereas others are thought to protect against conversion. The acquired resistance of the complex against RNA-induced aggregation explains some of the unique properties of the PrP interaction with GAGs. 相似文献
130.