Hydrogen-bonded Intramolecular Charge Transfer Excited State of Dimethylaminobenzophenone using Time Dependent Density FunctionalTheory

Density functional theory and time-dependent density-functional theory have been used to investigate the photophysical properties and relaxation dynamics of dimethylaminobenzophe-none (DMABP) and its hydrogen-bonded DMABP-MeOH dimer. It is found that, in non-polar aprotic solvent, the transitions from S₀ to S₁ and S₂ states of DMABP have both n→π^* and π→π^* characters, with the locally excited feature mainly located on the C=O group and the partial CT one characterized by electron transfer mainly from the dimethylaminophenyl group to the C=O group. But when the intermolecular hydrogen bond C=O…H-O is formed, the highly polar intramolecular charge transfer character switches over to the first excited state of DMABP-MeOH dimer and the energy difference between the two low-lying electronically excited states increases. To gain insight into the relaxation dynamics of DMABP and DMABP-MeOH dimer in the excited state, the potential energy curves for con-formational relaxation are calculated. The formation of twisted intramolecular charge trans-fer state via diffusive twisting motion of the dimethylamino/dimethylaminophenyl groups is found to be the major relaxation process. In addition, the decay of the S1 state of DMABP-MeOH dimer to the ground state, through nonradiative intermolecular hydrogen bond stretching vibrations, is facilitated by the formation of the hydrogen bond between DMABP and alcohols.     

Langmuir monolayers and Langmuir–Blodgett films of 1-acyl-1,2,4-triazoles

New 1-acyl-1,2,4-triazoles (ATs) with different n-alkyl chain lengths from C2 to C18 were synthesized. ATs with long n-alkyl chains (C12 and larger) are non-charged amphiphilic molecules with a polar triazole head group. The Langmuir isotherms of ATs at the air–water interface with 12 (DoT-C12), 14 (MyT-C14), 16 (PaT-C16) and 18 (StT-C18) carbon atoms in their n-alkyl chains were studied using surface pressure-mean molecular area (π-mmA) measurements. Characteristic for the Langmuir isotherms of PaT-C16 and StT-C-18 was the first sharp increase of the surface pressure at a mmA value of 20 Å² marking a transition of the ATs from the gaseous state with n-alkyl chains already oriented perpendicular to the water surface to a condensed state. The collapse of the monolayers occurred between 20 and 36 mN m⁻¹ with a typical ‘spike’ in the isotherms of MyT-C14, PaT-C16 and StT-C18 which can be assigned to the buckling and subsequent folding of the monolayer. After the collapse point a pseudo-plateau region of slightly increasing surface pressure appeared for all ATs from C12 to C18 indicating a trilayer formation by the roll-over mechanism for MyT-C14, PaT-C16 and StT-C18. Upon further compression the final collapse occurred at π values between 59 and 67 mN m⁻¹. From reversibility studies it was found that the Langmuir isotherms of the ATs were irreversible. The morphology of Langmuir–Blodgett films of ATs transferred onto silicon wafers was studied by atomic force microscopy.     

表面活性剂在水溶液中性质的质子核磁共振研究

综述了质子核磁共振的几种方法在表面活性剂水溶液研究中的应用.自从上世纪六十年代以来的许多研究表明核磁共振的各种技术是研究表面活性剂溶液的有效手段.它可以提供表面活性剂在水溶液中的cmc、胶束的结构、尺寸、水化、加溶性质和位置，不同表面活性剂胶束之间的相互作用，以及胶束与生物分子和高聚物的相互作用.化学位移已经成为惯常方法，弛豫测量提供动态信息，自扩散系数测量是研究胶束尺寸的很好手段.近来由于核磁共振技术的不断发展，用于研究生物大分子的2D NOESY和HOESY也逐渐应用到研究表面活性剂聚集结构中.由此可以得到有关表面活性剂在水溶液中行为的分子水平信息，是其它谱学方法所不能及的.     

Poly(butylene terephthalate)–polyarylate blends

In this paper we focus on miscible blends of two engineering polymers: poly(butylene terephthalate) (PBT) and a polyarylate (PAr). The issue of transesterification in these blends will be addressed, followed by a discussion of the crystallization kinetics of PBT, poly(ethylene terephthalate) and several PBT/PAr blends. The ability to estimate polymer–polymer interaction parameters in blends from melting point depression will also be discussed. The amorphous phase behavior of the PBT/PAr blends has been explored primarily using dielectric spectroscopy. For blends in which PBT has crystallized, we observe two relaxations associated with T_g-like motion, and this behavior is interpreted in light of our recent work on order–disorder interphases in crystalline blends.     

