本体聚合反应全过程苯乙烯增长自由基的ESR谱的研究

本文对苯乙烯本体聚合全过程增长自由基ESR谱进行了研究,对全过程ESR谱的模拟和分析及构象能的计算表明:反应初期12线谱由产生6线谱构象R_1和8线谱的构象R_2叠加而成,其相对含量R_1>R_2。反应中期4线谱和6线的ESR谱的模拟结果为:R_1相似文献   

甲基丙烯酸甲酯自由基本体聚合反应动力学(Ⅰ)——自由基的构象和浓度、链增长速率常数kp

采用TM₁₁₀谐振腔和φ2mm样品管,记录了以N,N-二甲基苯胺与过氧化苯甲酰为引发体系的甲基丙烯酸甲酯本体聚合反应过程中增长自由基的ESR谱。由此得到反应过程中的增长自由基浓度及其构象。计算了链增长反应速率常数k_p。结果表明:链增长反应为扩散控制过程。     

聚合反应增长自由基ESR谱的交替线宽现象研究

用驰豫矩阵方法处理了甲基β质子各向同性超精细偶合常数在扭曲振荡调翻作用下所引起的ESR谱的交替线宽问题, 得到了构象成连续分布β质子的相关函数, 谱密度函数及在快交换条件下的ESR线宽表达式, 并用其对苯乙烯本体聚合反应的全过程ESR谱的交替线宽现象进行了分析, 结果解释了交替线宽随本体聚合反应的变化, 支持了对苯乙烯增长自由基ESR谱超精细偶合常数的归属.     

不同波段的紫外辐射对DNA构象影响的拉曼光谱研究

研究了小牛胸腺DNA水溶液经不同时问不同波段紫外辐射后的拉曼光谱。结果表明：仅仅经过9min强度为18．68W／m^2。的全波段紫外辐射,DNA就遭到了严重损伤：表征PO2^-对称伸张振动的1094cm^-1谱线分裂成4条谱线．说明DNA构象遭到破坏,构型发生了变化。UV—A＆UV—B波段的紫外辐射对DNA的影响比全波段的紫外辐射对DNA的影响小得多,但经过较长时间辐射后,仍对DNA构型构象产生了影响,即A型构象增强,B型构象减弱．经过2h的UV—A辐射,出现了表征A型构象的805cm^-1和816cm^-1谱线,且816cm^-1峰与未经辐射的表征A型的803cm^-1峰相比,强度大得多。经过16h的UV—A辐射后,805cm^-1谱线消失,816cm^-1谱线移到了813cm^-1,且强度减弱50％,表明水溶液中的DNA在UV—A照射中A型构象不稳定,处于变化之中。     

喹诺酮药物与血清蛋白相互作用的三维荧光光谱研究

应用三维荧光光谱和三维荧光偏振光谱研究了数种喹诺酮药物与牛血清白蛋白(BSA)分子间的相互作用。由三维荧光(偏振)光谱得到的指纹信息说明了喹诺酮药物与BSA结合反应对BSA分子构象的影响。通过研究喹诺酮药物发生相互作用前后BSA荧光偏振度及各向异性的变化,定量说明了喹诺酮药物-BSA所发生的结合反应。     

芳香叠氮化合物对牛血清白蛋白的化学修饰

合成了一种芳香叠氮化合物的活性酯，利用该酯催化4－叠氮基苯甲酸的羧基与牛血清白蛋白的氨基之间的反应形成酰胺键。研究了不同反应时间内BSA的修饰率及其构象的变化。此外、紫外光谱证实了修饰的结果，荧光光谱检测了BSA构象变化。     

N3H5异构化及构象分析

采用量子化学的方法, 对氮氢化合物N3H5所有可能的二面角变化进行松散势能面扫描, 获得了相应的能量和构象之间的关系, 研究了N3H5的异构化机理和构象的变化. 分子中的原子(AIM))理论计算得到的键临界点电荷密度的增大和减小,及其拉普拉斯值的正负变化, 可以清楚地反映构象转化过程中键的增长、断裂和新键生成的相关信息. 自然键轨道(NBO)理论分析表明, 立体排斥作用使分子能量升高, 而超共轭作用使分子能量降低, 它们对分子构象的相对稳定性起了重要作用.     

