Manumycin的2D NMR研究

应用1D NMR 和梯度2D NMR技术（gCOSY，gNOESY，gHSQC，gHMBC）深入研究了从链霉菌发酵物中分离提取得到的Manumycin的结构，并对其¹H和¹³C NMR化学位移进行了全归属. 计算机分子模拟与NMR研究取得一致结论.     

南海海绵Dysidea fragilis中两个倍半萜内酯的NMR研究

用一维¹H、¹³C NMR谱、DEPT ¹³C NMR谱、选择性远程DEPT ¹³C NMR、¹H-¹H COSY和¹³C-¹H COSY二维核磁共振技术研究了南海海绵Dysidea fragilis中的两个倍半萜herbadysidolide(1)和furodysinin lactone(2),确认了化学结构,并对其¹³C NMR和¹H NMR谱进行了归属.药理活性试验表明:1和2具有一定的心血管活性.     

线性高分子体系中高分子链间排除体积效应的模型化

提出了线性高分子体系中高分子链间排除体积效应的一个它回避模型，并且针对具体的四个模型系统进行了计算机模拟. 计算结果表明：1)线团的均方末端距〈R²〉与行走步数(N)仍然保持着与无规线团模型一样的线性关系；2)但与无规线团相比，线团的空间尺寸被压缩；3)与两侧方向的回避相比，在行走的前进方向的回避而导致的压缩效应更加明显. 关键词： 排除体积效应 回避行走 无规线团 线性高分子     

聚醚酰亚胺(YS-30)链结构的1D和2DNMR谱分析

聚醚酰亚胺(YS-30)是一种可溶性的聚酰亚胺,本文对它的¹³C NMR谱,¹NNMR谱和COSY谱进行了研究.经过分析,对¹³C NMR和¹H NMR谱作出了归属,确认了聚醚酰亚胺的链结构.     

天然结晶辣椒碱的NMR谱研究

用一维¹H NMR谱、¹H-¹H COSY谱和一维¹³C NMR谱、DEPT谱研究辣椒碱分子和二氢辣椒碱分子及其混合物,得到¹H和¹³C的化学位移,采用¹H NMR谱测定天然辣椒碱中辣椒碱和二氢辣椒碱的相对含量.     

丙烯腈γ辐射聚合的NMR研究

用¹H NMR、¹³C NMR谱、自旋-晶格弛豫时间（T₁）和自旋-自旋弛豫时间（T₂）研究了丙烯腈在⁶⁰Co γ射线辐射聚合后的大分子结构变化与大分子链的运动. 结果表明随着辐射剂量增大，在单体形成聚合物的过程中，聚合物主链上出现了少量的-OH基团，继续增大辐射剂量， -OH部分被氧化. 对聚合物溶液的变温氢谱的研究表明，溶剂中的残余水与上述-OH形成氢键，且随着温度升高氢键被破坏，同时H₂O与-OH之间还存在着质子交换. 利用¹³C NMR谱对丙烯腈辐射聚合的产物进行了序列结构分析. 对T₁和T₂的研究表明，辐射剂量的增大并未影响到聚丙烯腈的链运动，证明了在丙烯腈的辐射聚合过程交联反应未发生.     

先进固体NMR技术研究高分子结构与动力学

随着固体NMR理论和谱仪硬件技术的不断发展,近年来固体NMR技术在高分子多尺度结构与动力学研究领域中正发挥着越来越重要的作用. 多脉冲及高速魔角旋转（MAS）等质子高分辨技术的发展使得高灵敏度的¹H谱可有效地用于高分子化学结构与链间相互作用的检测;基于化学键（J-耦合）相关和通过空间（偶极耦合）相互作用的各种二维异核相关谱NMR新技术,使得复杂高分子的链结构得以严格解析. 基于MAS下同核和异核偶极-偶极相互作用、化学位移各向异性等各向异性相互作用重聚的系列新技术,使得研究者可在采用高分辨¹H或¹³C 检测信号的同时检测准静态下的各向异性相互作用,进而获得与之密切相关的结构和动力学信息. 通过质子偶极滤波技术可有效检测多相聚合物中的界面相与相区尺寸、高分子共混物中的相容性等问题. 在动力学的研究中,通过质子间自旋扩散的有效压制技术和化学位移各向异性的重聚,目前已经可以有效地获取链段上单个化学键的快速局域运动以及链段的超慢分子运动. 上述丰富的多尺度NMR技术可以使研究者在不同空间和时间尺度上对高分子聚合物的微观结构、相分离和动力学行为等进行详细的研究,进而阐明高分子微观结构与宏观性能的关联. 该文以固体NMR中最主要的2类核（¹H和¹³C）的检测技术为主线,简单介绍近年来固体NMR领域的一些最新研究进展及其在高分子结构和动力学研究中的应用.     

