手性卟啉化合物聚集体与DNA 的相互作用: 电子吸收光谱 和圆二色光谱研究

使用电子吸收光和圆二色(circulardichroism,CD)光谱研究了手性氨基酸卟啉锌配合物(Thr---TPPZN)聚集体与DNA之间的相互作用,这种螺旋结构的手性卟啉聚集体能与DNA结合,L－Thr----TPPZN聚集体与DNA作用量是通过氨基酸残基与DNA的磷酸链形成氢键,结合模式为外部结合,而D----Thr--TPPZN聚集体与DNA作用除了存在以上这种氢键作用之外,卟啉单元还能部分地插入DNA中,与DNA的碱基对形成π-π堆积作用。L--Thr---TPPZN和D--Thr--TPPZn聚集体与DNA结合模式不同是由于L-------Thr----TPPZn聚集体的左手螺旋结构与DNA的右手螺旋结构不匹配,而右手螺旋结构的D--Thr-----TPPZN聚集体能嵌入同样是右手螺旋结构的DNA中。     

三种不同元素掺杂的碳点与DNA相互作用及其机制研究

碳点(carbon dots,CDs)在材料学及生物医学相关领域的研究已引起科研人员的广泛关注.本文采用一步水热法,制备了三种具有不同元素掺杂的CDs、N-CDs、N,S-CDs,并结合多种光谱法、熔链温度法和黏度法,系统地研究了三种不同元素掺杂的碳点与ctDNA结合模式以及结合能力的差异.荧光实验证明三种不同性质的碳点CDs、N-CDs、N,S-CDs与ctDNA的相互作用模式为沟槽结合,结合力主要为氢键和范德华力,并伴随着轻微的静电作用力.在强电解质和变性剂的存在下,会减弱碳点与ctDNA之间的沟槽结合.圆二色光谱实验和红外光谱实验反映了碳点与ctDNA的沟槽结合作用并不会明显改变ctDNA的构象.与未掺杂的碳点(CDs)相比,氮硫元素的掺杂可使N,S-CDs与ctDNA的沟槽结合能力减弱,但是加大碳点表面电荷,可增强N-CDs与ctDNA的结合.这一结论为碳点的设计及其在生物医学领域中的应用提供了理论参考.     

双酚A与小牛胸腺DNA的嵌插作用

在pH7.4Tris-HCl缓冲条件下,应用多种光谱学方法并结合化学计量学多元曲线分辨-交替最小二乘法(MCR-ALS)、DNA熔点测量、粘度分析以及分子模拟技术,研究了环境雌激素双酚A(BPA)与小牛胸腺DNA(ctDNA)的相互作用。由MCR-ALS解析扩展的紫外光谱数据矩阵,得到了3个反应组分(BPA、ctDNA及BPA-ctDNA复合物)的相对浓度及其光谱曲线,可评估BPA与ctDNA相互作用进程。BPA引起ctDNA熔点和粘度升高、与吖啶橙竞争结合ctDNA表明BPA通过嵌插模式与ctDNA作用。傅里叶红外光谱研究显示,BPA主要结合在ctDNA的A,T碱基富集区,这与分子模拟结果一致。圆二光谱分析表明,BPA与ctDNA作用诱导ctDNA的结构由B构象向A构象转变。     

沙丁胺醇与小牛胸腺DNA相互作用研究

在生理酸度条件下(pH7.4),运用紫外–可见吸收光谱、荧光光谱、圆二色谱(CD)和傅立叶红外光谱(FT–IR)并结合分子模拟、DNA熔点及粘度测定,研究了沙丁胺醇(Sal)与小牛胸腺DNA(ctDNA)的相互作用。结果表明,ctDNA以静态方法猝灭Sal的内源荧光,25℃时ctDNA与Sal的结合常数为1.26×104L·mol,氢键和范德华力是两者结合的主要驱动力。Sal存在下,ctDNA的熔点无明显变化,KI荧光猝灭效应和盐效应不明显,证实Sal与ctDNA主要通过沟槽模式结合。FT-IR与分子模拟结果显示,Sal倾向于与ctDNA的胸腺嘧啶(T碱基)结合。CD和凝胶电泳分析表明,Sal与ctDNA结合没有对DNA产生明显损伤,DNA仍维持B型构象。     

一种苊并杂环有机小分子嵌入DNA的几何学模式研究

利用圆二色谱(CD)、紫外-可见吸收光谱以及荧光光谱等方法对苊并杂环化合物8-氧-8H-苊并[1,2-b]吡咯-9-腈(A1) 与小牛胸腺DNA(CT DNA) 的相互作用进行了研究. 结果表明, 随着n(A1)/n(CT DNA)的变化存在两种不同的几何学结合构型. 当n(A1)/n(CT DNA)值低于0.20时, A1分子与DNA的结合方式是不均一的, 化合物分子以多种角度嵌入到DNA碱基对之间. 表现为A1-DNA复合物的诱导圆二色光谱图上较小的正峰和紫外吸收光谱图缺省等吸收点. DNA的特征圆二色谱图表明, 在n(A1)/n(CT DNA)≤0.20范围内, CT DNA的构象从标准的B型转化为A-like型; 当n(A1)/n(CT DNA)>0.20时, 诱导圆二色光谱由正峰转变为强度大、波形复杂的负峰, 表明A1分子开始堆积到DNA螺旋的表面, 同时DNA的二级结构发生了进一步变化.     

