The hydrolysis reactions of several title esters in water at 60 degrees C follow the rate law k(obs) = (k(a) + k(b)[OH(-)])/(1 + a(H)/K(a)), where K(a) is the ionization constant of the hydroxy group of the ester and k(b) is the second-order rate constant for the S(N)2(S) attack of hydroxide ion on the ionized ester. Hammett and Br?nsted correlations are consistent with a previous proposal that the mechanism related to k(a) is dissociative. An unusual relationship between k(a) values and redox equilibrium constants for substituted quinones is found to hold: this finding further supports the dissociative nature of the pathway related to k(a). 相似文献
A flow injection system was proposed to evaluate the transient product of a colorimetric reaction between hydrolysable tannin and potassium iodate (KIO3) solution. The system optimization was accomplished by using statistical methods based on experimental design. Flow rate of KIO3 solution, sample volume, carrier flow rate, and reaction coil were the selected factors for evaluation. On screening step, complete factorial 24 was used and two levels for each selected factor were studied. For the optimization phase, a centered face composite design 22 + star was employed to evaluate sample volume and flow rate of KIO3 solution, which were the factors identified in the screening phase as having more influence on the absorbance signal. After optimization, the proposed system was compared with batch determination. Some characteristics, such as analytical frequency, reagent consumption and chemical residues generation presented better results by the use of the proposed system if compared with batch method. The system presented good repeatability with standard deviation lower than 3%, for n = 10, linearity (R2 = 0.9974) for tannic acid standard, analytical frequency of 15 injections h− 1 and limit of quantification of 24 mg L− 1 of tannic acid. Good results were obtained when the proposed system was applied to hydrolysable tannin determination in Stryphnodendron barbatimão, Eucalyptus citriodora and Phyllanthus niruri, samples of plants commonly used in popular medicine. 相似文献
We present a macroscopic model for the spreading and rupture of a spherical lipid vesicle on a flat, isotropic, hydrophilic surface. Formulas for the free energy of the initial and final states are derived, and the details of spreading pathways are examined. We show that the activation barrier for vesicle rupture is too large to be overcome by thermal fluctuations at room temperature and the final configuration is more likely to consist of a deflated vesicle. In order for the vesicle to rupture into a planar bilayer, it would have to be aided by increased temperature, application of an external force, or preparation of a mixed hydrophilic/ hydrophobic surface. 相似文献
The influence of the acid catalyst concentration on the structural evolution of a sol-gel system was studied by doping TEOS
based starting solutions with two fluorescent probes: a polystyrene chain (Mn=1700) and a much shorter alkane chain (M=172), both of them labeled at both ends with 1-pyrenyl. For this purpose, each probe was incorporated in two TEOS∶H2O∶C2H5OH mixtures (molar ratios 1∶4∶1), one at pH 1.2 and the other at pH 2.5 (respectively below and above the isoelectric point
of silica). Very low concentrations of the probes were used (≤10−6M), so the pyrene dimmers and excimers were formed only intramolecularly. The ratios of excimer to monomer fluorescence intensities
at excitation wavelength of 360 nm (where mainly the ground state pyrene dimmers are excited) were studied as a function of
time. Different evolutions of these ratios were observed, which allowed us to predict that the silica structure developsvia the formation of primary particles, even at pH values below the isoelectric point of silica, where it is not possible to
directly detect their formation. 相似文献
The positive ion chemical ionization (CI (isobutane)), negative ion chemical ionization (NICI) electron attachment (CH4, He) and NICI (OH?) spectra of the title compounds have been studied in detail with the aid of deuterium-labelled derivatives. The obtained results show that under CI conditions the stereospecificity is retained. Interesting correlations with the condensed phase epimerization yields are emphasized. 相似文献
The reaction of [Rh(micro-Cl)(COD)]2 with 4,6-dimethyl-pyrimidinethiolate (Me2-pymt) and subsequent substitution of COD by CO yields [Rh(Me2-pymt)(CO)2]. The stacking pattern found in this compound is in contradiction with previously studied comparable square-planar complexes of type d8-[M(chelate)(monodentate)2] in which each ligand has different pi-acidic character. A theoretical study of the intermolecular interactions and conformation of the title compound has been carried out, combining semi-empirical band calculations on the real chains and ab initio(MP2 level) calculations on a model dimer. The combination of electronic and steric effects determines the rotation of the successive monomers and the deviation from linearity of the one-dimensional stacks. Its behaviour in solution is also special, developing a blue colour and forming micelles, when adding water to acetone solutions. 相似文献