通过宽线固体核磁共振氢谱研究半晶高分子的相结构

宽线固体核磁共振氢谱（¹H NMR）是一种研究半晶高分子相结构的经典方法.本文以半晶聚乙烯的宽线固体¹H NMR谱为例，探讨了通过Gaussian/Sinc、Gaussian和Lorentzian函数组合对宽线固体¹H NMR谱图进行拟合的方案，并根据半晶聚乙烯的相结构成分对拟合得到的各信号成分进行归属.并在此基础上探讨了各个相结构中分子链运动与信号线型的相关性，以及利用宽线固体¹H NMR谱测量半晶高分子结晶度存在的困难.     

EDTA衍生物冠醚的NMR研究

报道N,N'-二羧甲基大环醚双内酯(1-4)¹H NMR溶剂效应,¹H NMR跟踪的稳定性研究,溶剂极性影响标题化合物构象互变而表现为¹³C谱线特征.     

1-[2-(2,4-二氯苯基)-4-烷基-1,3-二氧戊环-2-基甲基]-1H-1,2,4-三唑的NMR研究

测定了戊环唑（1）、甲环唑（2）、丙环唑（3）的NMR谱,对其一般特征进行 了对比与讨论,用¹³C-¹H COSY、¹³C-¹H COLOC、DQF-COSY、DEPT等技术对它们的¹H、¹³C NMR谱峰进行了全归属,并应用¹H-¹H NOESY谱研究其立体结构.
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‘Monte Carlo’ computer simulation of chain molecules III. Simulation of n-alkane molecules

Considering a realistic model for isolated n-alkane molecules, their configurational behaviour has been explored employing a ‘Monte Carlo’ method. The present study shows that the behaviour of the short molecules is unlike that of the longer molecules in regard to the variation with temperature of the mean-square end-to-end distance and radius of gyration. For the short molecules the mean-square end-to-end distance and the radius of gyration are decreasing functions of temperature, but they increase with temperature in the case of the longer molecules. The macromolecules assume random-walk behaviour at approximately 600 K. The computed heat capacity versus temperature curves disclose configurational transitions in the chains.     

Elasticity transition and loop formation in vibrated bead chains: A simulation of polymer chains

By measuring the distribution function of the end-to-end distance, we find that strongly shaken bead chains exhibit many properties, such as the rigid-rod-to-Gaussian chain transition, scaling, fast drop of loop formation probability in the short-chain regime, and enhancement of loop formation probability for kinked chains, of long-chain polymers. Though there is difference in local details between our chains and the worm-like chains, our results are consistent with recent calculations based on the worm-like chain model in many respects.     

Dissipative Particle Dynamics Simulation of Microscopic Properties in Diblock Copolymer Films

利用耗散粒子动力学模拟方法研究了两嵌段共聚高分子薄膜中的一些微观性质. 结果表明：薄膜中共聚高分子链的均方根末端距2_e>^1/2、均方根回旋半径2_g>^1/2与薄膜厚度l、不同粒子间的相互作用强度a_ij、粒子与薄膜边界间的排斥作用强度a_pb均呈线性关系,而均方键长与a_ij、a_pb呈线性关系,随l增加则呈现出波浪形趋势. 2_e>^1/2与2_g>^1/2的变化趋势可以相互对应. 任一组分在薄膜中的密度分布可以通过其与薄膜边界间的相互作用来有效控制与调节.     

Configurational-conformational statistics of stereoirregular poly(methyl methacrylate)s

The mean-square radius of gyration of poly(methyl methacrylate) (PMMA) with Bemoullian statistics was theoretically investigated utilizing the method of periodic condition. The dependent curve of the characteristic ratio of mean-square end-to-end distance on periodic microstructure length increases monotonously with the length and goes gradually to its asymptotic value for atactic PMMA chains (P _m = 0.5). Conformational energies E _α ～1.3 kcal mol^?1 and E _β ～-0.6 kcal mol^?1 of the two-state scheme are acceptable, from which the derived meansquare end-to-end distance and mean-square radius of gyration conform to the experimental data. The ratio ?S²?/χ of atactic PMMA (P _m = 0.2) as a function of the degree of polymerization χ first increases with increasing chain length, then passes through a maximum at χ = 30, and finally decreases to its asymptotic value, which is in reasonable agreement with the experimental measurements reported elsewhere. The ratio ?S²?/χ as a function of stereochemical composition indicates that theoretical and experimental data are in accord for isotactic and atactic PMMA, but small-angle neutron scattering (SANS) measurements are higher than the calculated values for syndiotactic PMMA.     

