Pb~(2+)-牛血清白蛋白复合体系中蛋白质二级结构的研究

采用紫外光谱、红外光谱和圆二色谱法研究了Pb2+与牛血清白蛋白(BSA)之间的相互作用和蛋白质微观结构的变化。紫外光谱表明,Pb2+与BSA肽链上的CO存在相互作用,并使蛋白质疏水结构的微环境发生变化;红外光谱研究表明,Pb2+与BSA结合位点可能为—OH和—NH基团,利用二阶导、退卷积和谱线拟合技术对蛋白质红外谱图的酰胺Ⅰ带进行处理推测蛋白质二级结构的变化,结果表明蛋白质α螺旋和β折叠二级结构含量降低,β转角二级结构含量增加;圆二色谱(CD)也表明Pb2+与BSA的结合使蛋白质的构象发生了改变。     

Hg^2＋ -牛血清白蛋白复合体系中蛋白质微观结构的研究

研究了Hg2+在生物体内与牛血清白蛋白相互作用的毒性机理以及蛋白质的微观结构变化.测定了Hg2+与牛血清白蛋白(BSA)复合体系的红外光谱(FT-IR)和圆二色谱(CD),并对图谱进行拟合解析处理.红外光谱实验数据表明Hg2+与BSA发生作用的结合位点可能包括-SH、-OH和-NH基团,采用红外拟合技术对BSA二级结构的变化进行了研究,结果表明蛋白质α-螺旋结构含量降低,β-折叠结构含量升高.圆二色谱图也表明由于一定浓度的Hg2+与BSA结合,从而导致蛋白质的二级结构被破坏,这与拟合红外光谱得到的蛋白质二级结构数据相吻合.Hg2+与牛血清蛋白作用致使蛋白质的构象改变,形成金属离子与蛋白质作用的复合物,因而蛋白质失去活性导致生物体发生病变.     

三七总皂甙对牛血清白蛋白溶液构象的影响

应用衰减全反射傅立叶变换红外光谱结合荧光光谱和紫外光谱研究了中药三七 的有效成分三七总皂甙与牛血清白蛋白（BSA）的相互作用，采用对蛋白质红外光 谱酰氨Ⅰ带和酰氨Ⅲ带进行曲线拟合的方法，定量分析了不同浓度三七总皂甙对 BSA二级结构的影响，发现随着三七总皂甙浓度的增加，蛋白分子结构逐渐发生了 由螺旋向折叠的转化。a-螺旋结构减少了3%，β-折叠结构增加了约5%，其它二级 结构没有明显的变化，红外差谱和荧光光谱的结果为药物与蛋白质的作用引起牛血 清白蛋白溶液构象的变化提供了佐证，紫外光谱反映了单体皂甙与蛋白质的结合常 数的差异。     

蛋白质结构的FT-IR研究进展

随着蛋白质使用领域的增加,迫切需要知道它在不同环境中的结构特征及生物活性。目前,测定蛋白质结构的方法很多,包括X射线衍射技术、圆二色光谱(CD)、质谱、FT-IR等。FT-IR(傅立叶变换光谱)法不仅能够测定不同环境中的蛋白质结构及生物活性,而且能够测定其二级结构的相对含量。本文简要综述FT-IR技术用于蛋白质结构的研究进展。     

蛋白质和变性蛋白质二级结构的FTIR分析进展

蛋白质结构的研究一直是人们研究的一个热点,蛋白质在发生变性后,二级结构会改变,从而导致生物活性丧失,这些与医药学及食品科学等领域密切相关。傅里叶变换红外光谱(FTIR)作为一种无损、快速的分析方法在蛋白质二级结构的研究中发挥重要的作用,本文就FTIR对于蛋白质二级结构的研究作一初步概述,主要介绍FTIR研究蛋白质结构的主要方法、红外光谱的谱学特点。     

大豆蛋白的中红外和近红外光谱研究*

大豆蛋白在各领域的应用已得到广泛的关注,因此大豆蛋白及其改性材料在结构性能方面的研究显得越来越重要。中红外光谱(mid-infrared spectroscopy,MIR)和近红外光谱(near-infrared spectroscopy,NIR)正是对蛋白质进行定性定量分析的有力手段。中红外光谱可以有效地分析大豆蛋白在溶液和薄膜中的二级结构以及大豆衍生材料内蛋白质的结构变化情况。近红外光谱则在蛋白质定量分析方面有着独特的优势。本文介绍了运用这两种光谱技术进行研究的一些工作,这些实例表明了中红外和近红外光谱在大豆蛋白研究领域的重要应用价值。     

