Effects of thioamide substitutions on the conformation and stability of alpha- and 3(10)-helices

Thiopeptides, formed by replacing the amide oxygen atom with a sp(2) sulfur atom, are useful in protein engineering and drug design because they confer resistance to enzymatic degradation and are predicted to be more rigid. This report describes our free molecular dynamics simulations with explicit water and free energy calculations on the effects of thio substitutions on the conformation of alpha-helices, 3(10)-helices, and their relative stability. The most prominent structural effect of thio substitution is the increase in the hydrogen bond distance from 2.1 A for normal peptides to 2.7 A for thiopeptides. To accommodate for the longer C[double bond]S...H-N hydrogen bond, the (phi, psi) dihedral angles of the alpha-helix changed from (-66 degrees, -42 degrees) to (-68 degrees, -38 degrees), and the rise per turn increased from 5.5 to 6.3 A. For 3(10)-helices, the (phi, psi) dihedral angles (-60 degrees, -20 degrees) and rise per turn (6.0 A) changed to (-66 degrees, -12 degrees) and 6.8 A, respectively. In terms of relative stability, the most prominent change upon thio substitution is the decrease in the free energy difference, Delta A(alpha --> 3(10)), from 14 to 3.5 kcal/mol. Therefore, normal peptides are less likely to form 3(10)-helix than are thiopeptides. Component analysis of the Delta A(alpha --> 3(10)) reviews that the entropy advantage of the 3(10)-helix for both Ac-Ala(10)-NHMe and Act-Alat(10)-NHMe is attributed to the 3(10)-helix being more flexible than the alpha-helix. Interestingly, upon thio substitution, this differential flexibility is even more apparent because the alpha-helix conformation of Act-Alat(10)-NHMe becomes more rigid due to the bulkier sulfur atom.     

手性毛细管色谱法测定人尿中美芬妥英对映体的含量及其在代谢分型中的应用

 采用手性毛细管色谱柱和ＦＩＤ检测器建立了人尿中美芬妥英（ＭＰ）对映体的定量分析方法。尿样用二氯乙烷提取，用酸、碱洗涤得以纯化，测得各对映体的最低检测限为６０μｇ／Ｌ。在１１５～６９０μｇ／Ｌ浓度范围内，标准曲线呈良好的线性关系，ｒ＞０．９９，日内、日间精密度ＲＳＤ＜６．５％，Ｓ－ＭＰ的平均回收率为７４．４１％，Ｒ－ＭＰ的平均回收率为７３．７８％。并以ＭＰ为探针药物，对３２名志愿者的尿样进行了ＭＰ氧化代谢分型研究。     

流动注射在线柱预富集-电感耦合等离子体原子发射光谱测定痕量金属元素

本文报道了流动注射在线柱预富集ICP光谱测定痕量金属的方法,以meso-四(4-磺基苯)卟啉为柱前衍生试剂,硅胶作固定相和盐酸作洗脱液,对痕量金属离子Cu、Mn、Ni、Fe、Pb、Cd进行在线预富集检测。在给定实验条件下,方法的富集倍数为9.3～11.3,检出限和测定的相对标准偏差(n=6)分别在0.32～26.8ng/ml和1.3％～3.0％范围内。方法用于小牛肝和西红柿叶样品分析,结果与参考值吻合。     

热导式热量计特征热谱方程的建立

Based on the interfacial model of a conduction calorimeter, a characteristic thermogram equation is suggested in this paper. Measurements of only two quantities such as the maximum peak height △m and its time tm, enables us to calculate the peak height at any interval by using this model. Thermograms of alkaline hydrolysis of ethyl propionate and ethyl acetate have been measured at 25℃, respectively. The themographic data calculated by using the characteristic thermogram equation are in reasonable agreement with those read from the thermograms.     

光度法研究3,4,5—三羟基苯甲酸及其类似物与铀（Ⅵ）的配位反应

三羟基苯及其衍生物是一类重要配体,如3,4,5-三羟基苯甲酸(GA)与铀、钍及稀土生成沉淀,并可用于铀、钍、稀土的连续测定。我们在研究用GA离铀、钍、稀土时,GA与铀生成1种棕色配合物,早期曾用于铀的比色测定,它可能是一种单核与多核配合物的混合物,但对这类化合物与铀的配位反应迄今来作过详细研究。本文用光度法研究了GA、连苯三酚(PGA)、3,4,5-三羟基苯甲酸丙酯(PGE)与3,4,5-三甲氧基苯甲酸(TMBA)与铀(Ⅵ)的配位反应,研究了配合物的组成及其反应机理,测定了部分配合物的稳定常数。     

A novel small-molecule near-infrared II fluorescence probe for orthotopic osteosarcoma imaging

Osteosarcoma is the most common primary malignant tumor of bone, particularly among children and adolescents. Advances in imaging, surgical techniques, and implants have dramatically reduced the need for amputation in the past three decades.Recently, in vivo fluorescence imaging in the second near-infrared window(NIR-II, 1,000–1,700 nm) shows impressive advantages of deeper tissue penetration and higher spatial resolution, which makes it a promising tool for the early diagnosis and post-operative observation of Osteosarcoma. To the best of our knowledge, this paper is the first time to develop a novel NIR-II fluorescence probe conjugated with an osteosarcoma targeted oligopeptide for molecular tumor imaging in a xenograft orthotopic osteosarcoma mouse model.     

稀土配合物的时间分辨光谱分析法研究(Ⅰ)TFA-TOPO-农乳-100体系用于测定铕和钐

本文采用自己组装的时间分辨荧光光谱测定装置,研究了铕(钐)-三氟乙酰丙酮-三正辛基膦化氧(Eu(Sm)-TFA-TOPO)在非离子表面活性剂农乳-100存在下的光谱特性、荧光衰减动力学特性和发光机理。提出了能量传递机制和第二配体TOPO在荧光发射过程中的作用,制定出TFA-TOPO-农乳-100体系测定痕量铕和钐的时间分辨荧光光谱分析方法,用于测定高纯氧化钇中的痕量铕和钐,结果令人满意。     

高效液相色谱指纹图谱应用于地黄的研究

利用高效液相色谱建立了地黄的色谱指纹图谱。采用反相C1 8柱 (5 μm ,1 5 0mm× 4.6mm) ,流动相甲醇∶水 (V V =5∶95 ) ,检测波长为 2 80nm ,流速 1 .0mL min进行实验。根据相对保留值和相对面积值对色谱指纹图谱进行分析对比研究 ,建立了控制地黄药材质量的新方法。该法为中药样品的鉴定提供了较全面的信息 ,并为HPLC在复杂组分的样品分析领域开拓了新的应用途径。