13C及29Si核磁共振研究苯乙烯-二甲基硅氧烷嵌段共聚物的弛豫及分子运动

用¹³C及²⁹Si核磁共振研究了苯乙烯(S)及二甲基硅氧烷(Si)嵌段共聚物中硅氧烷软段的固体及溶液谱的自旋-晶格弛豫时间T₁。固态嵌段共聚物主链²⁹Si及侧甲基¹³C的T₁都与均聚物的T₁相近,但在CdCl₃溶液中各种嵌段共聚物的T₁与均聚硅氧烷相差颇大。用偶极-偶极相互作用来解释高聚物的自旋-晶格弛豫。苯乙烯-二甲基硅氧烷嵌段共聚物具两相结构,所以嵌段共聚物中软段及硬段微区中链段的运动与在均聚物分子中链段的运动模式基本相同。而CdCl₃对聚苯乙烯或聚硅氧烷都是良溶剂,软段硬段之间有相互影响。所以其链段运动与均聚物不同,从而导致链段运动的相关时间τ_c变短和T₁的增长。     

丙烯酰胺-甲基丙烯酸共聚物结构的NMR研究

用¹H NMR谱,¹³C NMR谱,DEPT谱,gHMQC,gHMBC二维谱和质子弛豫时间等方法研究了在紫外光辐照条件下丙烯酰胺(AM) -甲基丙烯酸(MAA)共聚合反应,讨论了AM-MAA共聚合反应时间与转化率的关系、共聚单体的连接方式、共聚物序列结构以及不同辐照时间下形成的共聚物链运动. 结果表明在紫外光辐照条件下,AM-MAA共聚物链节中同时存在多种连接方式,当反应时间为45 min时,共聚合转化率可达100%. 从自旋-晶格弛豫时间（T₁）和自旋-自旋弛豫时间（T₂）测定中得出,在辐照1小时范围内,时间越长聚合物长链分子运动速度越快,但主链的链段运动变化不明显.     

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.     

PVP在水/丙酮混合溶剂中分子运动行为的研究

通过对粘度、自旋-自旋弛豫时间以及1H NMR谱的测定,研究了PVP在不同体积配比的水/丙酮溶液中的特性粘数变化和分子运动规律,并讨论了引起这些变化的原因.结果表明:随着丙酮的不断加入,PVP的特性粘数[η]先增加后减小,而T2H先减小后增大.[η]出现最大值也是T2H出现最小值的时候,丙酮的体积百分数为40%.丙酮的加入破坏了水分子间自身氢键相互作用形成的网状结构,解离出来的水分子被PVP优先吸附到大分子链上,部分与羰基形成氢键,另一部分以自由水的形式被包裹在大分子线团内.水分子的不断进入以及与水形成新的氢键使PVP链逐渐伸展,引起特性粘数的增大,分子运动受阻.当丙酮含量增加到一定程度时,水的含量不足以使大分子链继续膨胀,故链呈卷缩状态,使大分子运动逐渐恢复自由.1H NMR谱中各质子的化学位移变化也证实了此过程中的氢键变化规律.     

利用光晶格自旋链中磁振子的激发模拟有限温度下光子的动力学 Casimir 效应

研究了在静磁场诱导的磁偶极-偶极相互作用和外部激光场诱导产生的偶极-偶极相互作用下光晶格自旋链中磁振子激发的动力学特征. 文中选取了蓝失谐光晶格, 提出了等效温度的概念, 并将系统中磁振子的激发过程与光学振动腔中光子的激发过程进行了类比. 研究表明, 通过选取适当的系统参数, 可以在磁振子系统中重现有限温度下光子的动力学Casimir效应. 关键词： 光晶格 偶极－偶极相互作用 磁振子 Casimir效应     

三种胺羧配合物的113Cd NMR研究

该文对Cd-HEDTA(N-(2-羟基乙基)乙二胺-N',N',N'-三乙酸),Cd-PDTA(1,2丙二胺四乙酸)和Cd-DTPA(二乙三胺五乙酸)的¹¹³Cd NMR谱和自旋晶格弛豫时间T₁,及NOE因子进行了研究.结果表明,Cd-HEDTA和Cd-PDTA结构与Cd-EDTA类似,Cd-PDTA双线归因于其可能的两种异构体.Cd-DTPA大的化学位移表明其具有七配位的五角双锥结构.在这种结构中DTPA可用三个氮原子参加配位.对¹¹³Cd自旋晶格弛豫时间分析表明,Cd-DTPA配合物中质子偶极作用机理的贡献较大,这归因于Cd DTPA有更多的乙酸根亚甲基质子参与偶极作用.     

