疏水-亲脂相互作用对化学反应性的影响 7: 十四元和十八元环的邻基参与

本工作研究了不同链长的ω-取代羧酸对硝基苯酯p-NO2-C6H4OCO(CH2)n-1Y(简称n-Y,n=17,13,11;Y=SH,H,OH,Br和SCH3)在Me2SO-H2O溶剂体系(有机溶剂体积组成分数φ=0.40,0.45,0.50,0.55)中的水解动力学,观察到疏水-亲脂作用影响下,由于13-SH和17-SH长链分子自身绕曲,可以实现十四元环和十八元环的大环邻基参与,至于11-SH的水解,则观察不到十二元环的邻基参与.因此,这些受物的邻基助效确与链长有关.溶剂组成对此现象也有影响.     

THE Λ-Λ INTERACTION AND THE STRUCTURE OF THE Λ HYPERNUCLEI ΛΛ6 HE AND Λ9 BE

In this paper, sae found a form of Λ-Λ interaction which gives the correct binding energy of double Λ's in ΛΛ⁶He. The energy contours and density distributions of the hypernuclei ΛΛ⁶He and Λ⁹Be are given.     

Synthesis of 6-aryl-3-cinchophenyl-1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles

In recent years, fused heterocycles have been found to possess many unique properties in synthesis and pharmacology. Especially, 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles derivatives have been attracting much attention of chemists and pharmacologists because of their broad-spectrum biological activities such as antibacterial¹, hypotensive and CNS depressant² activities. We have prepared some 3,6-substituted 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazoles and found that these compounds exhibited antimacrobial, insecticidal and promote plant growth.^3-5 Cinchophen had been used widely as medicine in clinic,but has been obsolete in recent years due to its by-effect. In order to seek for other uses of cinchophen, as a continuation of our preceeding studies, we used cinchophen as the starting material to synthesize ten new 6-aryl-3-cinchophenyl-l,2,4-triazolo[3,4-b]-l,3,4-thiadiazoles 5a-j. Compound 1 was prepared by the reaction of cinchophen and ethanol in the presence of sulfuric acid. 1 then reacted with hydrazine hydrate in absolute ethanol to give 2 which yielded 3 on treatment with CS₂ and KOH. On refluxing of 3 with excess hydrazine hydrate, 4 was obtained. 4 reacted with various substituted benzoic acids in the presence of POCl₃ to afifort 5a-j.     

Studies on Semisynthesis and Antibacterial Activities of 7β-(l-aryl-5-methyl-l,2,3-triazol-4-acylamido)-3-(2-substituted-1,3,4-oxadizol-5-thiomethyl) Cephalosporin

Cephalosporin derivatives have been a subject in the field of β-lactam antibiotics due to their broad-spectrum biological activities in recent years. Chemical manipulation of the C-3 and 7β-position in the cephalosporin molecule has resulted in the discovery of numerous novel antibiotics. In general, the C-3 position of the cephalosporin were substituted with heterocyclyl sulfurs or nitrogens and the 7β-position were substituted with heterocycles or aryl¹. The side chain at 7β-position determined their antibacterial activities and antibacterial spectrum, moreover, the substituted groups at C-3 position not only affect pharmacokinetic properties, but antibacterial activities and antibacterial spectrum as well.² Roche Reiner company found that the activities of cephalosporin can be improved by changing the R of RCONH- at 7β-position of 7ACA and introducing various thioazoleheterocycles into C-3 position of it.³ It is no doubt that these heterocycles increased their activities and wided their antibacterial spectrum. In the course of our studies on the modification of cephalosporin, our efforts have been focused on introducing heterocycles into C-3 and 7β-position of 7ACA with the hope of achieving better antibiotics.     

