小角x射线散射结晶聚合物结构的研究

利用结晶聚合物的“三相结构”模型计算了结晶聚合物的一维电子密度相关函数,结论是三相模型的片层厚度和不变量与两相结构的意义不同.利用计算结果分析了一批样品的结构参量,发现用Ruland方法得到的结晶过渡层的厚度与用一维电子密度相关函数的结果是一致的.用Bragg定律求出的结晶聚合物的长周期与相关函数法长周期相差很多.这是因为两种分析结晶过渡层厚度的方法都是以样品电子密度的不均匀区为基础的,本质是一致的.但是Bragg法的长周期与相关函数法的长周期代表的范围不同 关键词： 小角x射线散射 结晶聚合物 三相结构 相关函数     

解偶联剂CCCP对莱茵衣藻光照产氢过程的调控

本文研究莱茵衣藻在含硫和缺硫连续光照条件下, 不同浓度的CCCP对PSⅡ光化学效率、 光照产氢、 光合放氧以及光能的吸收和转换效率等的影响和调控规律.     

对甲苯磺酸催化合成二乙氧基甲烷

对甲苯磺酸催化合成二乙氧基甲烷;二乙氧基甲烷;对甲苯磺酸;催化合成;乙醇;甲醛     

A N-heterocyclic carbene derived highly regioselective ambident C-C-S and C-C-N 1,3-dipolar system

N-Heterocyclic carbene derived 2-phenylthiocarbamoyl benzimidazolium and imidazolinium inner salts are a unique ambident C-C-S and C-C-N 1,3-dipolar system able to undergo highly efficient and regioselective cycloaddition with dimethyl acetylenedicarboxylate and ethyl propiolate to furnish, respectively, spiro[imidazole-2,3'-thiophene] and spiro[imidazole-2,3'-pyrrole] derivatives in good to excellent yields.     

Effect of multi-walled carbon nanotubes on crystallization behavior of poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

The effect of multi-walled carbon nanotubes on the crystallization behavior of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) has been investigated. The results have shown that carbon nanotubes (CNTs) act as an effective heterogeneous nucleation agent, inducing an increase in crystallinity and crystallite sizes. Comparing with the double melting peaks in pure PHBV, there is only one peak in the melting curves of nanocomposites. The isothermal crystallization kinetics of PHBV and its nanocomposite containing 0.5% CNTs were examined based on Avrami equation, indicating that the crystallization half-time decreases while the overall crystallization rate k increases dramatically with CNTs addition. The spherulitic nucleation and growth kinetics were also discussed grounded on Lauritzen–Hoffman equation. It is found that there is a spherulitic growth rates (G) maximum within selected temperature range in our study. Also, the temperatures corresponding to G maximum shift to a high level with addition of CNTs. The parameters of the equilibrium melting temperature T_m⁰ T_m^0 , the nucleation parameter K _g , the lateral surface free energy σ, the fold surface free energy σ _e , and the work of chain folding q of PHBV and its composite containing 0.5% CNTs were all calculated. The reductions of K _g , σ _e and q values of nanocomposite are in agreement with the fact that the crystallization rate of PHBV increases greatly by addition of CNTs.     

Carboxyester hydrolysis catalyzed by a novel dicopper(II) complex with an alcohol-pendant macrocycle

A novel hexaaza macrocycle bearing two hydroxyethyl pendants (L), 3,6,9,16,19,22-hexaaza-6,19-bis(2-hydroxyethyl)tricyclo[22,2,2,2(11,14)]triaconta-1,11,13,24,27,29-hexaene, was synthesized as a potential binucleating ligand. The corresponding Cu(II) complex [Cu(2)LCl(2)]Cl(2) small middle dot5.5H(2)O was isolated as a blue crystal, triclinic, space group P with a= 9.4920(19) A, b = 4.783(3) A, c = 16.553(3) A, alpha = 63.87(3) degrees, beta = 86.10(3) degrees, gamma = 83.8(3) degrees, V = 2072.8(7) A(-3), Z = 2, R1 = 0.0658, and wR2 = 0.1839. Both Cu ions adopt the geometry of a distorted trigonal bipyramid in a pentacoordinated environment. A complexation study on the novel title complex has revealed that the alcoholic OH groups of the complex Cu(2)L exhibit an obvious acidity with rather low pK(a) values at 25 degrees C. The Cu(II)-bound alkoxides, which act as reactive nucleophiles toward the hydrolysis of 4-nitrophenyl acetate in 10% (v/v) CH(3)CN at 25 degrees C, with I = 0.10 (NaNO(3)) and pH 9.3, have shown a second-order rate constant, 0.41 +/- 0.02 M(-1) s(-1), a value that is approximately 10 times greater than the corresponding value for the mononuclear Cu(II) complex formed by a relatively simple tripodal ligand (L1). The pH-rate profile gave a sigmoidal curve. The possible catalytic mechanism has been proposed, and the reason for the high catalytic activity of the title complex has been discussed.     

An unprecedented tandem 1,3-dipolar cycloaddition-cheletropic elimination: a facial approach to novel push-pull olefins

The interaction of 2-(phenylthiocarbamoyl) imidazolium inner salts with dimethyl acetylenedicarboxylate produced dimethyl 2-(imidazolin-2-ylidene)-3-thioxobutanedioates in moderate to good yields. The process involved a tandem reaction comprising a 1,3-dipolar cycloaddition and an unprecedented cheletropic elimination of the phenyl isonitrile from a 2-phenyliminodihydrothiophene moiety. NMR and X-ray diffraction studies confirmed that the 2-(imidazolin-2-ylidene)-3-thioxobutanedioates are novel push-pull olefins and have potential applications in nonlinear optical materials.     

Substrate-controlled and site-selective [3+2] cycloadditions of N-heterocyclic carbene derived ambident dipoles

2-aryl thiocarbamoyl benzimidazolium and imidazolinium inner salts derived from benzimidazole and imidazoline carbenes are unique ambident C-C-S and C-C-N 1,3-dipolar systems, which undergo highly efficient and site-selective cycloaddition reactions with dimethyl acetylenedicarboxylate or dibenzoylacetylene to furnish spiro(imidazole-2,3'-thiophene) derivatives in excellent yields. When treated with ethyl propiolate, methyl acrylate or acrylonitrile, spiro(imidazole-2,3'-pyrrole) derivatives were formed in good yields. Theoretical studies revealed an asynchronous concerted mechanism for both the C-C-S and C-C-N 1,3-dipolar cycloaddition reactions. The site selectivity in the [3+2] cycloaddition reaction of ambident 1,3-dipoles was predictably regulated by both the electronic and steric effects of dipolarophiles.