玻色凝聚的原子自旋链中的非线性自旋波

研究了囚禁在光晶格中的旋量玻色-爱因斯坦凝聚体(BEC)形成的原子自旋链中的相干非线性自旋波的激发与调制不稳定性.通过解析分析，得到了调制不稳定性的一般判据以及其对原子自旋的长程耦合的依赖关系.在蓝失谐和红失谐光晶格的情况下，分别具体分析了长程非线性自旋耦合，包括光诱导的和静磁诱导的偶极-偶极相互作用对相干自旋波调制不稳定性的影响.     

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.     

紫外光辐照镍系聚丁二烯的NMR研究

用¹H NMR谱,¹³C NMR谱,二维谱,X-射线衍射等方法研究了镍系高顺式聚丁二烯橡胶(NiBR) 在强紫外（UV）光辐照前后的微观结构变化和分子运动情况. 分析表明NiBR样品随着UV光辐照时间的增加,侧链乙烯基端基双键比主链端基双键更易发生氧化反应;并且随着NiBR样品的各基团的半峰宽值逐渐增加,表明NiBR在UV辐照过程中发生了部分交联反应. 样品的X-射线衍射谱图中结晶峰强度随UV光辐照时间的增加逐渐降低,表明样品的晶形无序程度增加了. 自旋-晶格弛豫时间（T₁）和自旋-自旋弛豫时间（T₂）值给出了有关NiBR辐照前后分子运动变化的信息.      

聚酰胺66溶液弛豫行为的NMR研究

用1D和2D NMR技术归属了聚酰胺66的1H和13C的NMR共振信号,并通过聚酰胺66溶液温度和浓度改变对氢核弛豫时间的影响,得到了其分子运动信息.结果表明随着温度的升高,聚酰胺66链间氢键逐渐解离,大分子链间相互作用逐渐减弱.而解离出来的链段又与溶剂小分子可以形成新的氢键,使聚酰胺66链卷曲并包含着部分溶剂分子一起运动.随着溶液浓度的增大,由于分子链间距变小,使得分子间作用力增强,链缠结程度加大,使链运动受限.     

Proton spin relaxation in bisphenol-a polycarbonate,butyl rubber,and their composites

Proton spin-lattice relaxation times of bisphenol-A polycarbonate, butyl rubber, and blends of the two polymers were studied at 18 Mc/sec in the temperature range 90°-450°K. The proton spin-lattice relaxation is primarily dipolar in each polymer, due to methyl group reorientation and to reorientation of chain segments. In a blend of bisphenol-A polycarbonate with 7 and 10 wt of butyl, a nonexponential decay of magnetization was observed in the temperature range 280°-380°K. This was explained by the existence of two spin temperatures in these blends, indicating that processes which bring about the equilibrium within the spin system are slow compared to the spin-lattice relaxation times of the two components of the blend.     

NMR relaxation study of molecular dynamics in columnar and smectic phases of a PAMAM liquid-crystalline co-dendrimer

We present the first results obtained by proton (¹H) nuclear magnetic relaxation studies of molecular dynamics in a supermolecular liquid-crystal dendrimer exhibiting columnar rectangular and smectic-A phases. The ¹H spin-lattice relaxation time (T₁) dispersions are interpreted using two relaxation mechanisms associated with collective motions and local molecular reorientations of the dendritic segments in the low- and high-frequency ranges, respectively. The T₁ values show a drop around 2.3 MHz that is attributed to a contribution coming from cross-relaxation between ¹H and nitrogen nuclear spins. In the high-frequency range the motions appear to be of similar nature in both mesophases and are ascribed to reorientations of dendritic segments (belonging to the core and/or to the mesogenic units) characterized by two correlation times. Notable differences in the dynamics between the columnar and layered phases are observed in the low-frequency range. Depending on the mesophase they are discussed in terms of elastic deformations of the columns and layer undulations. In this study we find that the dendritic core influences the dynamics of the mesogenic units both for local and collective motions. These results can be understood in terms of spatial constraints imposed by the dendritic architecture and by the supermolecular arrangement in the mesophases.     

Molecular reorientations of 1-bromo- and 1-iodo-adamantanes 1H N.M.R. relaxation study

Second moments and spin-lattice relaxation times, T ₁ and T _1ρ, have been measured from 100 K to 400 K for the protons in powdered 1-bromo and 1-iodo-adamantanes. Analysis of these data have shown that the reorientations are uniaxial in the low temperature phases. In the high temperature disordered phase of bromo-adamantane, the reorientation is endospherical and a slow molecular translational motion also exists. In the high temperature disordered phase of iodo-adamantane the reorientation is 12-fold uniaxial, in agreement with the Incoherent Quasi-elastic Neutron Scattering (I.Q.N.S.) experiments. All the results correspond to the crystallographic structures deduced from X-ray scattering.     