聚甲基丙烯酸甲酯与聚醋酸乙烯酯共混的红外光谱研究

用红外光谱(FTIR)研究了聚甲基丙烯酸甲酯(PMMA)与聚醋酸乙烯酯(PVAc)共混体系相容性,在160℃以上共混体系发生相分离;分相体系与非分相体系的FTIR谱明显不同;共混体系的FTIR谱不能从两统组分红外光谱简单加和得到;结果表明大分子构象发生了变化,PMMA/PVAc体系相容可能是大分子构象熵变所致。     

有机反应的构象效应

本文引用“分子最少变形原理”和“最少移动原理”解释了有机反应中相当普遍存在的一种情况。即:在一个动力学控制的反应中,与反应物的进入反应的构象对比,生成构象尽可能少改变的初产物,经常是该反应的主要方向。叙述了这一构象效应与动力学控制的产物的立体化学关系。并建议将这一效应称为“构象最少改变原理”。同时,还介绍了“禁止构象”的概念,和这类构象对有机反应的效应。     

耐高温α-淀粉酶结合Ca2+的研究

测定了耐高温α-淀粉酶分子中含10个Ca2+,脱钙酶逐量补钙后的活力及稳定性研究表明:酶分子中前8个Ca2+参与酶的催化作用,后2个Ca2+抖对酶结构起稳定作用.脱钙酶加钙后室温下的荧光光谱和CD谱表明:酶的构象虽有变化,但不显著,说明酶的构象对ca2+的依赖性很小.脱钙酶结合不同数目的Ca2+,于90℃加热15 min后,测其荧光光谱,结果表明,结合10个Ca2+时,酶保持最大的稳定构象;CD谱表明脱钙酶加热时仍具有一定的螺旋结构.这再次说明,酶的构象对ca2+依赖性较低.     

Probability Properties of Multi－contact in Protein Molecules

The compact conformations of polymers are important because the native conformations of all bio-polymers with certain function are highly compact. The properties of mutil-contact bio-polymer chains were studied by Gaussian statistics of the random-flight chain. The theoretical expressions(were given, also), the calculations of probability distributions and correlation functions for different topologic cases were derived and made respectively. Comparison between single, double and triple contacts was also made. By means of setting the parameters, the results of the current calculations of the multiple contacts are just the same as those calculated by single, double or tripe contacts separately. It is a useful method to investigate native conformations of biopolymers. The probabilities of multi contacts and correlation functions between chain‘s contacts were calculated for the Gaussian chains. Because the bond probability distributions are Gaussian‘s distributions, the probability distributions of the separations of various points along the chains are always consecutive. All the contacts may break up into several groups, and each group consists of many contacts. Here we investigated the probability distribution from one group to three groups of contacts.     

Toward absolute density of states calculations for proteins

The density of states (DOS), which gives the number of conformations with a particular energy E, is a prerequisite in computing most thermodynamic quantities and in elucidating important biological processes such as the mechanism of protein folding. However, current methods for computing DOS of large systems such as proteins generally yield only the ratios of microstate counts for different energies, which could yield absolute conformation counts if the total number of conformations in phase space is known, thus motivating this work. Here, the total number of energy minima of 50-mer polyalanine, whose size corresponds to naturally occurring small proteins, was estimated under an all-atom potential energy function based on the cumulative distribution function (CDF) of conformational differences to be approximately 10(38). This estimate can place any DOS function, such as the Gaussian DOS distribution in the random energy model, on an absolute scale. Comparing the absolute conformational counts from a Gaussian DOS function with those from the CDF derived from quenched molecular dynamics ensembles shows that the former are far greater than the latter, indicating far fewer low-energy minima actually exist. In addition to showing how CDF and relative DOS calculations can yield absolute DOS for a discrete system, we also show how they can yield absolute DOS for continuous variable systems to a specified atomic variance. In the context of protein folding, knowing this phase-space "volume" of conformations in a DOS function, as well as characteristic transition times, constrains the set of possible folding mechanisms.     