Off-lattice Monte Carlo simulation of supramolecular polymer architectures

We introduce an efficient, scalable Monte?Carlo algorithm to simulate cross-linked architectures of freely?jointed and discrete wormlike chains. Bond movement is based on the discrete tractrix construction, which effects conformational changes that exactly preserve fixed-length constraints of all bonds. The algorithm reproduces known end-to-end distance distributions for simple, analytically tractable systems of cross-linked stiff and freely jointed polymers flawlessly, and is used to determine the effective persistence length of short bundles of semiflexible wormlike chains, cross-linked to each other. It reveals a possible regulatory mechanism in bundled networks: the effective persistence of bundles is controlled by the linker density.     

Tracer studies on f-actin fluctuations

We present a study on the fluctuations of semiflexible actin filaments using fluorescence videomicroscopy, focusing on the end-to-end fluctuations of single filaments. In order to specifically measure the position of the polymer's ends, we developed a novel noninvasive method that consists of annealing short end tags to the filaments. This allows us to probe polymer fluctuations to a very high accuracy. We compared the distribution of the end-to-end distance with recent theoretical results, and found excellent agreement. We also studied the dynamics of the mean-square end-to-end distance deltaR2(t) and orientation of the ends, deltaTheta(2)(t), finding power laws t(3/4) and t(1/4), respectively. Scaling behavior for deltaR2(t) is observed over several decades in relaxation time in agreement with theoretical results.     

Correction-to-Scaling Exponents for Two-Dimensional Self-Avoiding Walks

We study the correction-to-scaling exponents for the two-dimensional self-avoiding walk, using a combination of series-extrapolation and Monte Carlo methods. We enumerate all self-avoiding walks up to 59 steps on the square lattice, and up to 40 steps on the triangular lattice, measuring the mean-square end-to-end distance, the mean-square radius of gyration and the mean-square distance of a monomer from the endpoints. The complete endpoint distribution is also calculated for self-avoiding walks up to 32 steps (square) and up to 22 steps (triangular). We also generate self-avoiding walks on the square lattice by Monte Carlo, using the pivot algorithm, obtaining the mean-square radii to ≈ 0.01% accuracy up to N=4000. We give compelling evidence that the first non-analytic correction term for two-dimensional self-avoiding walks is Δ₁=3/2. We compute several moments of the endpoint distribution function, finding good agreement with the field-theoretic predictions. Finally, we study a particular invariant ratio that can be shown, by conformal-field-theory arguments, to vanish asymptotically, and we find the cancellation of the leading analytic correction.     

Scaling exponent and Kuhn length of pinned polymers by single molecule force spectroscopy

The end-to-end distance and the contour length of single polymers in dynamic adsorbate layers were measured with a mechanical approach. Individual polysaccharide chains were covalently pinned to the surface with one segment and picked up randomly with an atomic force microscope tip. The polymer section between pinpoint and the pickup point was stretched by retracting the tip from the surface. The pinpoint was derived by measuring the normal force while laterally scanning the surface at constant height. For carboxy-methyl-amylose, a Kuhn length of 0.44 nm and a scaling exponent of 0.74 were found.     

Fluorescence quenching kinetics in short polymer chains: Dependence on chain length

Monte Carlo simulations of chain conformations and the diffusion equation were used to analyze the fluorescence kinetics of short polymer chains labeled with a probe and a quencher at opposite ends. In simulations, three chain models were considered: an ideal chain (without volume interactions); a self-avoiding chain taking into account the exclusive volume effect; and a self-avoiding chain with limited flexibility between nearest segments. For each model, end-to-end distance distribution functions were obtained, which were different from Gaussian ones. The distribution functions were used in a diffusion equation to simulate the fluorescence kinetics of the probe affected by intramolecular end-to-end collisions of short chains. The kinetics has been numerically calculated for a representative experimental system in a nonviscous solution. The simulated time-resolved fluorescence decays were monoexponential except at very short times (<2 ns). Diffusion coefficients were calculated for different chain models and different chain lengths. The experimental data could be reproduced by assuming systematically smaller end-to-end diffusion coefficients for the shorter chains.