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901.
A theozyme for antibody aldolases has been studied at the MP2/6-31G** computational level. Formation of two cooperative hydrogen-bonds between the acidic hydrogen atoms of the enamine and of a methanol molecule with the oxygen atom of the aldol acceptor markedly favors the C-C bond-formation associated with the aldol reaction. A comparative analysis of the geometry, the charge distribution and the shape of the molecular electrostatic potential of the transition structure (TS) with the covalent adduct, resulting from the reaction of methylamine and the beta-diketone used as a hapten allows us to characterize the transition-state analogue (TSA) generated at immunization. This finding allows us to propose a hapten based on a chiral beta-ketosulfoxide that could give the formation of a TSA that addresses the tetrahedral geometry of the TS. 相似文献
902.
Silva MM Vale MG Damin IC Welz B Mandaji M Fett JP 《Analytical and bioanalytical chemistry》2003,377(1):165-172
The amount of sample that is available for analysis in laboratory plant cultivation experiments is usually very limited. Highly sensitive analytical techniques are therefore required, even for elements that are present in the plants at mg g–1 concentrations, and graphite furnace atomic absorption spectrometry (GFAAS) was chosen in this work because of its micro-sampling capability, and its relatively simple operation. Four micro-methods were investigated for the determination of iron in roots and leaves of rice plants: i) a micro-digestion with nitric and hydrochloric acids, ii) a slurry procedure using tetramethylammonium hydroxide (TMAH) tissue solubilizer, iii) a slurry prepared in 1.4 mol L–1 nitric acid, and treated in an ultrasonic bath, and iv) the direct analysis of solid samples. The micro-digestion was suffering from high blank values and contamination problems, so that it could not be recommended for routine purposes. The TMAH method exhibited poor precision and occasional low recoveries, particularly for real samples. Direct solid sampling analysis gave results similar to those obtained with the slurry technique with ultrasonic agitation for the determination of iron in certified reference materials with iron content up to about 100 g g–1, but was too sensitive for the investigated rice plants, which had an iron content up to several mg g–1. The slurry technique with ultrasonic treatment of the samples, suspended in dilute nitric acid, was finally adopted as the method of choice.The method was then applied for the determination of iron in the leaves and in different compartments of the roots of two rice cultivars, one sensitive to iron toxicity, an important nutritional disorder, and the other one resistant to iron toxicity. The results suggest that the higher resistance to iron toxicity of the second cultivar is due to a smaller uptake of iron from the soil, resulting in lower iron levels in all compartments of the plant. 相似文献
903.
The expression of results with an uncertainty through the "bottom-up" approach, involving the estimation and combination of all the sources of uncertainty, represents a challenge when the analytical method includes mass transfer steps (MTS). These steps (e.g. extraction, evaporation, digestion, etc.) with inherently different from 100% recoveries lack models capable of describing their precision and efficiency. Recently, a new methodology was published aimed at the estimation of the performance of these critical steps. Comparison of the experimental dispersion from the replicated analysis of spiked samples with the combination of the uncertainty associated with gravimetric, volumetric and instrumental quantification steps (described by well established models) allows the estimation of the MTS uncertainty. Evaluation of the behaviour of the MTS within the analytical range supports the use of developed estimations over a wide concentration range. This methodology was applied, with success, to the determination of pesticide residues in melon in one particular proficiency test organised by the Food Analysis Performance Assessment Scheme (FAPAS) between November 2000 and February 2001. 相似文献
904.
