一种反铁电液晶薄膜相变过程的变温红外光谱研究

通过变温红外光谱对反铁电液晶MHOCPOOB薄膜相变过程中的分子构象、排布及相互作用的变化进行了研究.结果表明,室温时,薄膜中的分子烷基链同时含有zigzag和gauche两种构象.随着温度的升高,有序的zigzag构象转化为无序的gauche构象,链的扭曲程度增加.但S^*IA到S^*CA的转变并不引起烷基链构象和取向发生明显变化.刚性核中的羰基与相邻的苯环形成共轭体系,苯环之间相互倾斜排列,在相变过程中羰基与苯环的共平面作用逐渐被打破,且在相变点苯环间的二面角明显增大.     

十六烷基三甲基溴化铵水溶液热致相变的红外光谱研究

在280～320K的温度范围内考察了30％十六烷基三甲基溴化铵水溶液的红外光谱随温度的变化。结果表明该体系的凝聚胶-液晶相转变温度为300K。在300K以下的凝聚胶相,分子的极性头部基团处于高度“固定”的状态,分子的碳氢链以有序的相互平行方式排列,极性头与碳氢链之间有一定的倾斜角。在300K以上的液晶相,极性头内部CH_3-(N~+)基团以及整个极性头与碳氢链之间发生了旋转,碳氢链变为以六方亚晶胞填充形式存在,旦扭曲式构象异构体数量显著增多,极性头与碳氢链之间已不存在倾斜角,分子的亲水极性头和疏水碳氢链部分都处于“融化”状态。     

月桂胺盐酸晶体相变的红外光谱研究

在290-365K的温度区间内考察了月桂胺盐酸盐晶体红外光谱随温度的变化规律。结果表明:月桂胺盐酸盐在339K发生了固-固结构相变, 该相变的预相变起始点为327K。在327K以下的低温相中, 晶体中分子的碳氢链以高度有序的全反式构象存在, 极性头部的三个N-H-Cl氢键是不等价的。在327-339K的中间过渡相, 碳氢链中出现了旁式构象, 分子链间相互作用减弱。不等价的N-H-Cl氢键的差异减小。在339K以上的高温相中, 分子旁式链构象的增多导致了分子链横向堆积无序性的明显增加, 三个N-H-Cl氢键已变得等价。     

月桂胺盐酸晶体相变的红外光谱研究

在290-365K的温度区间内考察了月桂胺盐酸盐晶体红外光谱随温度的变化规律。结果表明:月桂胺盐酸盐在339K发生了固-固结构相变, 该相变的预相变起始点为327K。在327K以下的低温相中, 晶体中分子的碳氢链以高度有序的全反式构象存在, 极性头部的三个N-H-Cl氢键是不等价的。在327-339K的中间过渡相, 碳氢链中出现了旁式构象, 分子链间相互作用减弱。不等价的N-H-Cl氢键的差异减小。在339K以上的高温相中, 分子旁式链构象的增多导致了分子链横向堆积无序性的明显增加, 三个N-H-Cl氢键已变得等价。     

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.     

大豆磷脂中磷脂酰胆碱的脂肪酸组成分析

1　引　　言磷脂是生物膜的主要成分 ,是由甘油骨架、极性基团和不饱和脂肪酸组成的脂质类化合物。磷脂种类 (ＰＣ ,ＰＥ等 )的化学组成决定磷脂的物理特性 ,进而影响生物膜的功能。研究表明 :磷脂脂肪基团中不饱和碳 碳键是决定其相变温度的关键因素 ,同时 ,环境因素影响磷脂的脂肪酸组成 ,随环境温度的变化 ,磷脂的脂肪酸组成也作出相应的调整。因此 ,测定磷脂酰胆碱的脂肪酸组成 ,对研究大豆的遗传性及环境因素对其所造成的影响具有重要意义。磷脂脂肪酸组成的分析已有报道 ,但对于大豆磷脂酰胆碱脂肪酸组成的分析国内至今未见报道。本…     

月桂胺盐酸盐结构相变机理的红外光谱研究

月桂胺盐酸盐晶体的红外光谱研究表明,标题化合物两个结构相变的起始温度分别为327和339K。在327K以下晶体中分子以TT构象存在并以分子链相互平行的叉指状形式填充,339K以上分子以TG构象和部分GTG'构象存在并以非叉指状的六方形式填充,在327～339K之间则是一个分子构象由有序到无序、链填充由叉指状到非叉指状转变的中间过渡相。     

DPPC双分子层相转变行为的分子动力学模拟研究

应用分子动力学模拟技术,对二棕榈酰磷脂酰胆碱双分子层进行退火模拟,从微观水平上深入研究磷脂双层膜的相转变行为.在相变温度附近,磷脂双层膜的物理性质发生突变.在两相各自的温度范围内,凝胶相磷脂双层膜的物理性质随温度变化不明显,但液相呈缓和变化.凝胶相与液相磷脂双层膜的分子构象与其排布方式截然不同:从侧视图来看,前者脂质分子尾链纵向伸展,上下两叶未见交错,叶间隙清晰,后者脂质分子尾链横向弯曲,上下两叶并有交错,叶间隙消失;从俯视图来看,前者脂质分子烃链以极其规律的"六角边形"方式排列,而后者脂质分子烃链排列杂乱无章.     

