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161.
González RR Gambarotti C Liguori L Bjørsvik HR 《The Journal of organic chemistry》2006,71(4):1703-1706
A telescoped process for the preparation of 2-methoxy-3-methyl-[1,4]benzoquinone is disclosed. When this novel process is compared to the prevailing method that utilizes Na2Cr2O7 as the oxidant, the novel process represents a high yielding (95%), green, and environmentally benign alternative with H2O2 and HNO3 as the oxidants and CH3COOH as the reaction medium. 相似文献
162.
Xanthippi Markenscoff Cristian Dascalu 《Journal of the mechanics and physics of solids》2012,60(8):1478-1485
The paper investigates the overall damage amplification effect due to micro-crack interaction in a framework of two-scale modeling. A homogenization method based on asymptotic expansions is employed to deduce the macroscopic damage equations. The damage model completely results from energy-based micro-crack propagation laws. We consider a locally periodic microstructure with periods containing pairs of micro-cracks separated by small ligaments. The asymptotic solution in the ligament region allows the study of the effect of micro-crack interaction on the effective coefficients. The local macroscopic response expresses the collective coalescence of a periodic microstructure with interacting micro-cracks. We show that the slope of the homogenized coefficients is inversely proportional to the square root of the distance between the tips of the interacting micro-cracks, accounting for the singularity in the stress fields as the micro-cracks approach each other. This leads to damage amplification as the result of the interaction of micro-cracks. 相似文献
163.
Zapata-Torres G Fierro A Miranda-Rojas S Guajardo C Saez-Briones P Salgado JC Celis-Barros C 《Journal of chemical information and modeling》2012,52(5):1213-1221
Although substrate conversion mediated by human monoaminooxidase (hMAO) has been associated with the deprotonated state of their amine moiety, data regarding the influence of protonation on substrate binding at the active site are scarce. Thus, in order to assess protonation influence, steered molecular dynamics (SMD) runs were carried out. These simulations revealed that the protonated form of the substrate serotonin (5-HT) exhibited stronger interactions at the protein surface compared to the neutral form. The latter displayed stronger interactions in the active site cavity. These observations support the possible role of the deprotonated form in substrate conversion. Multigrid docking studies carried out to rationalize the role of 5-HT protonation in other sites besides the active site indicated two energetically favored docking sites for the protonated form of 5-HT on the enzyme surface. These sites seem to be interconnected with the substrate/inhibitor cavity, as revealed by the tunnels observed by means of CAVER program. pK(a) calculations in the surface loci pointed to Glu32?, Asp32?, His???, and Asp132 as candidates for a possible in situ deprotonation step. Docking analysis of a group of inhibitors (structurally related to substrates) showed further interactions with the same two docking access sites. Interestingly, the protonated/deprotonated amine moiety of almost all compounds attained different docking poses in the active site, none of them oriented to the flavin moiety, thus producing a more variable and less productive orientations to act as substrates. Our results highlight the role of deprotonation in facilitating substrate conversion and also might reflect the necessity of inhibitor molecules to adopt specific orientations to achieve enzyme inhibition. 相似文献
164.
Nora Thies Dr. Cristian G. Hrib Prof. Dr. Edgar Haak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(20):6302-6308
Several ruthenium‐catalyzed atom‐economic transformations of propargyl alcohols with pyrroles or indoles leading to alkylated, propargylated, or annulated heteroaromatics are reported. The mechanistically distinct reactions are catalyzed by a single ruthenium(0) complex containing a redox‐coupled dienone ligand. The mode of activation regarding the propargyl alcohols determines the reaction pathway and depends on the alcohols’ substitution pattern. Secondary substrates form alkenyl complexes by a 1,2‐hydrogen shift, whereas the transformation of tertiary substrates involves allenylidene intermediates. 1‐Vinyl propargyl alcohols are converted by a cascade allylation/cyclization sequence. The environmentally benign processes are of broad scope and allow the selective synthesis of highly functionalized pyrroles and indoles generating water as the only waste product. 相似文献
165.
166.