Hervás C Toledo R Silva M 《Journal of chemical information and computer sciences》2001,41(4):1083-1092
The suitability of pruned computational neural networks (CNNs) for resolving nonlinear multicomponent systems involving synergistic effects by use of oscillating chemical reaction-based methods implemented using the analyte pulse perturbation technique is demonstrated. The CNN input data used for this purpose are estimates provided by the Levenberg-Marquardt method in the form of a three-parameter Gaussian curve associated with the singular profile obtained when the oscillating system is perturbed by an analyte mixture. The performance of the proposed method was assessed by applying it to the resolution of mixtures of pyrogallol and gallic acid based on their perturbating effect on a classical oscillating chemical system, viz. the Belousov-Zhabotinskyi reaction. A straightforward network topology (3:3:2, with 18 connections after pruning) allowed the resolution of mixtures of the two analytes in concentration ratios from 1:7 to 6:2 with a standard error of prediction for the testing set of 4.01 and 8.98% for pyrogallol and gallic acid, respectively. The reduced dimensions of the selected CNN architecture allowed a mathematical transformation of the input vector into the output one that can be easily implemented via software. Finally, the suitability of response surface analysis as an alternative to CNNs was also tested. The results were poor (relative errors were high), which confirms that properly selected pruned CNNs are effective tools for solving the analytical problem addressed in this work. 相似文献
905.
906.
D. Stauffer A. Aharony L. da Fontoura Costa J. Adler 《The European Physical Journal B - Condensed Matter and Complex Systems》2003,32(3):395-399
Neural networks are supposed to recognise blurred images (or patterns) of N pixels (bits) each. Application of the network to an initial blurred version of one of P pre-assigned patterns should converge to the correct pattern. In the “standard" Hopfield model, the N “neurons” are connected to each other via N2 bonds which contain the information on the stored patterns. Thus computer time and memory in general grow with N2. The Hebb rule assigns synaptic coupling strengths proportional to the overlap of the stored patterns at the two coupled
neurons. Here we simulate the Hopfield model on the Barabási-Albert scale-free network, in which each newly added neuron is
connected to only m other neurons, and at the end the number of neurons with q neighbours decays as 1/q
3. Although the quality of retrieval decreases for small m, we find good associative memory for 1 ≪ m ≪ N. Hence, these networks gain a factor N/m ≫ 1 in the computer memory and time.
Received 12 January 2003 Published online 11 April 2003
RID="a"
ID="a"e-mail: stauffer@thp.uni-koeln.de 相似文献
907.
An O(n
2) Active Set Algorithm for Solving Two Related Box Constrained Parametric Quadratic Programs
Manuel A. Gómez 《Numerical Algorithms》2001,27(4):367-375
Recently, O(n
2) active set methods have been presented for minimizing the parametric quadratic functions (1/2)x
Dx–a
x+|
x–c| and (1/2)x
Dx–a
x+(/2)(
x–c)2, respectively, subject to lxb, for all nonnegative values of the parameter . Here, D is a positive diagonal n×n matrix, and a are arbitrary n-vectors, c is an arbitrary scalar; l and b are arbitrary n-vectors such that lb. In this paper, we show that each one of these algorithms may be used to simultaneously solve both parametric programs withno additional computational cost. 相似文献
908.
Maria Manuel Clementino 《Applied Categorical Structures》2001,9(6):539-556
This paper describes a convenient modification of the approach presented in the paper Closure operators and connectedness by G. Castellini and D. Hajek, which is shown to give a suitable generalization of left- and right-constant subcategories, both at the object and the morphism levels. We show in particular that the framework we introduce here allows the simultaneous study of the classes of connected topological spaces, of concordant continuous maps and of monotone continuous maps. 相似文献
909.
The kinetic foundations of Tsallis' nonextensive thermostatistics are investigated through Boltzmann's transport equation approach. Our analysis follows from a nonextensive generalization of the "molecular chaos hypothesis." For q>0, the q-transport equation satisfies an H theorem based on Tsallis entropy. It is also proved that the collisional equilibrium is given by Tsallis' q-nonextensive velocity distribution. 相似文献
910.
We report magnetization measurements performed on graphite-sulfur composites which demonstrate a clear superconducting behavior below the critical temperature T(c0) = 35 K. The Meissner-Ochsenfeld effect, screening supercurrents, and magnetization hysteresis loops characteristic of type-II superconductors were measured. The results indicate that the superconductivity occurs in a small sample fraction, possibly related to the sample surface. 相似文献