海藻糖与脂质膜体系的红外光谱分析

冻干保护剂海藻糖对磷脂脂双层有保护作用，它可以降低磷脂主相变温度，抑制膜脂侧相分离和膜融合。本实验以蛋黄卵磷脂(EPC)为模型，通过相变发生时磷脂吸热量的变化，以及磷脂脂肪酸链CH2基团的对称伸展振动频率的变化，研究海藻糖对蛋黄卵磷脂(EPC)脂质膜相变时影响，并通过FTIR红外光谱分析得到进一步验证。     

两亲性分子聚集体的相变及其协同性

两亲性分子聚集体是一类重要的软物质,它们有着丰富而复杂的相行为.本文主要从两个方面综述了作者所在的研究组在两亲性分子聚集体相变研究方面的工作进展.(1)磷脂相关体系相变热力学:归纳了多种小分子(二甲基亚砜、甘油、海藻糖、尿素等)对于磷脂体系相行为的调控,比较并讨论了固醇类分子和葡萄糖神经酰胺分子诱导磷脂分子形成液态有序相的能力,还介绍了计算机模拟磷脂相行为的工作进展.(2)两亲性分子聚集体相变的协同性:先介绍了相变协同性(即分子头部、尾部、界面等基团在相变过程中的一致性)问题的提出,然后通过双十八烷基二甲基溴化铵分子和硬脂酰溶血卵磷脂两个体系的研究实例,说明两亲性分子聚集体相变过程中存在着头尾不一致的现象.对这个问题的研究,将为我们打开挑战相态转变的一系列重大问题(如相变动力学、相态多型性、相态稳定性以及相变可逆性等)的新窗口.     

First-order magnetic phase transition of LaFe11.6Si1.4C0.2studied by Mössbauer spectroscopy

Summary Temperature induced magnetic phase transition in the interstitial compound LaFe_11.6Si_1.4C_0.2 was studied by zero-field M?ssbauer spectroscopy. A paramagnetic doublet and a magnetically split sextet co-existed in the zero-field spectra in the temperature region of 213-218 K, and a thermal hysteresis was observed in the heating and cooling cycles. The spectra indicate that the magnetic phase transition induced by temperature is of first order for this sample.     

Spectroscopic studies of the phase transition in ammonia borane: Raman spectroscopy of single crystal NH3BH3 as a function of temperature from 88 to 330 K

Raman spectra of single crystal ammonia borane, NH3BH3, were recorded as a function of temperature from 88 to 300 K using Raman microscopy and a variable temperature stage. The orthorhombic to orientationally disordered tetragonal phase transition at 225 K was clearly evident from the decrease in the number of vibrational modes. However, some of the modes in the orthorhombic phase appeared to merge 10-12 K below the phase transition perhaps suggesting the presence of an intermediate phase. Factor group analysis of vibrational spectra for both orthorhombic and tetragonal phase is provided. In addition, electronic structure calculations are used to assist in the interpretation and assignment of the normal modes.     

Crystal structure, differential scanning calorimetry and vibrational low temperature investigation of C(NH2)3 x HSeO4

The first X-ray and vibrational spectroscopic analysis of a new molecular complex between guanidinium and selenic acid is reported. The crystal of guanidinium hydrogenselenate at room temperature belongs to P2(1)/n space group of the monoclinic system with Z=4, a=8.330A, b=5.109A, c=14.855A and beta=92.65 degrees . Room temperature powder infrared and Raman spectra for the titled complex (1:1) were measured. The observed IR and Raman spectra are in accordance with this crystallographic structure. The differential scanning calorimetric (DSC) experiment on powder samples indicates on continuous phase transition at ca. 160K. To explain in detail the behavior of the crystal during the phase transition the infrared and Raman powder spectra in low temperature range (10-300K) were measured. The temperature dependencies of bands position and intensities for obtained spectra are analysed.     

Interfacial interactions between poly[L-lysine]-based branched polypeptides and phospholipid model membranes

The interaction of five poly[L-lysine]-derived branched chain polypeptides of poly[Lys(X(i))] (X(i)K) or poly[Lys(X(i)-DL-Ala(m))] (XAK) with lipid bilayers (DPPC and DPPC/PG, 8:2) was studied by fluorescence polarization techniques. Two fluorescent probes, DPH and TMA-DPH, were utilized to monitor changes of motion in the internal and/or in the polar head regions, respectively. Results indicate that the interaction of polypeptides with neutral (DPPC) bilayers is mainly dependent on the polarity and electrical charge of side chains. The amphoteric E(i)K shows the highest level of interaction. Polycationic polypeptides (H(i)K, P(i)K, TAK) have a relatively small effect on the transition temperature of the lipids, while the polyanionic Succ-EAK has no effect at the alkyl chain region of the bilayer. Data with TMA-DPH indicate the lack of pronounced interaction between the polypeptides and the outer surface of the liposome. Similar tendency was documented for DPPC/PG vesicles. Polypeptides, H(i)K, and P(i)K induce significant changes in the transition temperature, thus indicating their insertion into the hydrophobic core of the bilayer without marked effect on the polar head region. Results suggest that these polypeptides (except E(i)K) have no destabilizing effect on liposomes studied. These properties are considered as beneficial for their use as safe carriers for bioactive molecules.     

