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971.
972.
Among the polyhedral [closo-BnHn]2- ion series (n = 5-12 inclusive) the aromatic [closo-B10H10]2- ion is both readily available and quite reactive. Among its many reactions which retain its cage structure one finds the oxidative dimerization reaction in which two [closo-B10H12]2- ions each formally lose a hydride ion and undergo dimerization of the resulting [closo-B10H9]- ions to produce the [trans-B20H18]2- ion. The two-component [closo-B10H9]- ions of the latter are linked together by a pair of unique B-B-B bonds which provide unprecedented reactivity to the structure. Among these reactions are the two-electron reduction to a set of three interconvertible [B20H18]4- ions having intercage B-B bonds and the related reductive substitution reaction in which [trans-B20H18]2- undergoes attack by nucleophile, L, to produce [B20H18L]2-. The latter species is formally a substituted [B20H19]3- (L = H) ion formed by B-B bond protonation of one of the isomeric [B20H18]4- ions. These and a variety of novel reactions are described here along with interrelated reaction mechanisms considered for the first time. 相似文献
973.
Linear scaling local correlation approach for solving the coupled cluster equations of large systems
A linear scaling local correlation approach is proposed for approximately solving the coupled cluster doubles (CCD) equations of large systems in a basis of orthogonal localized molecular orbitals (LMOs). By restricting double excitations from spatially close occupied LMOs into their associated virtual LMOs, the number of significant excitation amplitudes scales only linearly with molecular size in large molecules. Significant amplitudes are obtained to a very good approximation by solving the CCD equations of various subsystems, each of which is made up of a cluster associated with the orbital indices of a subset of significant amplitudes and the local environmental domain of the cluster. The combined effect of these two approximations leads to a linear scaling algorithm for large systems. By using typical thresholds, which are designed to target an energy accuracy, our numerical calculations for a wide range of molecules using the 6-31G or 6-31G* basis set demonstrate that the present local correlation approach recovers more than 98.5% of the conventional CCD correlation energy. 相似文献
974.
A beta-iron oxyhydroxide (FeOOH) was synthesized via a hydrolyzing route and investigated as a lithium intercalation host.
It delivers a capacity of about 170 mAh/g and exhibits good cycling performance when charged/discharged in the voltage range
from 1.6 V to 3.3 V. For the first time we have confirmed that FeOOH is suitable for using it as a negative electrode for
hybrid electrochemical supercapacitor assembled with an activated carbon positive electrode in 1.0 M LiPF6 ethylene carbonate/dimethyl carbonate (EC/DMC, 1:2 in volume) solution. The cell reveals a slightly sloping voltage profile
from 0 V to 2.8 V and gives an estimated specific energy of 45 Wh/kg based on the total weight of two electrode materials,
approximately two times of carbon/carbon electrochemical double layer capacitors. The hybrid supercapacitor shows a good cycling
performance, it remains approximately 96% of initial capacity after 800 cycles at a charge/discharge rate of 4 C. The capacitor
also shows a desirable rate capability, even at 10 C discharge rate, it holds 80% of capacity compared with that at 1 C discharge
rate. 相似文献
975.
镓(Ⅲ)-茜素氨羧络合剂在碳糊电极上的阳极吸附伏安法研究及应用 总被引:1,自引:0,他引:1
研究了镓(Ⅲ)-茜素氨羧络合剂(ALC)在碳糊电极上的阳极吸附伏安行为,并以此建立了一种高灵敏度、高选择性测定镓的吸附伏安法.在0.12 mol/L HAc-NaAc-0.24 mol/L邻苯二甲酸氢钾底液(pH 4.5)中,-0.10 V (vs.SCE) 富集90 s (或180 s),以250 mV/s扫速线性扫描至0.90 V, Ga3+-ALC在碳糊电极上产生灵敏的与ALC的峰电位相差近230 mV的吸附氧化峰,其二次导数峰电流与镓浓度在5.0×10-10~8.0×10-7 mol/L范围内呈线性关系;富集240 s检出限达3.0×10-10 mol/L(S/N=3).探讨了电极反应机理.该法用于粮食样品中镓的测定,结果满意. 相似文献
976.
An easily prepared and highly efficient monodentate phosphoramidite ligand derived from BINOL, (S)-2,2'-O,O-(1,1'-binaphthyl)-dioxo-N,N-diethylphospholidine, was examined in the hydrogenation of both enamides and alpha-dehydroamino acid derivatives. The catalyst provided remarkably high enantioselectivities (up to 99.6% ee for enamides and >99.9% ee for alpha-dehydroamino acid derivatives). 相似文献
977.
The biological effects of aluminium have received much attention in recent years. Speciation of Al is of basic relevance as it concerns its reactivity and bioavailability. A differential pulse voltammetry (DPV) procedure is proposed for speciation analysis of Al(III) in natural waters and biological fluids using six catechols (L-dopa, dopamine, epinephrine, norepinephrine, caffeic acid and o-benzenediol) as electroactive ligands. The decrease of the DPV anodic peak current for each catechol ligand is linear with the increase of Al concentration. This speciation analysis idea is based on the measurement of the complexation capacity, namely, different affinities of Al(III) for catechols and organic ligands under two pH conditions. The labile monomeric Al fraction (mainly inorganic aluminium) is determined at pH 4.6, while the total monomeric Al fraction is determined at pH 8.5. The principle for Al(III) speciation analysis by an electrochemical method is discussed. This sensitive and simple fractionation method is successfully applied to the speciation analysis of Al in natural waters and the results agree well with those of Driscoll's method. The speciation analysis of Al in biological fluids is also explored and the results are compared with those obtained by ultrafiltration and dialysis. Compared with other speciation protocols the electrochemical method possesses some remarkable advantages: rapidity, high sensitivity, cheap instrumentation and a simple operation procedure. 相似文献
978.
气相色谱法测定三聚氰氯的研究李秀梅赵树岚*田锦霞*孙维星(东北师范大学化学系长春130024)关键词气相色谱法三聚氰氯三聚氰氯(CNCl)3是活性染料的重要中间体及合成树脂、橡胶、塑料等的防老剂,也常用于除草剂、增白剂、药物、炸药等的生产中。传统的分... 相似文献
979.
Xin Sheng Li Yan Xin Chen Yao Jun Zhang Chun Xin Ji Qin Xin 《Reaction Kinetics and Catalysis Letters》1996,58(2):391-396
Hydrogen adsorption-desorption over Mo2N has been studied using a temperature-programmed technique. It is revealed that hydrogen on Mo2N exhibits very high mobility leading to migration of the surface hydrogen into the sublayer and bulk of the sample or the reverse. The surface hydrogen species are preferentially formed when adsorption is carried out below 573 K. On increasing the adsorption temperature to above 573 K, the quantity of hydrogen species located in the sublayer or/and bulk of the Mo2N sample increases significantly. 相似文献
980.
本文建立了2,2’-二羟基联苯(DHP)和4-羟基联苯(HP)的胶束增敏导数-可变角同步荧光同时分析方法,可变角同步扫描所得到的DHP和HP的谱峰位置均对应于常规光谱中的最佳激发-发射位置,经二阶求导后,消除分析谱带干扰,所得的二阶导数-可变角同步光谱即可用于两物质的同时测定,方法快速灵敏,DHP测定范围为0.05~0.5mg/L,HP测定范围为0.07~2mg/L。 相似文献