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11.
Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used for the characterization of a partially transesterified poly(beta-hydroxyalkanoate), PHA, polymer produced by the bacterial strain Alcaligenes eutrophus using saponified vegetable oils as the sole carbon sources. The transesterification was carried out separately under acidic and basic conditions to obtain PHA oligomers weighing less than 10 kDa. The intact oligomers were detected in their cationized [M + Na](+) and [M + K](+) forms by MALDI-TOFMS. A composition analysis, using the MALDI-TOF spectra, indicate that the oligomers obtained via acid catalysis were terminated with a methyl 3-hydroxybutyrate end group, and those obtained by base catalysis had a methyl crotonate (olefinic) termination. In addition to HB (hydroxy butyrate), the oligomers were found to contain a small percentage of HV (hydroxy valerate). This was independently confirmed using gas chromatography/mass spectrometry (GC/MS). In comparison, the analysis of a commercial PHA polymer, transesterified under identical conditions, only showed the presence of HB, i.e. a pure PHB homopolymer. Copyright 1999 John Wiley & Sons, Ltd.  相似文献   
12.
利用Legendre正交多项式作为形函数基底函数,开发了两种新型的通用p型板单元.单元矩阵的解析积分保证了p型有限单元解的精确性及单调收敛性,计算实例表明所开发的p型有限单元计算结果随基底函数中附加项数量的增加而快速收敛,且它们的计算精度远高于一般线性单元.另外,p型板单元不使用缩减积分也能分析薄板的振动问题,利用它们收敛率高的特点,分析了结构破坏的时频特性.p型有限单元仿真结果与实测结果良好的吻合证明了它们用于结构振动响应分析的有效性.  相似文献   
13.
向能军  沈宏林  许永  高茜  梁万里  龚孟濂 《化学学报》2008,66(11):1361-1365
通过多步反应合成了一种新型的具有“双极(bipolar)”性质和发光性能的以N原子为中心的星型有机小分子低聚物——三(4-(5-(4-(5-(4-(二苯胺基)苯基)-1,3,4-噁二唑-2)苯基)-1,3,4-噁二唑-2)苯基)胺. 用1H NMR, MS和元素分析进行了表征, 研究了化合物的热稳定性和固体粉末的光致发光性质, 并用循环伏安法测定了其电化学性能. 结果表明, 这种合成的同时具备空穴传导和电子输入双重功能基团的星型有机小分子光致发光性能优良(量子效率92%), 热稳定性好, 可以作为制作有机电致发光器件的候选材料.  相似文献   
14.
Geometry optimization and harmonic vibrational frequency calculations at the CASSCF, MP2 and CCSD(T) levels with basis sets up to 6-311G(2df) quality were carried out on the X1Σ+states of FCN and ClCN and the X2Π and A2Σ+ states of their cations. Adiabatic ionization energies were calculated up to the CCSD(T)/6-311G(3df)//CCSD(T)/6-311G(2d) level. Some B3LYP calculations were performed also for the ground states of the neutral molecules and the cations. Franck-Condon simulations were performed for the first two bands in the He I photoelectron spectra of FCN and ClCN by employing the ab initio computed geometries and frequencies. By comparing the observed and the simulated spectra obtained from different CN and CX (X = F or Cl) ionic bond lengths chosen on the basis of the ab initio computed values, the following structural parameters are obtained for the two lowest-lying states of FCN+ and ClCN+ (the method of deriving the uncertainties is described):  相似文献   
15.