Monolayers of a solvent-free polymer brush: Part 1. Thermodynamics at the air/water interface

Hydrophobie polymers with low glass transition temperature (polyisoprenes) and a single head group (sulfonate) have been synthesised and characterised as insoluble monolayers on a water surface. A single ionic head group is sufficient to make these hydrophobic polymers surface-active and isotherms of an expanded type have been recorded. These isotherms can be described quantitatively by using a theory based on constant density of the hydrophobic region, Gaussian chain statistics and affine deformation: at a fixed area per head group, the surface pressure is proportional to the length of the hydrophobic tail. The slope of this relationship is proportional to the third power of the area per head group. Chains shorter than 300 repeat units exhibit a systematic deviation from the theory.     

Impurity-stimulated heterogeneous nucleation of supercooled H2 clusters

The sizes and mass spectra of large (N=1900-13,700 molecules) cold (approximately 3.1 K) H2 clusters have been measured after scattering from CO molecules. Cluster-size measurements after between 2 and 8 collisions indicate that 7% of the H2 molecules are evaporated. This loss agrees with calculations for the number of H2 molecules evaporated by the heat released in the transition from an initial liquid state to a final solid state. Even though heterogeneous nucleation is initiated after only a few collisions with CO molecules, the mass spectra show that additional captured CO molecules coagulate to form large CO clusters with up to n=11 molecules, suggesting that the outer layer is sufficiently liquidlike to facilitate mobility of the CO molecules. Since the calculated H2 cluster temperature (approximately 3.1 K) is below the superfluid transition temperature predicted for pH2 with density between 40% and 80% of the triple-point density, a shell-like region of low density near the cluster surface can be expected to be superfluid.     

Polarization and temperature dependent spectra of poly(3-hydroxyalkanoate)s measured at terahertz frequencies

Temperature-dependent terahertz (THz) absorption spectra of poly(3-hydroxyalkanoate)s (PHAs) were measured by using a Fourier transform far-infrared (FT-FIR) spectrometer and a THz time-domain spectrometer over a temperature range of 10 K to 465 K with a liquid helium cryostat and a heating cell. Clear differences were observed between the spectra of crystalline and amorphous polyhydroxybutyrate (PHB), indicating that the absorption peaks observed in the THz spectra originated in the higher-order conformation of PHB. The polarization spectra of a stretched PHB sample were measured, and the direction of the vibrational transition moment was determined. The temperature dependences of the spectra reveal frequency shifts and broadening of the absorption peaks with temperature, suggesting large anharmonicity of the vibrational potential. The temperature shift behaviour is quite different in each transition. Some of the transitions show a blue shift, which cannot be explained by a simple anharmonic potential model. Frequency shifts of the peaks were mainly observed below 10 THz, which suggests a large anharmonicity of the vibrational potential at lower frequencies.     

Raman study of phase transitions in (n-C4H9NH3)2BiCl5

The Raman spectra of (n-C₄H₉NH₃)₂BiCl₅ were recorded and analysed from 4 K to 390 K. The phase transition (α → β) at 370 K to the metastable form is manifested by changes in the low-frequency Raman spectra, indicating the changes in the anionic structure of the crystal. The phase transition at 215 K is clearly manifested by the temperature evolution of the internal modes of the butylammonium cation. The phase transition is likely to be due to a reorientational motion of the cation.     

Orientational phase transition in a charge-transfer crystal: Triplet excitons as probes for lattice dynamics

The orientational phase transition in the charge-transfer (CT) crystal anthracene-TCNB (s-tetracyanobenze) is investigated by ESR and by Raman spectroscopy. ESR spectra of triplet excitons are observed and analysed with respect to orientational changes during the transition between two different phases. The data yield the mean molecular orientations fx (relative to a crystal fixed axis) as a function of temperature. Besides a gradual orientational change with temperature there is also an abrupt change (Δ fx ≈ 5° within 1 K) at the transition temperature suggesting a first order phase transition. A model is presented that uses exciton dynamics as a probe for lattice dynamics. The size of domains of equally oriented molecules is obtained as a function of temperature. The phase transition is also detected from the appearance of different phonon lines in the Raman spectra. These spectra gain their special value from a comparison with the behaviour of an order parameter fx, characterizing the phase transition.