A Novel Conformation Investigation on Newly Synthesized Compound of Diethyl Puerarin-7-yl Phosphate

1INTRODUCTION Puerarin(4?,7-dihydroxy-8-β-D-glucosylisoflavo ne),whose chemical structure is shown in Fig.1,is a C-glycoside compound.It is present in a large amount of active components of Puerariae radix,a com-monly used Chinese herb,which exerts sedative and antipyretic actions and is often used to treat influ-enza,wrist stiffness and headache[1].A number of investigations were carried out internationally to iden-tify the physiological activities of puerarin such as antiproliferative…     

Conformational distribution of a 14-residue peptide in solution: a fluorescence resonance energy transfer study

We demonstrate here that a nitrile-derivatized phenylalanine residue, p-cyanophenylalanine (Phe(CN)), and tryptophan (Trp) constitute a novel donor-acceptor pair for fluorescence resonance energy transfer (FRET). The F?rster distance of this FRET pair was determined to be approximately 16 A and hence is well suited for determining relatively short separation distances. To validate the applicability of this FRET pair in conformational studies, we studied the conformational heterogeneity of a 14-residue amphipathic peptide, Mastoparan X (MPx peptide), in water and 7 M urea solution as well as at different temperatures. Specifically, seven nitrile-derivatized mutants of the MPx peptide, each containing a Phe(CN) residue that replaces different positions along the peptide sequence (i.e., from position 5 to 11) and serves as a resonance energy donor to the native Trp residue at position 3, were studied spectroscopically. The FRET efficiencies obtained from these peptides allowed us to gain a global picture regarding the conformational distribution of the MPx peptide in different environments. Our results suggest that the MPx molecules exist in water as an ensemble of rather compact conformations, with a radius of gyration of approximately 4.2 A, whereas in 7 M urea the radius of gyration increases to approximately 6.5 A, indicating that the peptide conformations become more extended under this condition. However, we found that temperature had only a negligible effect on the size of the MPx peptide, underlining the difference between the thermally and chemically denatured states of polypeptides. The application of the Gaussian chain or the wormlike chain model allowed us to further obtain the probability distribution function of the separation distance between any two residues along the peptide sequence. We found that the effective bond length of the MPx peptide, obtained by using the Gaussian chain model, is 2.78 A in water and 4.28 A in 7 M urea.     

DFT study of ferroelectric properties of the copolymers: Poly(vinylideneflouride‐trifluoroethylene) and poly(vinylidene fluoride‐chlorotrifluoroethylene)

A theoretical study of poly(vinylidene flouride‐trifluoroethylene) and poly(vinylidene fluoride‐chlorotrifluoroethylene, is presented. By density functional theory calculations, some of the properties of these materials have been obtained. Among such properties, the dipolar moment and the energies associated to the structural changes. The B3LYP functional and 6311+G(d,p) bases set were used with Gaussian program. Calculations associated to different conformations were carried out to get insight about the involved phase changes. The energetic, charges, and dipole moment were calculated. The conformations, namely, I = T_p, II = TG_a, and III = TG_p, where T means trans and G means gauche, for the two polymers aforementioned were compared with the poly(vinilydene fluoride) studies previously obtained. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2411–2417, 2010     

Shot-noise limited single-molecule FRET histograms: comparison between theory and experiments

We describe a simple approach and present a straightforward numerical algorithm to compute the best fit shot-noise limited proximity ratio histogram (PRH) in single-molecule fluorescence resonant energy transfer diffusion experiments. The key ingredient is the use of the experimental burst size distribution, as obtained after burst search through the photon data streams. We show how the use of an alternated laser excitation scheme and a correspondingly optimized burst search algorithm eliminates several potential artifacts affecting the calculation of the best fit shot-noise limited PRH. This algorithm is tested extensively on simulations and simple experimental systems. We find that dsDNA data exhibit a wider PRH than expected from shot noise only and hypothetically account for it by assuming a small Gaussian distribution of distances with an average standard deviation of 1.6 A. Finally, we briefly mention the results of a future publication and illustrate them with a simple two-state model system (DNA hairpin), for which the kinetic transition rates between the open and closed conformations are extracted.     

