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61.
62.
本文报导共价链相连的X-P-Y“三合板”型化合物在二甲基甲酰胺(DMF)和苯溶液中的发光特性.结果发现:引入取代基X=Cl—,CH3O—和Y=苯、硝基苯对中心卟啉的吸收和荧光光谱均无明显影响,仅其峰值频率将因溶剂不同而有所偏移.此外,由Cl—取代的卟啉—苯的荧光强度总比CH3O—取代时高;若将Y取代基由苯改换为硝基苯时,将使CH3O—P—Y化合物的荧光增强,但在Cl—P—Y化合物中则出现相反的趋势.不论在何种化合物中,在Y取代基中的苯环上引入NO2—基后,均可使其消光系数减小,而且当硝基在邻位取代时,这一效应更为显著.所有这些变化规律均不因溶剂不同而异.如果我们认为X—P—Y化合物的发光强度变化和其中心的卟啉大环上的π电子云密度偏移有规律性的关联,那么上述的一些取代基效应是可以理解的.进而,我们认为:本文所报导的事实将有助于充实巧妙设计高效利用太阳能的分子体系的科学依据. 相似文献
63.
Optimal birth control of population dynamics 总被引:9,自引:0,他引:9
The authors studied optimal birth control policies for an age-structured population of McKendrick type which is a distributed parameter system involving 1st order partial differential equations with nonlocal bilinear boundary control. The functional analytic approach of Dubovitskii and Milyutin is adopted in the investigation. Maximum principles for problems with a free end condition and fixed final horizon are developed, and the time optimal control problems, the problem with target sets, and infinite planning horizon case are investigated. 相似文献
64.
速差动力学同时测定铬(Ⅵ)和铬(Ⅲ)的研究 总被引:6,自引:0,他引:6
基于铬(Ⅵ)和铬(Ⅲ)与5′-硝基水杨基芝光酮,溴化十六烷基三甲铵的显色反应速度差异,在pH5.7~6.2和65℃加热条件下用速差动力学比例方程法同时光度测定铬(Ⅵ)和铬(Ⅲ),两配合物均为假一级动力学形成反应,表观活化能量分别为49.09kJ/mol和103.68kJ/mol,测定铬(Ⅵ)和铬(Ⅲ)的线性范围为分别为0~0.20mg/L和0~0.65mg/L。方法用于废铬酸洗液中铬(Ⅵ)和铬(Ⅲ 相似文献
65.
总结毛者提出的线型缩聚中当量系数的新定义及引入缩聚体系单体平均官能度的新方法,本文总结出了一套讲授数均聚合度计算问题的简单方法。 相似文献
66.
在硼氢化钾碱性溶液中对金属氢化物(MH)电极的表面进行化学还原处理,提高了MH电极的放电容量、活化性能和电催化活性.用其为负极组装的AA型MH-Ni电池进行了封口化成,电池放电容量达到1150mAh,5C下电池的放电容量达到0.2C下容量的80%以上,电池在1C100%DOD(放电深度)充放电条件下,循环寿命由原来的100次左右提高到200次以上 相似文献
67.
Rate constants (k's) of the thermal cyclodimerization of ten meta-substituted trifluorostyrenes (m-Y-TFS's) have been measured in the temperature range 110–160°C. On the basis of these k's and the σmb values derived from 19F NMR data the spin-delocalization substituent constant σ˙m values of these ten meta-substituents have been calculated. The averaged σ˙m values are: m-Et, 0.09; m-t-Bu, 0.11; m-F, 0.03; m-Cl,?0.05; m-Br, 0.12: m-CF3, ?0.07; m-OMe, 0.10; m-NO2, ?0.002; m-CN, 0.11 and m-CO2Me, 0.08. Both the smallness of these values and the nonexistence of correlation between Hammett-Type polar σX and these σ˙m values support our belief that the σj?J approach is reliable and trustworthy. 相似文献
68.
Liu H Hu Y Yang S Guo W Lu X Zhao L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(21):6392-6406
We report herein a comprehensive study of photoinduced reactions in complexes of Mg+ with primary (n-propyl- and isopropylamine) and secondary amines (dipropyl- and diisopropylamine) in the spectral range of 230-440 nm. Similar to the methyl- and ethylamine complexes studied previously, N-H bond activation of these complexes is very unfavorable. Instead, the C(alpha)-C, C-N, and C(alpha)-H bond-cleavage photoproducts are observed after photoexcitation of the Mg+ complexes (3(2)P<--3(2)S). For Mg+(primary amine) complexes, for example, Mg+-NH2CH2CH2CH3, and Mg+-NH2CH(CH3)2, the photoproducts resulting from C(alpha)--C rupture prevail after P(z) and charge-transfer excitations, whereas the Mg+ photofragment is predominant upon P(x,y) excitation. However, with further N-alkyl substitution, as in Mg+(secondary amine) complexes, for example, Mg+-NH(CH2CH2CH3)2 and Mg+-NH[CH(CH3)2]2, a novel intracomplex C-C coupling photoreaction dominates on P(x,y) excitation of Mg+, which is believed to arise from Mg+* insertion into the C-N bond. With P(z) and charge-transfer excitation, the Mg-R elimination photoproducts, arising from C(alpha)-C bond cleavage, predominate. The energetics and possible mechanisms of the intracomplex photoreactions are analyzed in detail with the help of extensive quantum mechanics calculations. 相似文献
69.
The qualitative analysis of bufadienolides in the Chinese drug ChanSu was performed using high-performance liquid chromatography with atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS/MS). Bufadienolides are the major bioactive constituents of ChanSu, which is used to treat heart failure and cancer in traditional Chinese medicine. The APCI-MS fragmentation behavior of bufadienolides was studied. For bufadienolides with only hydroxyl substituents, the fragmentation was characterized by successive eliminations of H(2)O and CO molecules, and the profile of MS/MS product ions was correlated with the number of hydroxyl groups. If a C-16 acetoxyl group was present, the fragmentation of [M+H](+) ions was triggered by initial loss of 60 Da (HOAc). The elimination of CO was significant for bufadienolides with a 19-formyl group, and the 19-hydroxyl group could be characterized by the loss of 30 Da (HCHO). These fragmentation rules were applied to the identification of bufadienolides in a methanolic extract of ChanSu, which was separated on a C(18) column with gradient elution. A total of 35 bufadienolides were identified, including four new constituents. The method established here facilitated the convenient and rapid quality control of ChanSu crude drug and its pharmaceutical preparations. 相似文献
70.
Quantitative structure-activity/property relationships (QSAR/QSPR) studies have been exploited extensively in the designs of drugs and pesticides, but few such studies have been applied to the design of colour reagents. In this work, the topological indices A(x1) - A(x3) suggested in this laboratory were applied to multivariate analysis in structure-property studies. The topological indices of 43 phosphone bisazo derivatives of chromotropic acid were calculated. The structure-property relationships between colour reagents and their colour reactions with cerium were studied using A (x1 a (x)3) indices with satisfactory results. The purpose of this work was to establish whether QSAR can be used to predict the contrasts of colour reactions and in the longer term to be a helpful tool in colour reagent design. 相似文献