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231.
Hariklia Papadaki Evangelos G. Bakalbassis John C. Jeffery 《Journal of organometallic chemistry》2008,693(7):1203-1214
The Sn(IV) R2SnCl2(γ-pyrone)n [R = Me or Ph; γ-pyrone = 4H-pyran-4-one (PYR) or 2,6-dimethyl-4H-pyran-4-one (DMP); n = 1 or 2] adducts have been synthesized and investigated. The adducts Ph2SnCl2(PYR) (1), Me2SnCl2(PYR)2 (2), Ph2SnCl2(DMP) (3) and Me2SnCl2(PYR)(PNO) (4), (PNO = 4-methylpyridine N-oxide) have been prepared by the addition of the corresponding γ-pyrone to chloroform solution of R2SnCl2. The new compounds have been characterized by elemental analysis and spectroscopic (IR, 1H, 13C NMR and Mössbauer) means. The single-crystal diffraction study of 1 shows the Sn(IV) to be five-coordinate, [Sn-O and Sn-Cl(1), Sn-Cl(2) distances of 2.3190(13) and 2.4312(6), 2.3653(7), respectively], and the Cl-Sn-Cl bond angle to be 91.17°. The reactivity of 2 towards bipy, Ph3PO, QNO (Q = quinoline) resulted in complete displacement of PYR and formation of already known compounds whereas, the PNO displaced only one equivalent of PYR, causing the preparation of the new mixed complex 4, possibly through a SN1 formation mechanism. DFT/B3LYP molecular orbital calculations were carried out for the 1-4 complexes, their precursors, Ph2SnCl2, (5) and Me2SnCl2, (6) and the ligands, PYR, DMP and PNO in an attempt to explain the structures and reactivity of the complexes. Optimized resulting geometries, vibrational frequencies, and the electron-accepting ability of the complexes and the precursors towards nucleophiles are discussed. 相似文献
232.
de Lemos E Porée FH Bourin A Barbion J Agouridas E Lannou MI Commerçon A Betzer JF Pancrazi A Ardisson J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(35):11092-11112
An efficient and modulable total synthesis of discodermolide (DDM), a unique marine anticancer polyketide is described including related alternative synthetic approaches. Particularly notable is the repeated application of a crotyltitanation reaction to yield homoallylic (Z)-O-ene-carbamate alcohols with excellent selectivity. Advantage was taken of this reaction not only for the stereocontrolled building of the syn-anti methyl-hydroxy-methyl triads of DDM, but also for the direct construction of the terminal (Z)-diene. Of particular interest is also the installation of the C13=C14 (Z)-double bond through a highly selective dyotropic rearrangement. The preparation of the middle C8-C14 fragment in two sequential stages and its coupling to the C1-C7 moiety was a real challenge and required careful optimization. Several synthetic routes were explored to allow high and reliable yields. Due to the flexibility and robust character of this approach, it might enable a systematic structural variation of DDM and, therefore, the elaboration and exploration of novel discodermolide structural analogues. 相似文献
233.
Myofibroblasts are differentiated fibroblasts that hold a key role in wound healing and remodeling following myocardial infarction (MI). A large repertoire of stimuli, such as mechanical stretch, growth factors, cytokines, and vasoactive peptides, induces myofibroblast differentiation. Myofibroblasts are responsible for the production and deposition of collagen, leading to the establishment of a dense extracellular matrix that strengthens the infarcted tissue and minimizes dilatation of the infarct area. In addition, cells contributing to fibrosis act on sites distal from the infarct area and promote collagen deposition in noninfarcted tissue, thus contributing to adverse remodeling and consequently to the development of congestive heart failure (CHF). Current drugs that are used to treat post-MI CHF do influence fibroblasts and myofibroblasts; however, their therapeutic efficacy is far from being regarded as ideal. Novel therapeutic agents targeting (myo)fibroblasts are being developed to successfully prevent the cardiac remodeling of sites remote from the infarct area and therefore hinder the establishment of CHF. The purpose of this review article is to discuss the basic concepts of the myofibroblasts' actions in cardiac wound healing processes, factors that influence them, currently available pharmacological agents, and future challenges in this area. 相似文献
234.
Giannakopoulos E Stathi P Dimos K Gournis D Sanakis Y Deligiannakis Y 《Langmuir : the ACS journal of surfaces and colloids》2006,22(16):6863-6873
Humic acids have stable radicals that are indigenous to their structure. Hydroxybenzoic acid derivatives such as gallic acid (GA) and protocatechuic acid are appropriate models for the radical properties of humic acids. Here we show that the adsorption or intercalation of gallic acid in Laponite clay results in a significant thermodynamic stabilization of gallic acid radicals. Moreover, the formed organoclay shows enhanced stability against acid dissolution. The structural details of the association of gallic acid with Laponite depend on the GA/Laponite loading. At low GA/Laponite ratios (approximately 10(-6) M of gallic acid per gram of clay), gallic acid is adsorbed at the variable charge sites of Laponite. This adsorption can be adequately described by surface complexation modeling. At higher GA/Laponite ratios (approximately 10(-3) M of gallic acid per gram of clay), X-ray diffraction data show that gallic acid is intercalated at the interlamellar sites of Laponite. In the presence of Pb2+ ions, the formed GA/Pb complex is associated with Laponite in an analogous structural manner, that is, adsorption at variable charge sites or intercalation at the interlamellar sites of Laponite, depending on the loading. Laponite stabilizes the GA/Pb radicals. At prolonged exposure to ambient O2, Laponite promotes the formation of stable oligomeric GA/Pb radical species, which are intercalated into interlamellar sites. 相似文献
235.
236.
Andreas-Stefanos I. Margetis Evangelos M. Papoutsis-Kiachagias Kyriakos C. Giannakoglou 《国际流体数值方法杂志》2023,95(1):23-43
The unsteady adjoint method used in gradient-based optimization in 2D and, particularly, 3D industrial problems modeled by unsteady PDEs may have significant storage requirements and/or computational cost. The reason for this is that the backward in time integration of the adjoint equations requires the previously computed instantaneous flow fields to be available at each time-step. This article proposes remedies to this problem, by extending/upgrading relevant techniques proposed by the group of authors as well as other researchers. Their applicability is wide, even if these remedies are herein demonstrated in shape optimization problems in unsteady fluid mechanics. Check-pointing is in widespread use as it reduces the memory footprint and CPU cost of the optimization with a controllable computational overhead. Alternatively, flow field time-series can be stored in a lossless or lossly compressed form. The novelty of this article is the development of a Compressed Coarse-grained Check-Pointing strategy for second-order accurate schemes in time, by optimally combining check-pointing and lossy compression. The latter includes (a) the incremental Proper Generalized Decomposition (iPGD) algorithm and (b) a hybridization of the iPGD with the ZFP and Zlib algorithms. This is implemented within OpenFOAM, which is used to solve the flow and adjoint equations and conduct the optimization, and assessed in 2D/3D aerodynamic shape optimization problems on unstructured grids. Effectiveness in data reduction, computational cost, and reconstruction accuracy are compared, vis-à-vis also to the “standard” binomial check-pointing technique after adjusting it to second-order accurate schemes in time. 相似文献
237.