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111.
Bagrat A. Shainyan Elena N. Suslova Erich Kleinpeter 《Journal of Physical Organic Chemistry》2011,24(12):1188-1192
4,4‐Dimethyl‐4‐silathiane and its S‐oxides [n = 0 ( 1 ), 1 ( 2 ), 2 ( 3 )] were studied experimentally by variable temperature dynamic NMR spectroscopy down to 103 K and the frozen ring inversion was revealed for all three compounds. The barriers for the degenerate ring inversion in 1 and 3 were measured to be 4.8 and 5.0 kcal/mol at the coalescence temperatures of 111 and 116 K, respectively, and practically coincide with the calculated barriers of 4.60 kcal/mol in 1 and 4.46 kcal/mol in 3 . The frozen equilibrium mixture 2‐ax/2‐eq contains 37% of the 2‐ax and 63% of the 2‐eq conformer. The ring inversion barrier proved to be ca. 4.8 kcal/mol. Calculations at the B3LYP/6‐311+G(d,p) level of theory showed the 2‐ax conformer to be 0.90 kcal/mol more stable than the 2‐eq conformer in the gas phase whereas in solution the relative stability of the conformers calculated using the PCM model at the same level of theory is inverted to become 0.19 (in CHCl3) or 0.36 kcal/mol (in DMSO) in favor of the 2‐eq conformer. The chair–chair interconversion mechanism of sulfoxide 2 includes two intermediate energetically equivalent 1,4‐twist forms and the 2,5‐boat transition state: 2‐ax (chair) ? 2 (1,4‐twist) ? [ 2 (2,5‐boat)]≠ ? 2 (1,4‐twist) ? 2‐eq (chair). The calculated ring inversion barriers are 5.1 ( 2‐ax → 2‐eq ) and 4.2 kcal/mol ( 2‐eq → 2‐ax ) in the gas phase, and 4.03 and 4.22 kcal/mol, respectively, in chloroform. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
112.
采用UV-Vis光谱法,研究在pH 4.2的H3PO4-KH2PO4缓冲溶液中血红蛋白(Hb)与铜(Ⅱ)-茜素红S(ARS)络合物的反应。结果表明:Hb与Cu(Ⅱ)-ARS络合物相互作用形成红色的离子缔合复合物,该复合物的最大吸收波长为537 nm。在此波长下测得复合物的组成为nHb∶nCu(Ⅱ)∶nARS=1∶4∶8,表观摩尔吸光系数为1.52×105 L·mol-1·cm-1,Hb浓度在1.0×10-7~2.0×10-6 mol·L-1范围内与吸光度呈线性关系,回归方程为A=0.026 9+151 675c(mol·L-1),相关系数r=0.997 2。考察了溶液酸度、试剂用量、反应时间与温度、离子强度、表面活性剂等因素对Hb-Cu(Ⅱ)-ARS复合物形成的影响,并对反应机理做了初步探讨,发现Hb与Cu(Ⅱ)-ARS络合物之间主要以静电引力相结合。进一步考察了常见氨基酸及金属离子对Hb-Cu(Ⅱ)-ARS复合物形成的影响。 相似文献
113.
In this report, we demonstrate scanning tunneling microscopy and spectroscopy on thin films of lauryl amine (LAM) and octadecane thiol (ODT) protected gold nanoparticles. We show that the zero current in the I-V curves (measure of Coulomb blockade (CB) of the nanoparticles) depends on the properties of the spacer molecule. In both the cases the gap voltage and the tunneling current at which the images are obtained are quite different which is further confirmed from the fitting performed based on the orthodox theory. The values for the capacitance and charging energy obtained from the fitting for ODT capped particles are comparable to the values obtained using spherical capacitor model. In contrast, values of these parameters were found to differ for LAM capped nanoparticles. While imaging, ODT capped nanoparticles were observed to drag along the scan direction leading to ordering of particles. Images of LAM capped gold nanoparticles show local ordering in self-assembly of particles although no evidence of large scale ordering in spatial Fourier transform was seen. These observations suggest that nanoparticles with larger CB would be imaged nonevasively in contrast to small CB systems for which tip induced effects will be dominant. In both the systems the current was found to rise faster than theoretical curves based on the orthodox theory suggesting that mechanism of charge transfer in this case may involve field emission rather than tunneling through a rectangular barrier. An attempt has been made to explain charge transfer based on Fowler-Nordheim (F-N) plots of the I-V curves. 相似文献
114.
We study the statistical properties of wave transport in a disordered waveguide. We first derive the properties of a “building block” (BB) of length δL starting from a potential model consisting of thin potential slices. We then find a diffusion equation—in the space of transfer matrices that describe our system—which governs the evolution with the length L of the disordered waveguide of the transport properties of interest. The latter depend only on the mean free paths and on no other property of the slice distribution. The universality that arises demonstrates the existence of a generalized central-limit theorem. We have developed a numerical simulation in which the universal statistical properties of the BB found analytically are first implemented numerically, and then the various BBs are combined to construct the full waveguide. The reported results thus obtained are in good agreement with microscopic calculations, for both bulk and surface disorder. 相似文献
115.
