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1.
Haq Nawaz Paulo A. R. Pires Thaís A. Bioni Elizabeth P. G. Arêas Omar A. El Seoud 《Cellulose (London, England)》2014,21(3):1193-1204
Rate constants for the acetylation of microcrystalline cellulose (MCC), by ethanoic anhydride in the presence of increasing concentrations of the ionic liquid (IL), 1-allyl-3-methylimidazolium chloride in dipolar aprotic solvents (DAS), N,N-dimethylacetamide (DMAC), and acetonitrile (MeCN), have been calculated from conductivity data. The third order rate constants showed a linear dependence on [IL]. We explain this result by assuming that the reacting cellulose is hydrogen-bonded to the IL. This is corroborated by kinetic data of the acetylation of cyclohexylmethanol, FTIR of the latter compound and of cellobiose in mixtures of IL/DAS, and conductivity of the binary solvent mixtures in absence, and presence of MCC. Cellulose acetylation is faster in IL/DMAC than in IL/MeCN; this difference is explained based on solvatochromic data (empirical polarity and basicity) and molecular dynamics simulations. Results of the latter indicate hydrogen-bond formation between the hydroxyl groups of the anhydroglucose unit of MCC, (Cl?) of the IL, and the dipole of the DMAC. Under identical experimental conditions, acetylation in IL/DMAC is faster than that in LiCl/DMAC (2.7–8 times), due to differences in the enthalpies and entropies of activation. 相似文献
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This work was focused on the influence of the morphology of composite natural rubber (NR)-based particles on the toughness of poly(styrene–co-acrylonitrile) (PSAN) blends. In order to be suitable for the reinforcement of PSAN blends, the NR-based particles were coated with a shell of crosslinked poly(methylmethacrylate) (PMMA). Furthermore, polystyrene (PS) subinclusions were introduced into the NR rubber core. PSAN blends were prepared by adding the wet latex directly into a twin screw-extruder. This new method allowed even tacky pure rubber particles to be dispersed as shown by transmission electron photomicrographs which confirmed the integrity of the soft particles after mixing. Solid NR particles or NR-based latex particles containing rigid PS subinclusions and no hard shell did not offer any impact improvement to PSAN. Only NR-based core–shell particles containing at least 25% PMMA in the shell toughened the brittle matrix. Prevulcanized NR-based latex particles which do not cavitate easily were less effective. Core–shell particles containing PS subinclusions within a natural rubber core allowed more effective use of the rubber phase. From the fracture surface morphology the failure mechanisms of PSAN blends containing the different composite NR particles could be deduced. Monodisperse poly(n-butylacrylate)-based core–shell particles were too small to toughen PSAN. However, a similar dependence of the fracture mechanisms on the morphology of the incorporated toughening agent could be established by scanning electron microscopy. 相似文献
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In conformational analysis, the systematic search method completely maps the space but suffers from the combinatorial explosion problem because the number of conformations increases exponentially with the number of free rotation angles. This study introduces a new methodology of conformational analysis that controls the combinatorial explosion. It is based on a dimensional reduction of the system through the use of principal component analysis. The results are exactly the same as those obtained for the complete search but, in this case, the number of conformations increases only quadratically with the number of free rotation angles. The method is applied to a series of three drugs: omeprazole, pantoprazole, lansoprazole-benzimidazoles that suppress gastric-acid secretion by means of H+, K+-ATPase enzyme inhibition. 相似文献
4.
Given two maps
h : X ×K ? \mathbbR{h : X \times K \rightarrow \mathbb{R}} and g : X → K such that, for all x ? X, h(x, g(x)) = 0{x \in X, h(x, g(x)) = 0} , we consider the equilibrium problem of finding [(x)\tilde] ? X{\tilde{x} \in X} such that h([(x)\tilde], g(x)) 3 0{h(\tilde{x}, g(x)) \geq 0} for every x ? X{x \in X} . This question is related to a coincidence problem. 相似文献
5.
