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941.
Igor S. Ignatyev Manuel Montejo Juan Jesús López González 《Journal of molecular modeling》2013,19(12):5439-5444
Experimental mass-spectrometry data on thermochemistry of methide transfer reactions (CH3)3M+ + M'(CH3)4 ? M(CH3)4?+?(CH3)3M'+ (M, M'?=?Si, Ge or Sn) and the formation energy of the [(CH3)3Si-CH3-Si(CH3)3]+ complex are used as benchmarks for DFT methods (B3LYP, BMK, M06L, and ωB97XD). G2 and G3 theory methods are also used for the prediction of thermochemical data. BMK, M06L, and ωB97XD methods give the best fit to experimental data (close to chemical accuracy) as well as to G2 and G3 results, while B3LYP demonstrates poor performance. From the first three methods M06L gives the best overall result. Structures and formation energies of intermediate “mixed” [(CH3)3M-CH3- M′(CH3)3] complexes not observed in experiment are predicted. Their structures, better described as M(CH3)4?[M′(CH3)3]+ complexes, explain their fast decompositions. Figure
Graphical representation of the molecular structureof the intermediates in the methide transfer reactions: (CH3)3M+ + M'(CH3)4 ? M(CH3)4 + (CH3)3M'+ (M,M'=Si, Ge, Sn) 相似文献
942.
Xiao Li Jianhua Li Yali Tan Dongrui Pan Zhihong Li Xuefeng Yu Juan Yao 《Annals of microbiology》2013,63(4):1247-1256
In this research, we first determined the three most significant nutrient factors affecting haloalcohol dehalogenase HheC production by Escherichia coli P84A/MC1061. These were glycerol, yeast extract, and ammonium sulfate. The steepest ascent method was then applied to obtain the optimal design intervals of the three factors. An application of center composite design was used, and the ingredients of the optimized medium were 1.8 g l?1 glycerol, 48 g l?1 yeast extract, 2.2 g l?1 ammonium sulfate, 5 g l?1 compound phosphate, 1 g l?1 magnesium sulfate, and 1.19?×?10?5?g l?1 ferric sulfate. The enzyme activity reached 109,365 U ml?1 under the most favorable conditions, which is a 277.7 % increase compared with the control group. Our study of cellular respiration parameters (oxygen uptake rate and carbon dioxide emission rate) revealed that the metabolic activity of the strain was strongly promoted under these optimal nutrient conditions and that yeast extract had a positive effect on respiratory intensity and the expression levels of HheC. 相似文献
943.
Xiao Ran Zhao Yu Jie Wu Juan Han Qian Jin Shen Wei Jun Jin 《Journal of molecular modeling》2013,19(1):299-304
MP2(full)/aug-cc-pVDZ(-PP) computations predict that new triangular bonding complexes (where X? is a halide and H–C refers to a protic solvent molecule) consist of one halogen bond and two hydrogen bonds in the gas phase. Carbon tetrabromide acts as the donor in the halogen bond, while it acts as an acceptor in the hydrogen bond. The halide (which commonly acts as an acceptor) can interact with both carbon tetrabromide and solvent molecule (CH3CN, CH2Cl2, CHCl3) to form a halogen bond and a hydrogen bond, respectively. The strength of the halogen bond obeys the order CBr4???Cl? > CBr4???Br? > CBr4???I?. For the hydrogen bonds formed between various halides and the same solvent molecule, the strength of the hydrogen bond obeys the order C-H???Cl? > C-H???Br? > C-H???I?. For the hydrogen bonds formed between the same halide and various solvent molecules, the interaction strength is proportional to the acidity of the hydrogen in the solvent molecule. The diminutive effect is present between the hydrogen bonds and the halogen bond in chlorine and bromine triangular bonding complexes. Complexes containing iodide ion show weak cooperative effects. Figure
The triangular bonding complexes consisting of halogen bond and hydrogen bonds were predict in the gas phase by computational quantum chemistry. 相似文献
944.
M. Rosario Darquier Cecilia F. Bessega Mariano Cony Juan C. Vilardi Beatriz O. Saidman 《Tree Genetics & Genomes》2013,9(1):307-320
Prosopis flexuosa is an arboreal Leguminosae that grows in arid and semiarid temperate zones of Argentina, in the Monte eco-region. It is a promising native forest species for recovering arid and semiarid regions because it plays an important role in erosion control as well as in soil fertility. Furthermore, it provides diverse economical resources. The main challenge to the forestry sector is finding a balance between production and forest protection. For this purpose, it is necessary to gather information about genetic parameters. In this study, we measured the distribution of the variation of 14 quantitative traits in an experimental half-sib stand, where families are representative of hierarchically structured populations. We applied a multivariate extension of the classical Q ST –F ST neutrality test to determine the relative importance of drift versus selection in the distribution of genetic variability. We found strong evidence that different selective regimes act on different traits and that selection favors different optima in each sampling site. The selection to different optima is much stronger among than within provenances. This result helps explain the possible causes for the regional variation observed in P. flexuosa and to define the management units and the evolutionarily significant units for this species. 相似文献
945.