磺化聚醚砜/磷酸硼复合质子交换膜的制备与性能

采用sol-gel法成功制备了一系列有望用于高温质子交换膜燃料电池的新型磺化聚醚砜(SPES)/磷酸硼(BPO4)复合膜, 并经热重分析(TGA)-傅立叶变换红外光谱(FTIR)联用技术、差示扫描量热仪(DSC)、扫描电子显微镜(SEM)等对膜的结构和性能进行了表征. 结果表明, 复合膜较纯SPES膜具有更高的热稳定性和玻璃化转变温度, 较低的溶胀性及较高的氧化稳定性; SEM图片显示BPO4在聚合物基体中的分布十分均匀, 这将有利于连续质子传输通道的形成; 复合膜的质子传导率随BPO4含量的增加而增加, 当温度超过120 ℃后, 复合膜仍保持着较高的质子传导率, 这表明该复合膜在高温质子交换膜燃料电池中具有良好的应用前景.     

胃和结直肠癌的傅里叶变换红外光谱研究

利用傅里叶变换红外光谱仪及带ATR探头的中红外光纤系统测定了手术切除的胃癌、结直肠癌及相应的正常组织共31对标本粘膜面的反射红外光谱. 结果表明, 与正常组织相比, 癌组织的红外光谱发生明显变化: (1) 与脂类相关的谱带2955, 2920, 2870, 2850和1740 cm-1出现几率明显低于正常组织(P<0.001), I1460/I1400(I为峰强度)明显降低(P<0.001), 表明癌组织的脂类相对含量降低; (2) 与蛋白质相关谱带N—H和O—H明显红移(P=0.025), 表明N—H和O—H的氢键化程度增加, 癌组织的I3375/I1460, I1640/I1460和I1550/I1460明显升高(P<0.01), 表明癌组织的蛋白质相对于脂类的含量增加, 癌组织的HW1550/I1550(HW为半高宽)明显升高(P=0.036), HW1550则明显降低(P=0.05), 表明癌组织中蛋白质的二级结构发生显著变化; (3) 与醣类相关谱带中癌组织的I1160/I1460降低(P=0.002), 结合组织化学染色, 推测可能是癌组织表面的糖蛋白明显减少造成的, 而I1120/I1460升高(P=0.019)则可能是癌组织表面的糖原颗粒增加所致. (4) 与核酸相关谱带中癌组织的PO的反对称伸缩振动蓝移(P=0.033), 表明癌组织中磷酸基团的氢键化程度降低. 研究结果表明, 红外光谱有望成为诊断恶性肿瘤的有力工具.     

磷脂酰胆碱与牛血清白蛋白相互作用的FT-IR研究

利用傅立叶变换红外(FT-IR)和拉曼(FT-Raman)光谱研究了高浓度磷脂酰胆碱(PC)与牛血清白蛋白(BSA)的相互作用,及Eu3＋对该作用的影响.FT-IR结果显示,PC/BSA混合体系中二者的相互作用主要发生在PC头部极性基团,且这一作用随BSA含量的增加而增强,作用后蛋白质二级结构中α螺旋的比例有所增加. FT-Raman光谱说明PC与BSA的相互作用影响磷脂CH链的排列有序程度. PC/BSA/Eu3＋体系的红外光谱显示, Eu3＋与PC的磷氧键发生了强相互作用,并使蛋白α螺旋的比例进一步增加.     

氯化钕对渗透胁迫引起的膜损伤和ABA含量的影响

小麦幼苗在聚乙二醇渗透胁迫下，叶片相对含水量下降，膜脂过氧化作用产物再会一醛含量增加，质膜相对透性升高，超氧化物歧化酶活性下降，过氧化物酶活性显著提高，脱落酸在渗胁迫处理的第３ｈ和第１５ｈ出现两个高峰，渗透胁迫下经氯化钕处理，提高了小麦幼苗ＲＷＣ，降低质膜相对透性及ＭＤＡ含量，提高ＳＯＤ和ＰＯＤ活性，ＡＢＡ在２４ｈ胁迫期间仅出现一个高峰，且峰值显著下降。     

二氧化碳和丙烯直接合成甲基丙烯酸的NiPMo/TiO2催化剂的研究

用溶胶-凝胶法以磷钼酸(MPA)的镍盐溶液水解钛酸四丁酯制备了NiPMo/TiO2催化剂.使用ICP、 XRD、 TG-DTA、 IR、 TPD-MS和微反应技术研究了催化剂的化学组成、热稳定性、化学吸附性质和催化反应性能.杂多钼酸盐与TiO2通过O2-在TiO2表面发生了键合.在623 K下,杂多阴离子仍保持原有的Keggin结构.CO2在Lewis酸位Ni(Ⅱ)和Lewis碱位Ni-O-Mo的桥氧协同作用下生成CO2卧式吸附态Ni(Ⅱ)←O-(CO)←(O--Ni).丙烯有多种吸附态在催化剂上吸附.在563 K、 1 MPa和空速1500 h-1的反应条件下,丙烯的摩尔转化率为3.2%,产物MAA选择性为95%.     

