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71.
72.
Using ClO2 as chemiluminescence (CL) oxidant, a novel homogeneous CL system in neutral and near neutral aqueous solution is proposed in this paper. ClO2 could oxidize sulfite in pH 5.0–8.5 acetate buffer to produce CL emission, and pipemidic acid could sensitize the CL system. The ClO2–SO32−–pipemidic acid reaction was used as a model CL system and explored the possibility of highly active and eco-friendly ClO2 being used as CL oxidant in neutral and near neutral aqueous solution. Combined with flow-injection analysis, the proposed CL system was applied to the automated dissolution testing of pipemidic acid tablet. Compared with the common strong acidic or strong basic CL system, this proposed CL owns its advantages. 相似文献
73.
Study of urinary nucleosides as biological marker in cancer patients analyzed by micellar electrokinetic capillary chromatography 总被引:10,自引:0,他引:10
Thirteen normal and modified nucleosides, primarily degradation products of transfer ribonucleic acid (tRNA), were evaluated as potential tumor markers for cancer patients. Their urinary concentrations were determined by means of micellar electrokinetic capillary chromatography (MEKC) in the urine from 54 healthy adults and 70 cancer patients, then quantitatively expressed as a function of creatinine excretion. It was found that urinary nucleosides for cancer patients were on the average significantly higher than those for healthy controls, however, no significant differences were found between male and female or between different ages. Based on 13 urinary nucleoside concentrations, principal component analysis (PCA) could be used to classify 72% of cancer patients from the healthy controls. The present study shows that the precise measurement of urinary nucleosides by MEKC in combining with PCA technique may provide a clinically useful approach for diagnosis of cancer. 相似文献
74.
过渡金属酞等配合物(MPC)用手均相液相氧化中作催化剂已有不少报导,象许多均相催化剂一样,MPC用于均相反应存在着难于从反应体系中分离出来的问题.把均相配合物催化剂固载在无机氧化物如硅股或有机高分子载体上是解决这一问题的一种方法.我们曾尝试把MP。固载在分子筛载体和硅胶载体上,并用ESR研究其对O2的活化作用[1,2].本文报导MPc通过共价键键联固载在SiO2上,并研究其对O2的活化作用.1实验部分1.1试剂HSIC13为日本东京化成株式会社产品,二级试剂·发烟硫酸(SO。质量分数大于20%)为分析纯试剂.PCl5为化学纯试… 相似文献
75.
选择性氧化含氰基的对硝基苯硫醚 总被引:2,自引:0,他引:2
选择性氧化含氰基的对硝基苯硫醚岳国仁,王建华,张正(南京大学化学系南京210008)关键词含氰基硫醚,选择性氧化,四水合过硼酸钠据报道[1]对硝基苯磺酰基乙腈的合成,反应时间长,可采用四水合过硼酸钠(NaBO3·4H2O)作为氧化剂,受到重视[2,3... 相似文献
76.
利用自组装的方法,实现碳纳米管的有序排列可以充分有效的促进碳纳米管在各个领域的应用。本文从自组装所依赖的驱动力着手,介绍了国内外近几年来基于功能化碳纳米管的自组装开展的研究工作及取得的成果,重点介绍了通过配位作用、静电力及氢键、亲水/疏水相互作用等实现的自组装。 相似文献
77.
Cycloaddition of carbon dioxdie and propylene oxide to propylene carbonate catalyzed by tetra-tert-butyl metal phthalocyanine in the presence of tributylamine(TBA) shows higher yield than catalyzed by unsubstituted metal phthalocyanine.Comparing different catalysts of diverse metals,(t-Bu)4PcMg is more active than (t-Bu)PcFe ,But(t-Bu)4PcCo and (t-Bu)4PcNi only have low catalytic activities towards the reaction.Moreover,the yield will increase as the temperature increases. 相似文献
78.
Xiu Hui Lu Hai Bin Yu Wei Rong Wu Yue Hua Xu 《International journal of quantum chemistry》2007,107(2):451-457
Mechanisms of the cycloaddition reaction between singlet difluoromethylene carbene and acetone have been investigated with the second‐order Møller–Plesset (MP2)/6‐31G* method, including geometry optimization and vibrational analysis. Energies for the involved stationary points on the potential energy surface (PES) are corrected by zero‐point energy (ZPE) and CCSD(T)/6‐31G* single‐point calculations. From the PES obtained with the CCSD(T)//MP2/6‐31G* method for the cycloaddition reaction between singlet difluoromethylene carbene and acetone, it can be predicted that path B of reactions 2 and 3 should be two competitive leading channels of the cycloaddition reaction between difluoromethylene carbene and acetone. The former consists of two steps: (i) the two reactants first form a four‐membered ring intermediate, INT2, which is a barrier‐free exothermic reaction of 97.8 kJ/mol; (ii) the intermediate INT2 isomerizes to a four‐membered product P2b via a transition state TS2b with an energy barrier of 24.9 kJ/mol, which results from the methyl group transfer. The latter proceeds in three steps: (i) the two reactants first form an intermediate, INT1c, through a barrier‐free exothermic reaction of 199.4 kJ/mol; (ii) the intermediate INT1c further reacts with acetone to form a polycyclic intermediate, INT3, which is also a barrier‐free exothermic reaction of 27.4 kJ/mol; and (iii) INT3 isomerizes to a polycyclic product P3 via a transition state TS3 with an energy barrier of 25.8 kJ/mol. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
79.
Lin Yan Wengang Chai Guanghui Wang Guanli Wu Kaijuan Lu Yue Luo 《Journal of mass spectrometry : JMS》1987,22(5):279-282
During a comparison study of the fast atom bombardment (FAB) and electron impact mass spectra of 1-organyl-2,9,10-trioxa-6-aza-1-silatricyclo[4.3.3.01,6]dodecanes, an unusual ion peak at m/z 164 was noticed in the FAB spectra. Accurate mass measurement indicated that m/z 164 corresponds to protonated 1-[N,N-bis(2-hydroxyethyl)amino]-1-propanol (BHAP), which is produced by a ring-rupture reaction. Further experiment showed that the intensity of the [BHAP + H]+ ion peak increased markedly as the 7keV Ar0 bombardment proceeded, suggesting a FAB-induced reaction. The possible mechanism is also discussed. 相似文献
80.
The coordination of silver cation to diphosphene Mes*P=PMes* ( 1 , Mes* = tBu3C6H2) was investigated in detail. The reaction of 1 with Ag[Al(ORF)4] (ORF = OC(CF3)3) in the ratios of 2 : 1, 3 : 2 and 1 : 2 led to the formation of the first cationic silver linked diphosphene complexes 2 — 4 . Complexes 2 and 3 contain two and three diphosphene molecules linked by the linear Ag(I) cation, respectively, and they feature unusual zig‐zag topologies. Complex 4 is a dinuclear silver complex, and each Ag(I) center features a tetrahedral geometry, coordinated by one phosphorus atom of diphosphene 1 and three chloro atoms of two CH2Cl2 molecules. 相似文献