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21.
The energy barriers for the addition to ethylene of a series of carbenes have been calculated at an ab initio level. using the STO-3G and 3-21G basis sets. It is shown that the usual extrapolation of experiment results, which predicts that the reactivity of carbenes decreases when increasing its nucleophilic character, is not valid. 相似文献
22.
Aloy P Mas JM Martí-Renom MA Querol E Avilés FX Oliva B 《Journal of computer-aided molecular design》2000,14(1):83-92
Knowledge-based energy profiles combined with secondary structure prediction have been applied to molecular modelling refinement. To check the procedure, three different models of human procarboxypeptidase A2 (hPCPA2) have been built using the 3D structures of procarboxypeptidase A1 (pPCPA1) and bovine procarboxypeptidase A (bPCPA) as templates. The results of the refinement can be tested against the X-ray structure of hPCPA2 which has been recently determined. Regions miss-modelled in the activation segment of hPCPA2 were detected by means of pseudo-energies using Prosa II and modified afterwards according to the secondary structure prediction. Moreover, models obtained by automated methods as COMPOSER, MODELLER and distance restraints have also been compared, where it was found possible to find out the best model by means of pseudo-energies. Two general conclusions can be elicited from this work: (1) on a given set of putative models it is possible to distinguish among them the one closest to the crystallographic structure, and (2) within a given structure it is possible to find by means of pseudo-energies those regions that have been defectively modelled. 相似文献
23.
Cadmium sulfide (CdS) films were deposited on rotating substrates by the chemical bath technique. The effects of the rotation speed on the morphological, optical, and structural properties of the films were discussed. A rotating substrate-holder was fabricated such that substrates can be taken out from the bath during the deposition. CdS films were deposited at different deposition times (10, 20, 30, 40 and 50 min) onto Corning glass substrates at different rotation velocities (150, 300, 450, and 600 rpm) during chemical deposition. The chemical bath was composed by CdCl2, KOH, NH4NO3 and CS(NH2)2 as chemical reagents and heated at 75 °C. The results show no critical effects on the band gap energy and the surface roughness of the CdS films when the rotation speed changes. However, a linear increase on the deposition rate with the rotation energy was observed, meanwhile the stoichiometry was strongly affected by the rotation speed, resulting a better 1:1 Cd/S ratio as speed increases. Rotation effects may be of interest in industrial production of CdTe/CdS solar cells. 相似文献
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26.
C Rodríguez-García A Oliva R M Ortu?o V Branchadell 《Journal of the American Chemical Society》2001,123(25):6157-6163
The reaction of diazomethane with ethylene in the presence of palladium diformate has been studied through density functional calculations. Several mechanistic paths leading to the formation of cyclopropane have been studied. The results obtained show that the reaction of palladium diformate with diazomethane is more favorable than the reaction with ethylene. The reaction with diazomethane may lead to two different isomeric complexes: a methylene-inserted complex and a palladium-carbene complex. Insertion of methylene is the most favorable process, but the resulting complex is not suitable for cyclopropanation. The reaction with two additional diazomethane molecules makes the formation of the bismethylene-inserted palladium-carbene complex favorable. Attack of ethylene on this palladium-carbene complex leads to the formation of cyclopropane. 相似文献
27.
We present a refinement ofthe bounded modified realizability which provides both upper and lower bounds for witnesses. Our interpretation is based on a generalisation of Howard/Bezem's notion of strong majorizability. We show how the bounded modified realizability coincides with (a weak version of) our interpretation in the case when least elements exist (e.g. natural numbers). The new interpretation, however, permits the extraction of more accurate bounds, and provides an ideal setting for dealing directly with data types whose natural ordering is not well‐founded (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
28.
M. Ramos Suzarte N. Rodríguez J. P. Oliva N. Iznaga A. Perera A. Morales N. Gonzalez O. Torres T. Rodríguez 《Journal of Radioanalytical and Nuclear Chemistry》1999,240(2):499-503
Monoclonal antibody ior egf/r3 is a IgG2a, recognizes the epidermal growth factor receptor. The aim of the present work was
to evaluate the diagnostic efficacy of the99mTc-labeled ior egf/r3 for the detection of epithelial tumors, its metastasis and its recurrences. The sensitivity by organs
was: brain 100%, diegestive tract 90%, head and neck 89%, lung 84% and breast 79%. The overall sensitivity, specificity, accuracy,
positive predictive value and negative predictive value of the immunoscintigraphic imaging were 84.1%, 100%, 86.5%, 100% and
52.4%, respectively. Immunoscintigraphy with99mTc-ior egf/r3 is useful for the diagnosis and follow-up of epithelial tumors. 相似文献
29.
Vladimir R. Rosenfeld Douglas J. Klein Josep M. Oliva 《Journal of mathematical chemistry》2012,50(7):2012-2022
Various sorts of isomer enumeration problems are addressed in the context of polycarboranes, with special illustrative focus on the case of dicarboranes, for which then various numerical results are given. A systematic and general Pólya-theoretic methodology is used to make the computations, including some new techniques being applicable to a wide range of nano-structures built from a framework of like local subunits. 相似文献
30.