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排序方式: 共有193条查询结果,搜索用时 15 毫秒
1.
Giuseppina Castronuovo Vittorio Elia Filomena Velleca 《Journal of solution chemistry》1995,24(12):1209-1217
Calorimetric measurements were carried out at 25°C on binary and ternary aqueous solutions containing L and D forms fo the following -aminoacids: tryptophan, cysteine, methionine, phenylalanine, histidine, threonine, and citrulline, which contain both hydrophilic and hydrophobic domains. Differences were found between the values of the homochiral and heterochiral pairwise enthalpic interaction coefficients for tryptophan, cysteine, and methionine. To the contrary, chiral recognition was not detected for phenylalanine, histidine, citrulline, and threonine. The data were interpreted in terms of a preferential configuration model. Chiral recognition is detected only when the interactions of the side chains in the homo- and heterochiral configurations are different. Chiral recognition disappears when a competition exists between zwitterion-zwitterion interactions and side chain-side chain interactions. In some cases, such as for citrulline, compensation effects can occur due to thermal contributions from different domains which mask chiral recognition. 相似文献
2.
Giuseppina Castronuovo Vittorio Elia Marcella Niccoli Filomena Velleca 《Thermochimica Acta》1998,320(1-2):13-22
The thermodynamics of dissolution in water of a set of substances has been studied calorimetrically. The examined substances were: potassium chloride, (glycyl-glycyl)diketopiperazine, (alanyl-alanyl)diketopiperazine, (leucyl-glycyl)diketopiperazine. They were chosen on the basis of their solubilities, going from a highly soluble electrolyte to the sparingly soluble diketopiperazines. It is shown that, using a commercially available calorimeter, it is possible to perform in a single calorimetric experiment the simultaneous determination of all thermodynamic parameters characterizing dissolution of a substance in a given solvent, i.e. solubility, dissolution enthalpy and dilution enthalpy. The solubility values in water obtained through the proposed method are in good agreement with those reported in the literature and obtained by other techniques. 相似文献
3.
Ruben Elvas-Leito Filomena Martins Leonor Borbinha Catarina Marranita Angela Martins Nelson Nunes 《Molecules (Basel, Switzerland)》2020,25(23)
Attempts to optimize heterogeneous catalysis often lack quantitative comparative analysis. The use of kinetic modelling leads to rate (k) and relative sorption equilibrium constants (K), which can be further rationalized using Quantitative Structure-Property Relationships (QSPR) based on Multiple Linear Regressions (MLR). Friedel-Crafts acylation using commercial and hierarchical BEA zeolites as heterogeneous catalysts, acetic anhydride as the acylating agent, and a set of seven substrates with different sizes and chemical functionalities were herein studied. Catalytic results were correlated with the physicochemical properties of substrates and catalysts. From this analysis, a robust set of equations was obtained allowing inferences about the dominant factors governing the processes. Not entirely surprising, the rate and sorption equilibrium constants were found to be explained in part by common factors but of opposite signs: higher and stronger adsorption forces increase reaction rates, but they also make the zeolite active sites less accessible to new reactant molecules. The most relevant parameters are related to the substrates’ molecular size, which can be associated with different reaction steps, namely accessibility to micropores, diffusion capacity, and polarizability of molecules. The relatively large set of substrates used here reinforces previous findings and brings further insights into the factors that hamper/speed up Friedel-Crafts reactions in heterogeneous media. 相似文献
4.
Pedro Miguel Lima M. Filomena Teodoro Neville J. Ford Patricia M. Lumb 《Numerical Algorithms》2010,55(2-3):301-320
This paper is devoted to the approximate solution of a linear first-order functional differential equation which involves delayed and advanced arguments. We seek a solution x, defined for t?∈?(0, k???1],(k?∈?IN ), which takes given values on the intervals [???1, 0] and (k???1, k]. Continuing the work started in previous articles on this subject, we introduce and analyse a computational algorithm based on the finite element method for the solution of this problem which is applicable both in the case of constant and variable coefficients. Numerical results are presented and compared with the results obtained by other methods. 相似文献
5.