Pessoa-Mahana H Núñez CU Araya-Maturana R Barría CS Zapata-Torres G Pessoa-Mahana CD Iturriaga-Vasquez P Mella-Raipán J Reyes-Parada M Celis-Barros C 《Chemical & pharmaceutical bulletin》2012,60(5):632-638
A series of 3-[3-(4-aryl-1-piperazinyl)-propyl]-1H-indole derivatives (12a-h) was synthesized and evaluated for binding affinity at the human 5-hydroxytryptamine(1A) receptor (5-HT(1A)R) compounds (12b) and (12h) showed the highest 5-HT(1A) receptor affinity (IC(50)=15 nM). Molecular docking studies with all the compounds in a homology model of 5-HT(1A) showed that the main interaction anchoring the ligand in the receptor was a charge-reinforced bond between the protonated nitrogen atom (N-4) of the piperazine ring and Aspartate(3.32). 相似文献
167.
Denis Mihaela Panaitescu Zina VulugaConstantin Radovici Cristian Nicolae 《Polymer Testing》2012,31(2):355-365
The effect of styrene-(ethylene-co-butylene)-styrene triblock copolymer (SEBS) on the mechanical, thermal and morphological properties of polypropylene (PP) composites filled with nanosilica particles is investigated. A simultaneous increase of all tensile characteristics is observed in PP/nanosilica composites without SEBS and containing 5%SEBS and a large plastic deformation in the nanocomposite with 10%SEBS. Different amounts of β-PP are detected by X-ray diffraction analysis and the calculated K-values correlate well with differential scanning calorimetry results. Quantitative mechanical characterization of nanocomposites is performed at nanolevel, using peak force QNM. This AFM technique allows the detection of nanosilica particles and SEBS domains at the surface of samples and gives indications of local interactions between nanosilica and the matrix from the correlation of modulus and adhesion maps, and the increased local values of elastic modulus on extended areas around nanoparticles. 相似文献
168.
Bertrand François Cristian Dascalu 《Journal of the mechanics and physics of solids》2010,58(11):1928-1946
This paper presents the theoretical developments and the numerical applications of a time-dependent damage law. This law is deduced from considerations at the micro-scale where non-planar growth of micro-cracks, following a subcritical propagation criterion, is assumed. The orientation of the crack growth is governed by the maximum energy release rate at the crack tips and the introduction of an equivalent straight crack. The passage from micro-scale to macro-scale is done through an asymptotic homogenization approach. The model is built in two steps. First, the effective coefficients are calculated at the micro-scale in finite periodical cells, with respect to the micro-cracks length and their orientation. Then, a subcritical damage law is developed in order to establish the evolution of damage. This damage law is obtained as a differential equation depending on the microscopic stress intensity factors, which are a priori calculated for different crack lengths and orientations. The developed model enables to reproduce not only the classical short-term stress-strain response of materials (in tension and compression) but also the long-term behavior encountering relaxation and creep effects. Numerical simulations show the ability of the developed model to reproduce this time-dependent damage response of materials. 相似文献
169.
Marisol Vergara-Mendoza Genny R. Martínez Cristian Blanco-Tirado Marianny Y. Combariza 《Molecules (Basel, Switzerland)》2022,27(12)
The global chocolate value chain is based exclusively on cacao beans (CBs). With few exceptions, most CBs traded worldwide are produced under a linear economy model, where only 8 to 10% of the biomass ends up in chocolate-related products. This contribution reports the mass balance and composition dynamics of cacao fruit biomass outputs throughout one full year of the crop cycle. This information is relevant because future biorefinery developments and the efficient use of cacao fruits will depend on reliable, robust, and time-dependent compositional and mass balance data. Cacao husk (CH), beans (CBs), and placenta (CP) constitute, as dry weight, 8.92 ± 0.90 wt %, 8.87 ± 0.52 wt %, and 0.57 ± 0.05 wt % of the cacao fruit, respectively, while moisture makes up most of the biomass weight (71.6 ± 2.29 wt %). CH and CP are solid lignocellulosic outputs. Interestingly, the highest cellulose and lignin contents in CH coincide with cacao’s primary harvest season (October to January). CB contains carbohydrates, fats, protein, ash, and phenolic compounds. The total polyphenol content in CBs is time-dependent, reaching maxima values during the harvest seasons. In addition, the fruit contains 4.13 ± 0.80 wt % of CME, a sugar- and nutrient-rich liquid output, with an average of 20 wt % of simple sugars (glucose, fructose, and sucrose), in addition to minerals (mainly K and Ca) and proteins. The total carbohydrate content in CME changes dramatically throughout the year, with a minimum of 10 wt % from August to January and a maximum of 29 wt % in March. 相似文献
170.
Meccanica - The goal of this paper is to present an approach to detect structural changes by using nonparametric models. The impulse response functions (IRFs) of mechanical systems in healthy... 相似文献