Molecular dynamics of poly(L-lactide) biopolymer studied by wide-line solid-state 1H and 2H NMR spectroscopy

The molecular dynamics of poly(L-lactide) (PLLA) biopolymer was characterized through analyses of 1H and 2H NMR line-shapes and spin-lattice relaxation times at different temperatures. At low temperatures (e.g. 90 K), the methyl group rotation is dominant leading to a significant reduction in the proton second moment. Fast methyl group reorientation occurs at ca. 130 K. In additional to the fast methyl group rotation, hydroxyl groups start to reorient as the temperature increases further, eventually leading to the breakdown of the segments of the biopolymer chains above its glass transition temperature Tg of 323 K. The analyses of the 2H NMR line-shapes indicate that both the methyl and hydroxyl reorientations can be described by the so-called cone model, in which the former has three equilibrium positions with theta(C-D) = 70.5 degrees and phi = 120 degrees while the latter one exhibits two equilibrium positions with theta(O-D) = 78 degrees and phi = 180 degrees .     

NMR study of molecular dynamics in selected hydrophilic polymers

The temperature dependencies of the 1H spin-lattice relaxation times T1 and of the proton NMR second moment M2 in the temperature range from about 90 to 420 K were measured for methyl cellulose, hydroxypropyl cellulose and hydroxypropyl methyl cellulose. The proton spin-lattice relaxation measurements reveal two minima due to the C3 reorientation of the methyl groups of the methoxy, methylenemethoxy or propylene oxide groups and the restricted motion of the segment of the polymer chain. The activation energy barriers for these motions were calculated.     

Proton spin-lattice relaxation in MBDBP

We have measured the proton spin-lattice relaxation rate R in 4,4′-methylenebis(2,6-di-t-butylphenol) (MBDBP) and MBDBP-OD (deuteriated hydroxyl proton) between 88 K and 380 K. The experimental results are compared with those from a previous study in the closely related but simpler molecule 4-methyl-2,6-di-t-butylphenol (MDBP). The present experiment is analysed in terms of relaxation resulting from intramolecular reorientation modulation of the proton spin-spin interaction. This intramolecular reorientation involves different combinations of superpositions of methyl, t-butyl, aromatic ring and hydroxyl group reorientation and a discussion is presented concerning the effects on the relaxation of superimposing these motions. The MBDBP-OD data is best fitted with the assumption that only methyl and aromatic ring reorientations occur. In MBDBP it is found that, in addition, an OH flip-flop motion is superimposed on the aromatic ring reorientation.     

Ammonium ion dynamics in NH4I at high pressure

Measurements of spin-lattice relaxation time T ₁ have been performed for polycrystalline ammonium iodide NH₄I as a function of hydrostatic pressure and temperature. Activation parameters were obtained for different models of ammonium ion reorientations. It was found that the dominant mechanism for ammonium reorientational motion in the ordered phases III and IV was the reorientation around C₃ axes. Reorientation activation volume and libration frequency of ammonium ions as a function of pressure were calculated for different phases.     

2-Nitroimidazole derivative studied by means of35Cl-NQR spectroscopy and molecular dynamics simulations

³⁵Cl nuclear quadrupole resonance as well as quantum chemical calculations were applied to study electronic structure and molecular dynamics of the imidazole derivative 1-(2-hydroxy-3-chloroprophyl)-2, 3-dinitro-5-methyl-imidazole. The spectra of this compound taken at 77 and 293 K show only one line, which means that there are no physically inequivalent positions of the chlorine atoms in the elementary cell. The line width was of about 28 kHz at 77 K and the relaxation time was about 320 ms at liquid-nitrogen temperature and about 8 ms at room temperature. As follows from the spin-lattice relaxation time measurements performed for the compound studied, in the range 77–200 K the libration mechanism of molecular vibrations is active, while above 200 K the activation process related to reorientation of the CH₂Cl group begins. The activation energy is 18.82 kJ/ mol. The activated process of the CH₂Cl group reorientations exerts rather insignificant effect on the averaging of the electric field gradient in the vicinity of the resonant³⁵Cl nucleus.     

Proton magnetic resonance study of the low-temperature phase transition in a LiNH4SO4 single crystal

The proton NMR line width and spin-lattice relaxation times for LiNH₄SO₄ single crystal were studied at low temperature range of 6 and 280 K. The changes in the proton relaxation behavior near the phase transition temperature indicates a change in the state of internal motion at the transition. The molecular motions obtained by the spin-lattice relaxation processes were found to be determined by molecular reorientation of the NH₄ ions in phases III, IV, and V. We also confirmed that the phase transitions occur at 26 and 133 K.