The effect of the quenching rate on the phase separation of partially miscible liquid mixtures is studied, showing that it may influence the growth rate of single-phase domains. In particular, the phase separation of metastable binary mixtures in the presence of strong emulsifiers appears to be heavily retarded. These effects constitute an important limitation to the phase transition extraction process introduced by the authors in previous works, which is based on the fact that phase separation of unstable mixtures is rapid, even in the presence of surface active compounds. 相似文献
6.
Amandine Aftalion Filomena Pacella 《Transactions of the American Mathematical Society》2004,356(11):4255-4272
We study the positive radial solutions of the Dirichlet problem in , 0$"> in , on , where , 1$">, is the -Laplace operator, is the unit ball in centered at the origin and is a function. We are able to get results on the spectrum of the linearized operator in a suitable weighted space of radial functions and derive from this information on the Morse index. In particular, we show that positive radial solutions of Mountain Pass type have Morse index 1 in the subspace of radial functions of . We use this to prove uniqueness and nondegeneracy of positive radial solutions when is of the type and .
7.
8.
Zotti M Schiavone S Tricarico F Colaianna M D'Apolito O Paglia G Corso G Trabace L 《Journal of separation science》2008,31(13):2511-2515
Nitric oxide (NO) is one of the most important mediators and neurotransmitters and its levels change under pathological conditions. NO production may be regulated by endogenous nitric oxide synthase (NOS) inhibitors, in particular asymmetric dimethylarginine (ADMA). Most of the interest is focused on ADMA, since this compound is present in plasma and urine and accumulation of ADMA has been described in many disease states but little is known about cerebrospinal fluid (CSF) concentrations of this compound and of its structural isomer symmetric dimethylarginine (SDMA). To determine the levels of methylarginines, we here present a new hydrophilic interaction chromatography (HILIC)-MS/MS method for the precise determination of these substances in CSF from microdialysis samples of rat prefrontal cortex (PFC). The method requires only minimal sample preparation and features isotope-labelled internal standards. 相似文献
9.
Low-frequency internal motions in protein molecules play a key role in biological functions. A direct relationship between low-frequency motions and enzymatic activity has been suggested for bovine pancreatic ribonuclease (RNase A). The flexibility-function relationship in this enzyme has been attributed to a subtle and concerted breathing motion of the beta-sheet regions occurring upon substrate binding and release. Here, we calculate an approximate value for the force constant and the wave number of the low-frequency beta-sheet breathing motion of RNase A, by using the Boltzmann hypothesis on a set of data derived from a simple conventional structural superimposition of an unusual large number of X-ray structures available for the protein. The results agree with previous observations and with theoretical predictions on the basis of normal-mode analysis. To the best of our knowledge, this is the first example in which the wave number and the force constant of a low-frequency concerted motion in a protein are directly derived from X-ray structures. 相似文献
10.
M. Gra?a Dias M. Filomena Cam?es Luísa Oliveira 《Accreditation and quality assurance》2012,17(2):183-189
For consistent interpretation of an analytical method result it is necessary to evaluate the confidence that can be placed
in it, in the form of a measurement uncertainty estimate. The Guide to the expression of Uncertainty in Measurement issued
by ISO establishes rules for evaluating and expressing uncertainty. Carotenoid determination in food is a complex analytical
process involving several mass transfer steps (extraction, evaporation, saponification, etc.), making difficult the application
of these guidelines. The ISO guide was interpreted for analytical chemistry by EURACHEM, which includes the possibility of
using intra- and interlaboratory information. Measurement uncertainty was estimated based on laboratory validation data, including
precision and method performance studies, and also, based on laboratory participation in proficiency tests. These methods
of uncertainty estimation were applied to analytical results of different food matrices of fruits and vegetables. Measurement
uncertainty of food carotenoid determination was 10–30% of the composition value in the great majority of cases. Higher values
were found for measurements near instrumental quantification limits (e.g. 75% for β-cryptoxanthin, and 99% for lutein, in
pear) or when sample chromatograms presented interferences with the analyte peak (e.g. 44% for α-carotene in orange). Lower
relative expanded measurement uncertainty values (3–13%) were obtained for food matrices/analytes not requiring the saponification
step. Based on these results, the saponification step should be avoided if food carotenoids are not present in the ester form.
Food carotenoid content should be expressed taking into account the measurement uncertainty; therefore the maximum number
of significant figures of a result should be 2. 相似文献