Chain conformation in two-dimensional dense state

In an effort to provide evidence concerning the conformation of many chains in strict two-dimensional (2D) dense state, we synthesized polymer chains of diameter of nanometers through an anionic polymerization process. The conformational characteristics of the long chain molecules in films of thickness h corresponding to the chain diameter a were directly obtained from atomic force microscopy observations. In 2D dispersed state, the conformations of the long chain molecules were typical Gaussian. However, in 2D dense state the long chain molecules were strongly interpenetrated. Their conformations were largely perturbed by the presence of neighbor chains and were not Gaussian. This result was in contradiction with the segregated globule model predicted by de Gennes. The central reason is that 2D space cannot be filled to normal density with 2D Gaussian globules; either the area must be greatly increased with consequently large voids, or the globule conformation must be expanded by allowing chains to interpenetrate each other.     

Polymer translocation through a cylindrical channel

A formalism of polymer translocation through a cylindrical channel of finite diameter and length between two spherical compartments is developed. Unlike previous simplified systems, the finite diameter of the channel allows the number of polymer segments inside the channel to be adjusted during translocation according to the free energy of possible conformations. The translocation process of a Gaussian chain without excluded volume and hydrodynamic interactions is studied using exact formulas of confinement free energy under this formalism. The free energy landscape for the translocation process, the distribution of the translocation time, and the average translocation time are presented. The complex dependencies of the average translocation time on the length and diameter of the channel, the sizes of the donor and receptor compartments, and the chain length are illustrated.     

Synthèse et étude conformationnelle de dioxa-1,3 aza-9 spiro[5,5]undecanes

Synthesis of the new l,3-dioxa-9-azaspiro[5.5]undecane ring, was realized by the scheme represented in Figure 2. Butyro-phenones 6 posses neuroleptic activity similar to that of halo-peridol. The pharmacological activity was reported in another publication (2). Conformational study of l,3-dioxa-9-azaspiro-[5.5]undecanes shows the existence of four conformations A, B, C and D, which are shown in Figure 4. The existence of these conformations depends on the nature of the substituents R and R' on the dioxane ring. Thus, in the compounds where R ≠ H, R' = H, the four conformations are possible with a preponderance of A and B. If R and R' are different from H only the conformation A is present in 99% concentration. Lastly, when R = R' = H, the four conformations are possible with equal population for the couple A, B and the couple C, D; the first couple predominating. The presence of a fluorophenylbutyric moiety on the piperidine nitrogen does not seem to stereochemically modify the heterocyclic group.     

Separating structural heterogeneities from stochastic variations in fluorescence resonance energy transfer distributions via photon distribution analysis

We establish a probability distribution analysis (PDA) method for the analysis of fluorescence resonance energy transfer (FRET) signals to determine with high precision the originating value of a shot-noise-limited signal distribution. PDA theoretical distributions are calculated explicitly including crosstalk, stochastic variations, and background and represent the minimum width that a FRET distribution must have. In this way an unambiguous distinction is made between shot-noise distributions and distributions broadened by heterogeneities. This method simultaneously and effectively extracts highly resolved information from FRET distributions. The theoretical histograms match the exact profile of histograms generated from constant transfer efficiency experimental data with a chi2 near unity. The chi2 surface suggests an ultimate level of precision with FRET of < 1% of the F?rster radius. Distributions of FRET signals in donor-acceptor-labeled DNA were unambiguously identified as being broader than shot-noise variations could explain. A model describing a Gaussian distribution of distances was tested with the PDA method and demonstrated 5 A inhomogeneities due to dye motions. The capability of this method to recover quantitative information from FRET distributions has potential applications for studying molecular conformations and dynamics. Potential sources for artifacts such as acceptor photobleaching, spectrally different observation volumes, and fluctuations of the F?rster radius are ruled out.