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991.
992.
Using the Brownian dynamics simulation technique, we study the rotational dynamics of a semiflexible broken rod. We employ a suitable bead model with stiff springs between beads and strong forces opposing to bending, except at the joint where flexibility is variable. We consider mostly broken rods with equal arms. From the simulated Brownian trajectories we obtain the correlation function for the second order Legendre polynomial of the reorientational angle of the end-to-end vector and of the arm vector. These correlation functions are closely related to fluorescence anisotropy decay and electric birefringence decay, respectively. In the first case, the relaxation time for a completely flexible rod agrees with the Harvey-Wegener theory, and in the second, the longest relaxation time agrees well with that obtained from the rigid-body treatment over the whole range of flexibility. Furthermore, we discuss the relative importance of flexibility in both types of decay. Finally, we present results for a case with unequal arms, confirming the validity of the Harvey-Wegener theory and the rigid-body treatment. 相似文献
993.
Meta-heuristics are a powerful way to approximately solve hard combinatorial optimization problems. However, for a problem, the quality of results can vary considerably from one instance to another. Understanding such a behaviour is important from a theoretical point of view, but also has practical applications such as for the generation of instances during the evaluation stage of a heuristic.In this paper we propose a new complexity measure for the Quadratic Assignment Problem in the context of metaheuristics based on local search, e.g. simulated annealing. We show how the ruggedness coefficient previously introduced by the authors, in conjunction with the well known concept of dominance, provides important features of the search space explored during a local search algorithm, and gives a rather precise idea of the complexity of an instance for these heuristics. We comment previous experimental studies concerning tabu search methods and genetic algorithms with local search in the light of our complexity measure. New computational results with simulated annealing and taboo search are presented. 相似文献
994.
Felipa M. Bautista Juan M. Campelo Angel Garcia Raquel M. Leon Diego Luna Jose M. Marinas Antonio A. Romero Jose A. Navio Manuel Macias 《Reaction Kinetics and Catalysis Letters》1998,65(2):245-251
Crystalline and amorphous vanadyl polyphosphates (VO(PO3)2) with a P/V ratio=2 were used as catalysts in the ammoxidation of toluene. The crystalline specimens exhibit a rather low
activity compared with the amorphous solid. The benzonitrile selectivities always reached nearly 90%. Noticeable benzaldehyde
amounts were detected that could be due to an inadequate ammonia activation on the solid surface. 相似文献
995.
Ruedas-Rama MJ Orte A Hall EA Alvarez-Pez JM Talavera EM 《Chemical communications (Cambridge, England)》2011,47(10):2898-2900
The first CdSe/ZnS quantum dot photoluminescence lifetime-based pH nanosensor has been developed. The average lifetime of mercaptopropionic acid-capped QD nanosensors showed a linear response in the pH range of 5.2-6.9. These nanosensors have been satisfactorily applied for pH estimation in simulated intracellular media, with high sensitivity and high selectivity toward most of the intracellular components. 相似文献
996.
Dr. Angel Cuesta 《Chemphyschem》2011,12(13):2375-2385
During an electrocatalytic reaction bonds are broken and formed, and this requires that the reactants, the intermediates formed at the elementary reaction steps, and the products interact with a given number of surface atoms of the catalyst. Modifying the number of groups with an adequate number of surface atoms in a suitable geometric arrangement for a determined reaction step to proceed may affect the activity and/or selectivity of the catalyst. Although separating purely geometric atomic ensemble effects from electronic effects is not straightforward, the insights extracted from a detailed investigation of atomic ensemble effects can have a profound impact in the determination of electrocatalytic reaction mechanisms and in the design of more active and more selective electrocatalysts. This Minireview illustrates, using cyanide‐modified Pt(111) electrodes as an archetype, how eliminating only one kind of site from the surface (the site‐knockout strategy) by means of a regular array of inert adsorbates can be used to successfully study atomic ensemble effects in electrocatalysis. The possible consequences for the design of more efficient and more selective electrocatalysts are also commented on. 相似文献
997.
Cuesta A Cabello G Gutiérrez C Osawa M 《Physical chemistry chemical physics : PCCP》2011,13(45):20091-20095
The electrooxidation of formic acid on Pt and other noble metal electrodes proceeds through a dual-path mechanism, composed of a direct path and an indirect path through adsorbed carbon monoxide, a poisoning intermediate. Adsorbed formate had been identified as the reactive intermediate in the direct path. Here we show that actually it is also the intermediate in the indirect path and is, hence, the key reaction intermediate, common to both the direct and indirect paths. Furthermore, it is confirmed that the dehydration of formic acid on Pt electrodes requires adjacent empty sites, and it is demonstrated that the reaction follows an apparently paradoxical electrochemical mechanism, in which an oxidation is immediately followed by a reduction. 相似文献
998.
Muñoz L Rodriguez AM Rosell G Bosch MP Guerrero A 《Organic & biomolecular chemistry》2011,9(23):8171-8177
Both enantiomers of several phenylethylamines, structurally related to amphetamine, have been prepared in good yields and excellent enantiomeric purity by enzymatic kinetic resolution using CAL-B and ethyl methoxyacetate as the acyl donor. In the case of the 4-hydroxyderivative of amphetamine (compound 4i), the S enantiomer racemized possibly in a dynamic kinetic resolution (DKR) under the enzymatic conditions used. 相似文献
999.
García Velázquez D González Orive A Hernández Creus A Luque R Gutiérrez Ravelo A 《Organic & biomolecular chemistry》2011,9(19):6524-6527
Novel C(3)-symmetrical heteroaromatic hexaazatrinaphthylene (HATNA) gelators symmetrically end-substituted with pendant aromatic and aliphatic amines were synthesized. Some of these π-conjugated structures induce self-assembly, forming fibers able to gelate solvents of different polarity at low wt% as demonstrated by spectroscopic and microscopic techniques. 相似文献
1000.
Petreska J Stefova M Ferreres F Moreno DA Tomás-Barberán FA Stefkov G Kulevanova S Gil-Izquierdo A 《Natural product communications》2011,6(9):1305-1314
This work was afforded from 2 points of view, phytochemical evaluation and relation to antioxidant activity and dietary burden of phenolics of a cup of "Mountain tea", a drink obtained by domestic infusion of Sideritis. Phytochemically, two extraction protocols using water and methanol as solvent were used for comparison. Methanol and boiling water extracts (by domestic infusion procedure) showed that extracts were rich in bound forms of phenolics such as hydroxycinnamic acids, phenylethanoid glycosides and flavonoid glycosides. The total phenolic content for Sideritis species ranged around 190 mg per serving (2 g infusion bag) for methanol extracts and around 72 mg per serving in water extracts. Among the two different Macedonian Sideritis species, Sideritis raeseri (wild growing) showed the highest phenolics content in both extracts (212 mg and 89 mg per serving, respectively). Concerning the phenolic content in the different aerial parts, leaf was the richest plant organ in phenolics followed by flower and stem with the lowest amount. The methanol extract from Sideritis raeseri (wild growing) showed the highest antioxidant capacity as shown by DPPH, ABTS and FRAP assays. The antioxidant capacity was linearly correlated with phenolic content. Nutritionally, the dietary burden of phenolics of a "Mountain tea" bag for domestic infusion (serving size) was established at 89 mg for an homogeneous and equal distribution of the different aerial parts (leaf, flower and stem). However, and according to our results a rate of 60% leaf and 40% flower would increase the content of bioavailable phenolics and also the total phenolics content of a serving bag of "Mountain tea". 相似文献