We examine the relative efficiencies of three- algorithms for performing Brownian Dynamics simulations without many-body hydrodynamics. We compare the conventional Brownian Dynamics algorithm of Ermak (CBD), Smart Monte Carlo (SMC) which incorporates Boltzmann sampling into essentially a CBD procedure, and the Stochastic Runge Kutta (SRK) method. We show, using the repulsive potential φ(r) = ε(σ/r) n , where n = 36 and 72, that the SRK algorithm gives the most accurate short-time dynamics for the mean-square displacements. The SRK algorithm static and dynamical properties converge better with a reducing time step to the exact values, than those generated by the CBD algorithm; giving efficiency gains typically of a factor of 3–4. Both CBD and SMC have the incorrect sign for the first correction term to the mean square displacement in a time step, whereas the SRK algorithm gives essentially the exact solution to order Δt 2, where Δt is the simulation time step. In fact, these correction terms are almost equal and opposite in sign. Expressions for these terms were derived in terms of the average interaction energy per particle. The force, shear and bulk stress autocorrelation functions were calculated. The average energy per particle and time correlation functions at short time have values in excess of the exact values, while the corresponding quantities for SRK are below this. This difference in behaviour can be traced back to the extent of compliance of the particle trajectories with the exact expansion of the Smoluchowski equation. The accuracy, at a given value of the time step, of the stochastic algorithms can significantly depend on the form of the interaction potential between particles. It is also demonstrated that the long time limits of various correlation functions are fairly insensitive to a particular scheme (SRK or CBD) used in the simulations. All the correlation functions have a stretched exponential region at intermediate to long times, and the values of the exponents on density and force law steepness have been determined.  相似文献   
16.
三种新的铕(Ⅲ)三元配合物的合成及发光性质研究   总被引:4,自引:0,他引:4  
合成了吡嗪[2,3-f] 并邻菲罗啉及其一系列衍生物,作为第二配体,并以二苯甲酰甲烷为第一配体,合成了3种新的铕(Ⅲ)三元配合物.通过元素分析、红外光谱、核磁共振光谱确定了它们的组成,研究了三种配合物的热稳定性、成膜性能和光致发光性能(发光强度、荧光量子效率和寿命),并初步从理论上探讨含有不同基团的第二配体的结构对铕(Ⅲ)配合物发光的影响,结果表明:这三种铕(Ⅲ)三元配合物均为优良的红色发光材料,而且在真空条件下均形成均衡的薄膜,这为以这三种铕(Ⅲ)配合物作为发光层材料制作有机电致发光器件提供了认识基础.  相似文献   
17.
18.
Light transmission spectra of THF solutions of poly (C_(60)-co-methyl methacrylate)s andpoly (C_(60)-co-styrene)s continuously red-shift with increasing concentration. Formation offullerene nanoclusters may be responsible for the unusual spectral shift with concentration.It has long been scientists' dream to "tune" material's properties by simple means, and theC_(60)-containing polymers represent such a group of novel materials whose optical propertiesare predictably and reversibly tunable by a simple change in concentration.  相似文献   
19.
合成了苯基乙烯基亚砜 (PVSO) ,并以萘 碱金属作为引发剂、丁二酸酐作为终止剂 ,进行阴离子聚合 ,制备出单分散、端羧酸盐的苯基乙烯基亚砜的遥爪聚合物 ,聚合物的功能度基本在 1 6 0以上 .在真空加热条件下 ,聚苯基乙烯基亚砜发生侧基热消除反应 ,从而获得末端为羧酸盐的遥爪聚乙炔  相似文献   
20.
单向纤维增强环氧复合材料的热膨胀系数   总被引:1,自引:0,他引:1  
本文在123—413K的温度范围内,测量了单向玻璃纤维和碳纤维增强环氧树脂复合材料α_P~C(纤维方向),α_(T1)~C(横截面板厚度方向),α_(T2)~2(横截面板宽度方向)三个热膨胀系数.研究了纤维体积分数V_f和纤维表面处理对α_P~C和α_T~C的影响.结果表明,α_P~C在整个温度范围内不受纤维表面处理影响,随V_f的增加而减小,变化规律符合Schapery方程.对于横向热膨胀系数,在T<基体玻璃化温度T_g~m时,有α_(T1)~C α_(T2)~C=α_(T)~C,在V_f 0.3时,有α_T~C>α_m(基体的),而后随V_f的增加而减小,经分析也符合Schapery理论.在T>T_g~m时,α_(T1)~C和α_(T2)~C呈各向异性,特别在纤维表面未处理时更为显著.形态研究表明,其原因是在纤维铺层之间存在片状树脂层.  相似文献   
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