Silla JM Cormanich RA Duarte CJ Freitas MP Ramalho TC Barbosa TM Santos FP Tormena CF Rittner R 《The journal of physical chemistry. A》2011,115(35):10122-10127
Suitable (3)J(H,H) coupling constants and theoretical calculations were used to define the conformational preferences of trans-2-bromoalkoxycyclohexanes (alkoxy = OMe, OEt, O(i)Pr, and O(t)Bu) for the isolated molecule and as a function of the medium. The diaxial conformer was preponderant, or at least similarly populated to the diequatorial form, for the tert-butoxy derivative only, while the diequatorial conformer was prevalent for the remaining alkoxy derivatives (except for the OMe derivative in CCl(4) solution). The conformational behavior of these compounds was analyzed on the basis of classical steric effects and attractive electron delocalizations, by means of natural bond orbital analysis. 相似文献
6.
Luís O. de B. Benetoli Henrique de Santana Cássia Thaïs B. V. Zaia Dimas A. M. Zaia 《Monatshefte für Chemie / Chemical Monthly》2008,139(7):753-761
In the present paper, the adsorption of nucleic acid bases (A, adenine; C, cytosine; U, uracil; and T, thymine) on clays (bentonite, kaolinite, and montmorillonite) was studied at different pH (2.00 and 7.20). It should be pointed out there is no reported study of adsorption of nucleic acid bases on clays using seawater
(with the major elements), and a wide range of pH. The main finding of this study was that the ratio of A and T adsorbed on clays ranged from 4.68 to 25.1, much higher than the ratio of their occurrence in organisms ranging from 0.95
to 1.05. The weaker adsorption of U and T on clays raises the question of the possibility of a genetic code based on purines only. The FT-IR spectra at pH 2.00 showed that the interaction of A, C, T, and U with the clays occurs through positively charged, protonated groups.
Correspondence: Dr. Dimas A. M. Zaia, Departamento de Química-CCE, Universidade Estadual de Londrina, 86051-990 Londrina-PR,
Brazil. 相似文献
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MSPD procedure for determining buprofezin,tetradifon, vinclozolin,and bifenthrin residues in propolis by gas chromatography–mass spectrometry 总被引:1,自引:0,他引:1
dos Santos TF Aquino A Dórea HS Navickiene S 《Analytical and bioanalytical chemistry》2008,390(5):1425-1430
A simple and effective extraction method based on matrix solid-phase dispersion (MSPD) was developed to determine bifenthrin,
buprofezin, tetradifon, and vinclozolin in propolis using gas chromatography–mass spectrometry in selected ion monitoring
mode (GC–MS, SIM). Different method conditions were evaluated, for example type of solid phase (C18, alumina, silica, and Florisil), the amount of solid phase and eluent (n-hexane, dichloromethane, dichloromethane–n-hexane (8:2 and 1:1, v/v) and dichloromethane–ethyl acetate (9:1, 8:2 and 7:3, v/v)). The best results were obtained using 0.5 g propolis, 1.0 g silica as dispersant sorbent, 1.0 g Florisil as clean-up sorbent,
and dichloromethane–ethyl acetate (9:1, v/v) as eluting solvent. The method was validated by analysis of propolis samples fortified at different concentration levels
(0.25 to 1.0 mg kg−1). Average recoveries (four replicates) ranged from 67% to 175% with relative standard deviation between 5.6% and 12.1%. Detection
and quantification limits ranged from 0.05 to 0.10 mg kg−1 and 0.15 to 0.25 mg kg−1 propolis, respectively. 相似文献
10.
Priscila I. Soares Thaís M. Lima Luiza. A. do Nascimento Rafael M. Coelho Diego L. Franco Arnaldo C. Pereira Lucas F. Ferreira 《Electroanalysis》2023,35(5):e202200302
Caffeic acid (CA)-modified graphite electrodes [GE/poly(CA)] was applied to the co-detection of copper and lead in artisanal sugarcane spirit using square-wave anodic stripping voltammetry (SWASV). Electrochemical and morphological studies were performed, and a mechanism for polymerization was proposed. Electropolymerization, SWASV, and analysis conditions parameters were optimized. Interferents, repeatability, reproducibility, and addition and recovery tests were carried out. GE/poly(CA) shows a linear range from 15 to 705 μg/L with a limit of detection of 3.01 μg/L for Pb(II) and 4.50 μg/L for Cu(II). Real samples of artisanal sugarcane spirit were used, and the electrochemical results were compared with atomic absorption spectroscopy experiments. 相似文献