Toward new camptothecins. Part 6: Synthesis of crucial ketones and their use in Friedländer reaction

In the context of the preparation of camptothecin and luotonin A analogs, the synthesis of some key keto-precursors and their use in Friedländer condensation are described. This paper also focuses on the stability of these keto intermediates and emphasizes the major differences between indolizinones and pyrroloquinazolinones series. Noteworthy is also the report of some original structures isolated as by-products of some experiments.     

CoFe2O4自形成磁性液体场致结构化对磁化的影响

The Langevin paramagnetic theory can’t describe the relation between magnetization of ferrofluids and applied magnetic field. The structuralization of ferrofluids, which is considered the main influence factor of the magnetization, is regarded. The part of magnetization works is deposited when the structure is forming. This action influences the magnetization of ferrofluids directly or indirectly. On the base of the “compressing” model, the Langevin function that usually describes the magnetization of ferrofluid is modified, and a well-fitted curve is obtained. An equation of the relation between the equivalent volume fraction after being “compressed” and the intensity of magnetic field is discovered, which approximately describes the process of magnetization. The relation between the approximate initial susceptibility and the volume fraction can be obtained from modified formula.     

Highly regioselective Buchwald–Hartwig amination at C-2 of 2,4-dichloropyridine enabling a novel approach to 2,4-bisanilinopyridine (BAPyd) libraries

The highly regioselective Buchwald–Hartwig amination at C-2 of the cheap and readily accessible reagent, 2,4-dichloropyridine with a range of anilines and heterocyclic amines is described. This new methodology is robust and provides a facile access to 4-chloro-N-phenylpyridin-2-amines on 0.25 mol scale. These intermediates undergo a further Buchwald–Hartwig amination at higher temperature to enable rapid exploration of the chemical space at C-4 and to provide a library of 2,4-bisaminopyridines.     

KMnO4-mediated oxidative CN bond cleavage of tertiary amines: Synthesis of amides and sulfonamides

KMnO₄-mediated oxidative CN bond cleavage of tertiary amines producing secondary amine was introduced, which was trapped by electrophiles (acyl chloride and sulfonyl chloride) to form amides and sulfonamides. The reaction could take place at mild condition, tolerating a wide range of function groups and affording products in moderate to excellent yields.     

Chemistry of heterocyclic compounds at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, over 50 years (Review)

The review contains a concise historical account and information on the most significant researches undertaken by the staff at the A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences on the Chemistry of Heterocyclic Compounds. Dedicated to Academician of the Russian Academy of Sciences B. A. Trofimov on his 70th jubilee. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1443–1502, October, 2008.     

Sulfur-directed metal-free and regiospecific methyl C(sp3)–H imidation of thioanisoles

Regiospecific and direct imidation of the methyl C(sp³)–H bond of thioanisoles is realized under mild and metal-free conditions with N-fluorobis(benzenesulfonyl)imide as an oxidant and nitrogen source. Proposed mechanism suggests that thionium ion intermediates and a Pummerer-type reaction are involved. The imidation has advantages such as high step-economy, excellent functionality tolerance, and regiospecificity, giving structurally diverse imidation products.     

Selective syntheses of 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones via temperature-dependent Rh(II)-carbenoid-mediated 2H-azirine-ring expansion

The Rh(II)-catalyzed reaction of 2-carbonyl-substituted 2H-azirines with ethyl 2-cyano-2-diazoacetate or 2-diazo-3,3,3-trifluoropropionate provides an easy access to 2H-1,3-oxazines and 1H-pyrrol-3(2H)-ones. These compounds can be selectively prepared from the same starting material using temperature as the only varied parameter. The 2-azabuta-1,3-diene intermediate, a common precursor for both heterocyclic products, isomerizes into 2H-1,3-oxazine under kinetic control, while 1H-pyrrol-3(2H)-one is the sole product of the reaction at elevated temperatures. According to DFT-calculations a one-atom oxazine ring contraction involving ring-opening to a 2-azabuta-1,3-diene intermediate, followed by a 1,5- and 1,2-prototropic shift leads to the consecutive formation of imidoylketene and azomethine ylide, which then further undergo cyclization to the pyrrole derivative.     

Synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives

Different approaches for the synthesis of 1-benzyloxypyrazin-2(1H)-one derivatives from simple amino acids have been investigated. A library of 33 precursors for the preparation of N-hydroxy pyrazinones was obtained in moderate to good yields.