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151.
Tran TT Zeng J Treutlein H Burgess AW 《Journal of the American Chemical Society》2002,124(18):5222-5230
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. 相似文献
152.
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 总被引:2,自引:0,他引:2
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。 相似文献
153.
热导式热量计特征热谱方程的建立 总被引:1,自引:0,他引:1
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. 相似文献
154.
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。 相似文献
155.
Lin Jiacheng Li Qianqian Zeng Xiaodong Chen Ziyang Ding Qihang Li Yang Zhou Hui Meng Xianli Chen Deliang Deng Zixin Hong Xuechuan Xiao Yuling 《中国科学:化学(英文版)》2020,63(6):766-770
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. 相似文献
156.
157.
158.
Using the polyglycol gel method, a series of Pr2 − x
SrxCoO4 ± y
(0.2 ≤ x ≤ 1.0) mixed oxides were prepared, and their catalytic activities were studied in the test reaction of NO reduction by CO.
The solid-state physicochemical properties, including crystal structure, defect structure, IR spectrum, valence state of B-site
ions, nonstoichiometry oxygen (y), oxygen species, and redox properties, were characterized by means of XRD, IR, TPD, TPR,
XPS, and chemical analysis. The results show that all mixed oxides display a K2NiF4 structure. When x = 0.2 and 1.0, the obtained samples still have little uncertain mixed oxides; however, the mixed oxides (x = 0.4, 0.6, 0.8) all represent a single A2BO4 phase. With the increase of x, lattice parameters, unit-cell volume, and average crystalline size decrease gradually, whereas microstrain density, the
concentration of Co3+, the amounts of lattice oxygen released and the concentration of oxygen vacancy increase. The catalytic activities of Pr2 − x
SrxCoO4 ± y
catalysts for NO reduction by CO are closely correlated with oxygen vacancy and the concentration of Co3+.
Published in Russian in Kinetika i Kataliz, 2006, Vol. 47, No. 3, pp. 431–437.
The text was submitted by the authors in English. 相似文献
159.
160.
使用射频磁控溅射方法在不同衬底温度下(ts=室温,350,500℃)于Si(001)衬底上沉积了CNx膜,并利用拉曼(Raman)光谱、傅里叶变换红外光谱(FTIR)及X射线衍射光电子能谱(XPS)对CNx膜的化学结合状态与温度的关系进行了研究。Raman光谱结果表明,随衬底温度(ts) 增加,D带向低频方向移动,G带向高频方向移动;它们的半高宽分别由375和150cm^-1减小至328和142cm^-1;ID/IG由3.76减小至2.88。FTIR谱中除无序D带(1400cm^-1)和石墨G带(1570cm^-1)外,还有-700cm^-1,~2210cm^-1(C=N),2330cm^-1(C-O)及3255-3351cm^-1(N-H)等峰。XPS测试结果表明:随衬底温度增加,N与C的物质的量比由0.49下降至0.38,sp^2(C-N)组分与sp^3(C-N)组分强度比呈增大趋势。低温(350℃)退火并未对CNx膜的化学结合状态产生较大影响;高温(900℃)退火样品则显示出较好的结晶化程度。 相似文献