The use of rice husks as an alternative adsorbent in an on-line preconcentration system for Cd (II) and Pb (II) determination by flame atomic absorption spectrometry (FAAS) is described. The potential of rice husks as a natural adsorbent was evaluated as a material modified with 0.75 mol l−1 NaOH solution and in the unmodified form. For this task, several techniques such as spectroscopy and thermogravimetry were used for elucidation of possible functional groups responsible for the uptake of Cd (II) and Pb (II). Furthermore, based on adsorption studies and adsorption isotherms applied to the Langmüir model, it was possible to verify that modified rice husks present a higher adsorption capacity for both metals. After establishing this material as a promising natural adsorbent, it was used for on-line preconcentration of Cd (II) and Pb (II) metals. The multivariate optimisation of chemical and flow variables was performed by using a full factorial design (24) including the following factors: preconcentration time, preconcentration flow rate, concentration and volume of eluent. The optimum pH values used for on-line preconcentration were taken from prior univariate experiments. Under optimised conditions for Cd (II) determination (4 min of preconcentration at a 6 ml min−1 preconcentration flow rate, in which comprises 24 ml of preconcentration volume, 200 μl elution volume and 1.0 mol l−1 HNO3 solution as eluent), the system achieved a detection limit of 1.14 μg l−1 and an enrichment factor of 72.4. Similar conditions were used for Pb (II) determination (4 min of preconcentration, 6 ml min−1 preconcentration flow rate, 300 μl elution volume and 1.0 mol l−1 HNO3 solution as eluent) from which a detection limit of 14.1 μg l−1 and enrichment factor of 46.0 were achieved. Also, rice husks have been shown to be a homogeneous and stable adsorbent in which more than 100 preconcentration/elution cycles provide a relative standard deviation (RSD) of less than 6.0% on the analytical signal. The satisfactory accuracy of the method developed was obtained by using spiked water samples (mineral water and lake water) and spiked red wine samples. These values were confirmed by electrothermal atomic absorption spectrometry (ETAAS). The certified reference material [pig kidney (CRM 186)] and the reference material [beech leaves (CRM 100)] were also used. 相似文献
Novel chiral 2′-pyridinyl alcohols derived from isopropylidene-protected carbohydrates are reported. They show different characteristics at the hydroxy group, but are all suitable ligands for chiral molybdenum(VI) complexes of the type MoO2L2 (L = chiral 2′-pyridinyl alcoholate). MoO2(acac)2 served as starting material in the complex syntheses. The structure of one ligand and one dioxo complex were exemplary established by X-ray crystallography. For catalytic runs in the enantioselective epoxidation catalysis trans-methylstyrene was used as model substrate, tert-butylhydroperoxide and cumolhydroperoxide, resp., as the oxidant. 相似文献
Sulfite is often added to beverages as an antioxidant and antimicrobial agent. In fermented beverages, sulfite is also naturally produced by yeast cells. However, sulfite causes adverse health effects in asthmatic patients and accurate measurement of the sulfite concentration is therefore very important. Current sulfite analysis methods are time- and reagent-consuming and often require costly equipment. Here, we present a system allowing sensitive, ultralow-volume sulfite measurements based on a reusable glass-silicon microdroplet platform on which microdroplet generation, addition of enzymes through chemical-induced emulsion destabilization and pillar-induced droplet merging, emulsion restabilization, droplet incubation, and fluorescence measurements are integrated. In a first step, we developed and verified a fluorescence-based enzymatic assay for sulfite by measuring its analytical performance (LOD, LOQ, the dynamic working range, and the influence of salts, colorant, and sugars) and comparing fluorescent microplate readouts of fermentation samples with standard colorimetric measurements using the 5,5′-dithiobis-(2-nitrobenzoic acid) assay of the standard Gallery Plus Beermaster analysis platform. Next, samples were analyzed on the microdroplet platform, which also showed good correlation with the standard colorimetric analysis. Although the presented platform does not allow stable reinjection of droplets due to the presence of a tight array of micropillars at the fluidics entrances to prevent channel clogging by dust, removing the pillars, and integrating miniaturized pumps and optics in a future design would allow to use this platform for high-throughput, automated, and portable screening of microbes, plant, or mammalian cells.