Pau Rodenas Taesup Song Pitchaimuthu Sudhagar Gabriela Marzari Hyungkyu Han Laura Badia‐Bou Sixto Gimenez Francisco Fabregat‐Santiago Ivan Mora‐Sero Juan Bisquert Ungyu Paik Yong Soo Kang 《Liver Transplantation》2013,3(2):176-182
TiO2 hollow nanowires (HNWs) and nanoparticles (NPs) constitute promising architectures for QDs sensitized photoanodes for H2 generation. We sensitize these structures with CdS/CdSe quantum dots by two different methods (chemical bath deposition, CBD and succesive ionic layer adsorption and reaction, SILAR) and evaluate the performance of these photoelectrodes. Remarkable photocurrents of 4 mA·cm and 8 mA·cm?2 and hydrogen generation rates of 40 ml·cm?2·day?1 and 80 ml·cm?2·day?1 have been obtained in a three electrode configuration with sacrificial hole scavengers (Na2S and Na2SO3), for HNWs and NPs respectively, which is confirmed through gas analysis. More importantly, autonomous generation of H2 (20 ml·cm?2·day?1 corresponding to 2 mA·cm?2 photocurrent) is obtained in a two electrode configuration at short circuit under 100 mW·cm?2 illumination, clearly showing that these photoanodes can produce hydrogen without the assistance of any external bias. To the best of the authors' knowledge, this is the highest unbiased solar H2 generation rate reported for these of QDs based heterostructures. Impedance spectroscopy measurements show similar electron density of trap states below the TiO2 conduction band while the recombination resistance was higher for HNWs, consistently with the much lower surface area compared to NPs. However, the conductivity of both structures is similar, in spite of the one dimensional character of HNWs, which leaves some room for improvement of these nanowired structures. The effect of the QDs deposition method is also evaluated. Both structures show remarkable stability without any appreciable photocurrent loss after 0.5 hour of operation. The findings of this study constitute a relevant step towards the feasibility of hydrogen generation with wide bandgap semiconductors/quantum dots based heterostructures. 相似文献
946.
Roads have many effects on the mammal populations of their surroundings. Prey species are thought to establish dense populations in road verges due to a predation release effect, which arise as a side-effect of roadside avoidance by predators and/or predator roadkill. A species that has been suggested to benefit from predation release and attain high densities near roads is the European rabbit, a keystone species in Mediterranean ecosystems. We monitored rabbit relative abundance at three distances from a motorway (50, 450 and 850 m) during a 6 month period, as well as hunting and predator pressures, in a suitable area for rabbits. The lowest rabbit abundance was found next to the motorway (6.76 ± 8.87 pellets/m2 per month) and the highest abundance at an intermediate distance (17.65 ± 23.11 pellets/m2 per month). Hunting and carnivore pressures were highest at the sampling transect located farthest from the infrastructure. Thus, variability in rabbit abundance did not match the predation release effect found close to the motorway, and some sort of road avoidance or other process must underlie the observed abundance pattern. We advocate for a formal measurement of prey populations response to roads prior to any generalization as, in the case of rabbit, the response to roads and the potential cascading effects on other species may depend on landscape characteristics. 相似文献
947.
948.
目的:了解巴中地区上消化道出血反复发作的原因,为治疗提供临床循证医学证据。方法:通过对2011年4月~2012年11月巴中地区1134例上消化道出血中132例反复发作的患者进行调查统计,分析这上消化道出血反复发作的132例患者的年龄、生理特征、生活饮食习惯、精神状态、生活压力等多种相关因素。结果:发现饮食不当、精神紧张、腹腔感染、腹腔内压增高、输液输血过速、过量等是造成病情反复发作的主要诱因。结论:通过消除疾病的诱发因素,认真做好健康教育指导,积极治疗原发病是预防反复发作的有效措施。 相似文献
949.
目的:分析重度妊娠期肝内胆汁淤积症(intrahepatic cholestasis of pregnancy,ICP)对母婴结局的影响,以提高对ICP的认识与治疗水平。方法:选择ICP产妇58例,根据ICP分度标准分为轻度组(n=26例)和重度组(n=32例),比较两组产妇的母婴结局。结果:与轻度组相比,重度组产妇剖宫产率、产后出血与平均产后出血量显著升高或增加,阴道分娩率显著降低,组间比较差异均具有统计学意义(P〈0.05);重度组新生儿早产、胎儿窘迫、羊水污染和新生儿窒息的发生率均显著上升,新生儿平均出生体重显著降低,组间比较差异均具有统计学意义(P〈0.05)。结论:ICP对产妇及新生儿均有不良影响,对ICP严重程度进行划分,有利于临床处理。对于重度ICP产妇,应尽早采取剖宫产分娩的方式终止妊娠。 相似文献
950.
目的:应用基因芯片技术筛选不同病毒载量的慢乙肝病人及健康人差异性表达的基因。方法:选用含有48000位点的人类表达谱cDNA基因芯片,筛选4例慢乙肝病人与2例健康人外周血差异性表达的基因。结果:与健康人相比,慢乙肝患者有838个差异表达的基因,其中高表达的基因有150个,低表达的基因有688个。结论:用表达谱基因芯片可有效地研究高、低病毒载量的慢乙肝患者间,以及它们与健康人之间基因表达的差异,通过进一步分析有望筛选出与慢性乙型肝炎相关的新基因靶点。 相似文献