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1.
Meccanica - In this work we study, from the numerical point of view, a one-dimensional thermoelastic problem where the thermal law is of type III. Quasi-static microvoids are also assumed within...  相似文献   
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The reaction mechanism for the hydrolysis of trimethyl phosphate and of the obtained phosphodiester by the di‐CoII derivative of organophosphate degrading enzyme from Agrobacterium radiobacter P230(OpdA), have been investigated at density functional level of theory in the framework of the cluster model approach. Both mechanisms proceed by a multistep sequence and each catalytic cycle begins with the nucleophilic attack by a metal‐bound hydroxide on the phosphorus atom of the substrate, leading to the cleavage of the phosphate‐ester bond. Four exchange‐correlation functionals were used to derive the potential energy profiles in protein environments. Although the enzyme is confirmed to work better as triesterase, as revealed by the barrier heights in the rate‐limiting steps of the catalytic processes, its promiscuous ability to hydrolyze also the product of the reaction has been confirmed. The important role played by water molecules and some residues in the outer coordination sphere has been elucidated, while the binuclear CoII center accomplishes both structural and catalytic functions. To correctly describe the electronic configuration of the d shell of the metal ions, high‐ and low‐spin arrangement jointly with the occurrence of antiferromagnetic coupling, have been herein considered.  相似文献   
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The traditional way to enhance signal-to-noise ratio (SNR) of nuclear magnetic resonance (NMR) signals is to increase the number of scans. However, this procedure increases the measuring time that can be prohibitive for some applications. Therefore, we have tested the use of several post-acquisition digital filters to enhance SNR up to one order of magnitude in time domain NMR (TD-NMR) relaxation measurements. The procedures were studied using continuous wave free precession (CWFP-T1) signals, acquired with very low flip angles that contain six times more noise than the Carr–Purcell–Meiboom–Gill (CPMG) signal of the same sample and experimental time. Linear (LI) and logarithmic (LO) data compression, low-pass infinity impulse response (LP), Savitzky–Golay (SG), and wavelet transform (WA) post-acquisition filters enhanced the SNR of the CWFP-T1 signals by at least six times. The best filters were LO, SG, and WA that have high enhancement in SNR without significant distortions in the ILT relaxation distribution data. Therefore, it was demonstrated that these post-acquisition digital filters could be a useful way to denoise CWFP-T1, as well as CPMG noisy signals, and consequently reducing the experimental time. It was also demonstrated that filtered CWFP-T1 method has the potential to be a rapid and nondestructive method to measure fat content in beef and certainly in other meat samples.  相似文献   
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By combining frontal polymerization and radical‐induced cationic polymerization, it was possible to cure thick samples of an epoxy monomer bleached by UV light. The effect of the relative amounts of cationic photoinitiator and radical initiator was thoroughly investigated and was related to the front's velocity and its maximum temperature. The materials obtained were characterized by quantitative conversion also in the deeper layers, not reached by UV light. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2066–2072, 2004  相似文献   
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Composition algebras with a unit element constitute a well-known class of algebras. In this paper, those composition algebras with a one-sided unit element are characterized and examples are given of arbitrary infinite dimension.

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This article will emphasize the particular role of organometallic radiopharmaceutical chemistry, namely the need for syntheses from water and the emerging implications for other (bio)organometallic fields. After some basic insights into the different directions of bioorganometallic chemistry, some facets of the [M(CO)3]+ (M = Tc, Re) moiety are reviewed and discussed in the respective context. The mechanism for the synthesis of [M(OH2)3(CO)3]+ which is still little understood, will be touched. The formation of additional M-C bonds is exemplified with cyclopentadienyl chemistry, the potential impact on targeted molecular imaging with the labelling of amino acids and the reactivity towards essential biomolecules such as guanine is shown. Future perspectives and implications for organometallic radiopharmaceutical chemistry will close this article.  相似文献   
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The review outlines the various different azaheterocycles available from 5-spirocyclopropane isoxazolidines. These compounds can be regarded as versatile direct precursors of tetrahydro-, dihydropyridone and azetidinone derivatives. The current scope and limitations, and the selectivity aspects of the different processes are discussed therein.  相似文献   
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