Interactions and mobility of copper(II)-imidazole-containing copolymers

Poly(1-vinylimidazole-co-methyl methacrylate) copolymers (PVM) were obtained from copolymerization of 1-vinylimidazole and methyl methacrylate with 2,2^′-azobisisobutyronitrile as an initiator. The formation of random copolymers was substantiated by the glass transition temperature (T_g) and the proton spin-lattice relaxation time in the rotating frame (T^H_1ρ). Cu(II)-PVM complexes were prepared by mixing tetrahydrofuran solution of PVM and copper sulfate solution. The formation of coordination bond between PVM and Cu²⁺ ions was studied using differential scanning calorimetry, infrared and ¹³C solid-stated nuclear magnetic resonance spectroscopy. A single composition dependent T_g was obtained for the PVM copolymers, and that increased with increasing VI content. The T_g value of the Cu(II)-PVM complex was much higher than that of the PVM copolymer with the same composition. The T^H_1ρ of the VI units and MMA units in the copolymers and complexes had one value, and that in the complexes was much lower than that in the copolymers. The dramatic decrease in T^H_1ρ for the Cu(II)-PVM complexes was due to Cu(II) complexation and electron-nuclear dipolar interactions.     

Phase transitions and relaxation processes in ethylene-vinyl acetate copolymers probed by fluorescence spectroscopy

The steady-state fluorescence of pyrene and anthracene are used to investigate the relaxation processes of several random ethylene-co-vinyl acetate copolymers, EVA, with defined comonomer compositions (EVA-9, EVA-18, EVA-25, EVA-33 and EVA-40). The temperature of the relaxation processes are compared with those of low-density polyethylene (LDPE) and poly(vinyl acetate) (PVAc). The polymer relaxation processes are assigned to T_g=300-310 K (glass transition temperature of the PVAc); T_α=270-300 K (relaxation processes of the ethylene units present in LDPE and EVA); T_g=220-250 K (glass transition of the LDPE and of the EVA); T_γ or T_β=160-190 K (relaxation processes of interfacial defects of methylenic chains of LDPE and rotation of the acetate group of the PVAc and the EVA); and T_γ=90-130 K (relaxation processes of small sequences of methylene units of LDPE and end groups of PVAc). An Arrhenius-type function was employed as an attempt to represent the experimental data of fluorescence intensity versus temperature above the γ-relaxation temperature. As obtained with other techniques, there is not a simple relationship between the polymer relaxation processes and the vinyl acetate content that can be explained by the morphology in these copolymers.     

The Rigid Core and Flexible Surface of Amyloid Fibrils Probed by Magic-Angle-Spinning NMR Spectroscopy of Aromatic Residues

Aromatic side chains are important reporters of the plasticity of proteins, and often form important contacts in protein–protein interactions. We studied aromatic residues in the two structurally homologous cross-β amyloid fibrils HET-s, and HELLF by employing a specific isotope-labeling approach and magic-angle-spinning NMR. The dynamic behavior of the aromatic residues Phe and Tyr indicates that the hydrophobic amyloid core is rigid, without any sign of “breathing motions” over hundreds of milliseconds at least. Aromatic residues exposed at the fibril surface have a rigid ring axis but undergo ring flips on a variety of time scales from nanoseconds to microseconds. Our approach provides direct insight into hydrophobic-core motions, enabling a better evaluation of the conformational heterogeneity generated from an NMR structural ensemble of such amyloid cross-β architecture.     

溶液小分子空间结构的NMR测定——Tranilast在丙酮溶液中的三维结构

本文应用矩阵分析的方法对相敏NOESY二维谱的峰强度进行处理, 从使用较长混合期的实验中获得了较为精确的交叉驰豫速率率, 进而得到有相关峰的各对核之间的距离, 此方法适用于研究处于极端窄化运动条件下的小分子的三维空间结构。本文运用此方法研究了药物TRANILAST在丙酮溶液中的三维空间结构, 并用分子力学计算方法对实验结果进行了验证。     

温度和场冷间隙对高温超导磁悬浮系统弛豫的影响

悬浮力是高温超导磁悬浮列车运行中的一个至关重要的参数.悬浮力的弛豫特性是高温超导磁悬浮列车安全运行的一大阻碍.适度降低工作温度是有效改善悬浮力弛豫特性的有效手段之一.本文从数值计算和实验两个层面研究了不同冷却温度和不同场冷间隙下的悬浮力的弛豫现象.发现悬浮力的弛豫现象随着超导块冷却温度的降低而减弱，随着场冷间隙的增大而略微增大，但是随着冷却温度的降低，增大程度会有所减弱.该研究有助于通过合理设计高温超导材料工作温度，以提高磁悬浮系统性能表现.