Wantana Klysubun Pinit Kidkhunthod Pongjakr Tarawarakarn Panidtha Sombunchoo Chanapa Kongmark Sukit Limpijumnong Saroj Rujirawat Rattikorn Yimnirun Gamolwan Tumcharern Kajornsak Faungnawakij 《Journal of synchrotron radiation》2017,24(3):707-716
The SUT‐NANOTEC‐SLRI beamline was constructed in 2012 as the flagship of the SUT‐NANOTEC‐SLRI Joint Research Facility for Synchrotron Utilization, co‐established by Suranaree University of Technology (SUT), National Nanotechnology Center (NANOTEC) and Synchrotron Light Research Institute (SLRI). It is an intermediate‐energy X‐ray absorption spectroscopy (XAS) beamline at SLRI. The beamline delivers an unfocused monochromatic X‐ray beam of tunable photon energy (1.25–10 keV). The maximum normal incident beam size is 13 mm (width) × 1 mm (height) with a photon flux of 3 × 108 to 2 × 1010 photons s?1 (100 mA)?1 varying across photon energies. Details of the beamline and XAS instrumentation are described. To demonstrate the beamline performance, K‐edge XANES spectra of MgO, Al2O3, S8, FeS, FeSO4, Cu, Cu2O and CuO, and EXAFS spectra of Cu and CuO are presented. 相似文献
116.
共享单车失效停放区使得用户无法取车或还车,影响共享单车系统运营稳定性。本文基于排队论与马尔科夫链构建了共享单车系统稳定状态平均场方程组并求解稳态解,发现停放区交互作用使得失效停放区对相邻停放区产生需求溢出效应,增加系统失效停放区比率,影响系统运营稳定性。本文以降低系统失效停放区比率目标,引入(M,S)交互策略,调节失效停放区对相邻停放区的交互作用程度。进一步,以算例分析比较相同类型与不同类型停放区交互作用、(M,S)交互策略下共享单车系统的失效停放区比率。结果表明(M,S)交互策略能够有效降低失效停放区比率,提高系统运营稳定性。本研究为共享单车企业运营稳定性决策提供了有价值的参考。 相似文献
117.
TARASENKO V F SITNIKOV A G PANCHENKO A N TEL'MINOV A E GENIN D E 李殿军 张来明 姜可 谢冀江 SARKISOV S Yu BEREZNAYA S A KOROTCHENKO Z V KAZAKOV A V 《中国光学与应用光学文摘》2011,(4)
描述了使用电感储能发生器和半导体转换开关泵浦的工作波长为10.6μm的高效CO2激光器。给出了激光泵浦的非线性晶体GaSe和GaSe0.7S0.3的二次谐波振荡的实验数据和理论估算结果。结果显示,GaSe晶体在输入能量为180mJ时,最大能量转换效率为0.38%,倍频激光的峰值功率为8 kW。 相似文献
118.
Xu Xiaoyong Zheng Guoguang Wang Qing-an 《Journal of Quantitative Spectroscopy & Radiative Transfer》2005,92(1):61-72
This paper experimentally and theoretically examines the scattering properties of simulated non-spherical hydrometeors including water oblates, ice oblates and ice sphere-cone-oblates, in terms of the backscattering cross-section and the differential reflectivity. The experimental measurements of the backscattering cross-sections of non-spherical hydrometeor samples were performed in the Electromagnetic Scattering Laboratory of China National Space Industrial Corporation. Meanwhile, the backscattering cross-sections have been computed with the transition (T) matrix method. The theoretical results are compared with the experimental data, showing that the calculations are consistent with the observations in general. Experimental and theoretical analyses indicate that the backscattering cross-section of non-spherical particles increases as the particle size parameter increases, and fluctuates when the sizes are larger under the effect of resonance scattering. Differential reflectivity ZDR of water oblates in natural rainfall is always greater than 0 dB whereas ZDR of hailstones may be negative. There is a good linear relationship between differential reflectivity and aspect ratio of a particle. These derivations agree with the literature and can be used to identify the presence of hail particles and distinguish between plate-type and columnar-type hydrometeors. In this study, the measuring experiment and the T-matrix method calculations for the scattering of simulated raindrop and ice particles are also briefly described. 相似文献
119.
120.
从所周知,循环卷积和离散富里叶变换(DFT)可以互相计算,只要得到其中一个的快速算法就可导出另一个的快速算法。循环卷积目前已有乘法量为O(N)的最佳算法(特别是当N较小时),为此关键是如何将DFT转化为循环卷积,当DFT的长度N=p(p为素数),Rader利用有限域GF(p)的乘法群是循环群就成功地将p点DFT转化为Q(p)(F(p)为户的Euler函数)点循环卷积;当N=p~e时,由于商环Z/(p~e)存在F(p~c)阶元素,人们也成功地将p~c点DFT转化为P(p~(c-1))一系列循环卷积,即一个y(p~c)点循环卷积,二个P(p~(c-1))点 相似文献