烷基酚与DNA相互作用的荧光光谱法研究

用荧光光谱法研究了环境激素辛基酚(OP)、壬基酚(NP)与小牛胸腺DNA(ctDNA)的相互作用.实验发现,随着ctDNA的加入,辛基酚、壬基酚的荧光光谱产生了有规律地猝灭,且最大发射峰红移.其中荧光猝灭是由于形成了烷基酚-DNA加合物而引起的静态猝灭.辛基酚、壬基酚与ctDNA均以插嵌模式相互作用,其结合常数分别为5.1×105 L·mol-1 和1.4×106 L·mol-1 ,结合位点分别为1.31和1.45.热力学参数确定了辛基酚及壬基酚与ctDNA的作用力类型主要是疏水作用力.     

荧光小分子2-氨基-7-甲基-1,8-萘啶与存在碱基缺失损伤的dsDNA相互作用的研究

摘要采用光谱法研究了小分子2-氨基-7-甲基-1,8-萘啶与存在单碱基缺失损伤的dsDNA的相互作用。紫外-可见光谱显示小分子与dsDNA结合后．其位于330nm处的吸收峰降低并在350nm处产生了新的吸收峰,表明二者有强烈的相互作用。dsDNA的圆二色光谱表明相互作用导致dsDNA的构象发生了变化。     

S-异丙甲草胺与小牛胸腺DNA的相互作用

应用紫外光谱、荧光光谱、DNA热变性法以及黏度法研究了S-异丙甲草胺与小牛胸腺DNA(ctDNA)的相互作用. 结果表明, S-异丙甲草胺使ctDNA在200 nm处的吸收峰发生明显改变, 表现出红移和减色效应, 而对260 nm处的吸收峰产生影响较小, 排除了嵌插作用的可能; ctDNA对S-异丙甲草胺内源性荧光表现出很强的猝灭作用, 且随温度的升高, 其猝灭程度有所下降, 表明S-异丙甲草胺是以形成加合物的方式与ctDNA结合的, 并求得了它们在不同温度下的结合常数; 将不同离子强度条件下S-异丙甲草胺与ctDNA作用以及不同S-异丙甲草胺浓度下ctDNA的热变性温度和黏度变化的研究结果与紫外光谱和荧光光谱相结合, 可以判断S-异丙甲草胺是以沟槽作用的方式与ctDNA结合的.     

多种光谱方法研究除草剂利谷隆与DNA的相互作用

在生理条件下(pH 7.4),采用紫外-可见光谱法、荧光光谱法、圆二色谱法(CD)和傅里叶红外光谱法(FT-IR)并结合粘度实验和熔点测量技术,研究了利谷隆与小牛胸腺DNA(DNA)的相互作用。实验发现,利谷隆可以置换出嵌入DNA中的亚甲基蓝,并使DNA的熔点和粘度升高,表明二者发生了嵌插作用。利谷隆的存在引起DNA的CD光谱收缩,表明DNA发生了B构象向C构象的转变;红外光谱分析表明嵌入DNA双链的利谷隆芳环主要作用于G、A碱基。     

分子光谱法研究漆黄素与DNA的相互作用

利用多种光谱技术及伏安技术研究了漆黄素与DNA之间的相互作用.由荧光光谱法可知,DNA对漆黄素的猝灭过程是静态猝灭,计算得到不同温度下二者的结合常数及结合位点数.ΔH,ΔS,ΔG的计算结果表明漆黄素与DNA的作用力为范德华力或氢键作用.循环伏安法进一步表明了DNA的加入使漆黄素的峰电位发生了移动,二者产生了有效结合.离子强度实验、黏度法、紫外光谱法、圆二色光谱法、DNA熔解温度实验和单双链DNA对比实验的结果均表明漆黄素与DNA的结合是嵌插结合模式.     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.

     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

解决能源问题的新途径——光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。     

黄酮化合物的合成研究进展

黄酮化合物是一类具有多种生物活性的天然产物,其经典的合成方法主要为查耳酮路线和β-丙二酮路线.近年来出现了许多新技术、新方法.本文介绍了2'-羟基查尔酮的氧化关环法、黄烷酮氧化法、改进的Baker-Venkataraman法及其他合成黄酮化合物的方法.