两性-非离子混合型表面活性剂在金属-铬天青S显色反应中的应用研究

使胶束增溶分光光度法在保持已有灵敏度的基础上,再提高其显色反应的选择性,是一个既有理论意义又有应用价值的新课题.作者在研究两性表面活性剂的分析应用时发现,如在其显色体系中同时引入非离子表面活性剂Triton X-100,则对体系的光化学性质有明显影响,有的灵敏度提高,有的选择性改善.实验表明,两性-非离子混合型表面活性剂的存在,可以扩大不同显色体系的差别,对提高增溶光度法的灵敏度,特别是选择性,是一种有效的途径.基于此,作者曾在钪、铀、钍等元素的分析测定方面作过一些研究. 本文以金属-铬天青S(CAS)-烷基二甲基乙酸铵两性表面活性剂的显色反应为例,研究非离子表面活性剂Triton X-100在体系中的作用;以及两性表面活性剂与大过量Triton X-100共存,提高CAS显色反应选择性的可能性;并对其作用机理进行初步探讨.     

螺旋构象的徽环境效应——6.在二甲基亚砜-水混合溶剂体系中糖淀粉包结作用对对硝基苯酚酯水解的催化效应

我们研究了在DMSO-H₂O混合溶剂内,在糖淀粉存在或不存在的条件下,对硝基苯酚乙酸酯、戊酸酯、辛酸酯、十二酸酯和十六酸酯的水解反应,所用的缓冲液体系为硼酸盐和碳酸盐两种.除乙酸酯外,糖淀粉对其它受物水解的催化都遵循饱和动力学.由动力学实验得出的络合物解离常数K_d和络合物催化效率κ_c/K_d^*;表明:包结络合物的稳定性随受物链长的增长而增大,与以葡萄糖为催化剂的二级反应速度常数κ₂相比,糖淀粉对十二酸酯和十六酸酯催化效率分别增加了280和5600倍.催化效率的来源可归因于糖淀粉宿主螺旋内穴提供的微环境效应.在硼酸钠缓冲液体系中,表观速度常数K_obs—糖淀粉浓度曲线在高浓度区域下降而偏离饱和动力学.实验证明,这是由于糖淀粉分子间或分子内烃基与硼酸根离子配位而引起的,并可近似地处理为“硼酸根离子加宿主抑制”机制,从而解出抑制络合物解离常数K_d^'.当用碳酸盐缓冲液代替硼酸盐缓冲液时,则得到典型的非抑制性饱和动力学曲线.     

螺旋构象的微环境效应——1.羧甲基糖淀粉钠对具有疏水性长链烷基的受物的包结作用

本文报道了具有类似环葡萄糖疏水内穴特性但长度及内穴尺寸为可变化的羧甲基糖淀粉钠(Na-CMA)螺旋构象对具有长链烷基的受物:十六烷基三甲基氯化铵(CTACl)、十二烷基三甲基碘化铵(LTAI)和十二烷基硫酸钠(NaLS)的包结作用.使用表面张力法求得Na-CMA—CTACl包结常数在1.27～2.30×10⁴M^-1左右,Na-CMA—LTAI为0.52×10³M^-1,Na-CMA—NaLS为0.73×10³M^-1,表明与阴或阳离子的受物均可形成稳定包结络合物,稳定程度由受物烃链疏水性决定.Na-CMA的最大结合部位对于CTACl,LTAI,NaLS分别为7.7,9.8,10与形成6-螺旋和受物分子相对长度推算出的数值很接近.从Na-CMA—CTACl包结常数与温度的关系求得包结过程的热力学参数为ΔG₂₉₈=-5.7kcal/mol,ΔH₂₉₈=3.5kcal/mol,ΔS₂₉₈=7.6 e.u..说明包结驱动力不同于典型疏水作用的熵控制和环葡萄糖包结的焓控制机制.根据粘度和表面张力的测定提出了这种包结过程伴随着Na-CMA链从紧密线团至间断螺旋的构象变化,反映出Na-CMA与环葡萄糖不同的特性,看来更适合于作为生物大分子识别受物的模型.