Crystallization behavior and electroactive properties of PVDF,P(VDF-TrFE) and their blend films

PVDF, poly(vinylidene fluoride), as a semi-crystalline polymer, has interesting electroactive properties but usual melt and solution processing techniques result in its thermodynamically favored non-polar α-phase. By comparison, poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE), PT for short, directly crystallizes in the polar β-phase under the same conditions as PVDF. In this study, blend thin films comprising PVDF and P(VDF-TrFE) were prepared by solvent casting method. The difference in the crystallization behavior is comprehensively investigated between the polymers: PVDF, P(VDF-TrFE), and the resulting blend films. It is found that replacement of the fluoride atom in TrFE monomer induces a strong steric hindrance that may alter the crystallization process to become more favorable for nucleation of the PVDF β-phase. To figure out the effect of TrFE content on the crystallization behavior and electroactive properties, films with different blend ratios of PVDF and P(VDF-TrFE) were prepared. We found that the PVDF films exhibit higher crystallization activation energy (ΔE) as PT content increases. The atomic force microscopy (AFM) in the piezoresponse force microscopy (PFM) mode illustrated that P5T5 films with equal contents of PVDF and P(VDF-TrFE) induced the highest d₃₃ values.     

Equilibrium folding and unfolding dynamics to reveal detailed free energy landscape of src SH3 protein by magnetic tweezers

Src SH3 protein domain is a typical two-state protein which has been confirmed by research of denaturant-induced unfolding dynamics. Force spectroscopy experiments by optical tweezers and atomic force microscopy have measured the force-dependent unfolding rates with different kinds of pulling geometry. However, the equilibrium folding and unfolding dynamics at constant forces has not been reported. Here, using stable magnetic tweezers, we performed equilibrium folding and unfolding dynamic measurement and force-jump measurement of src SH3 domain with tethering points at its N-and C-termini. From the obtained force-dependent transition rates, a detailed two-state free energy landscape of src SH3 protein is constructed with quantitative information of folding free energy, transition state barrier height and position,which exemplifies the capability of magnetic tweezers to study protein folding and unfolding dynamics.     

Effect of carbon chain length of monocarboxylic acids on cloud point temperature of poly(2-ethyl-2-oxazoline)

The temperature-induced phase transition of poly(2-ethyl-2-oxazoline) (PEtOx) aqueous solution under mixing with a series of small carboxylic acids has been studied by turbidity measurements and laser light scattering. It has been found that cloud point temperature (T _cp) of the PEtOx was changed to varying degrees depending upon the pH, ionic strength, molar ratio of acids to 2-ethyl-2-oxazoline unit, and carbon chain length of small carboxylic acids. Significant change in T _cp was observed in the case of hexanoic acid. At acidic pH, an increase in the molar ratio of hexanoic acid to the 2-ethyl-2-oxazoline unit gradually decreased the phase transition temperature of the polymer as compared to the T _cp of pure PEtOx. At original pH 6 (pH?>?pK _a), T _cp shifts to higher value than that of pure PEtOx for lower molar ratios and decreased later on with increasing the molar ratio. The shift in the T _cp is described based on the differences in the driving force of phase transition, including hydrogen bonding between small carboxylic acids and PEtOx polymer and hydrophobic interaction.     

Tensile properties of structural I clathrate hydrates: Role of guest–host hydrogen bonding ability

Clathrate hydrates (CHs) are one of the most promising molecular structures in applications of gas capture and storage, and gas separations. Fundamental knowledge of mechanical characteristics of CHs is of crucial importance for assessing gas storage and separations at cold conditions, as well as understanding their stability and formation mechanisms. Here, the tensile mechanical properties of structural I CHs encapsulating a variety of guest species (CH₄, NH₃, H₂S, CH₂O, CH₃OH, and CH₃SH) that have different abilities to form hydrogen (H-) bonds with water molecule are explored by classical molecular dynamics (MD) simulations. All investigated CHs are structurally stable clathrate structures. Basic mechanical properties of CHs including tensile limit and Young’s modulus are dominated by the H-bonding ability of host–guest molecules and the guest molecular polarity. CHs containing small CH₄, CH₂O and H₂S guest molecules that possess weak H-bonding ability are mechanically robust clathrate structures and mechanically destabilized via brittle failure on the (1 0 1) plane. However, those entrapping CH₃SH, CH₃OH, and NH₃ that have strong H-bonding ability are mechanically weak molecular structures and mechanically destabilized through ductile failure as a result of gradual global dissociation of clathrate cages.     

Insight into the chemomechanical coupling mechanism of kinesin molecular motors

Kinesin is a two-headed biological molecular motor that can walk processively on microtubule via consumption of ATP molecules. The central issue for the molecular motor is how the chemical energy released from ATP hydrolysis is converted to the kinetic energy of the mechanical motion, namely the mechanism of chemomechanical coupling. To address the issue, diverse experimental methods have been employed and a lot of models have been proposed. This review focuses on the proposed models as well as the qualitative and quantitative comparisons between the results derived from the models and those from the structural, biochemical and single-molecule experimental studies.     

飞秒时间分辨荧光非共线光参量放大光谱技术

时间分辨荧光光谱技术是研究激发态弛豫、能量传递以及电荷转移等光化学过程的重要且直接的工具．飞秒时间分辨荧光非共线光参量放大光谱技术是一种新发展的具有高时间分辨率、宽探测带宽、高增益的时间分辨光谱技术．本文对该技术的基本原理与工作特性、系统配置、荧光收集和会聚、数据采集模式、时问分辨光谱数据处理等进行了系统阐述．最后简单介绍了飞秒时间分辨荧光非共线光参量放大光谱技术在物理、生物和化学领域的3个典型应用,并以此展现该技术的高时间分辨率、宽光谱探测及高增益优势．     

果蝇昼夜生理节律之细胞质PER-TIM间隔定时器的大聚合物模型

昼夜生理节律使得生物体的生理和行为能够适应外界环境的昼夜循环变化. 实验发现在果蝇的细胞质中存在由PER-TIM复合体组成的间隔计时器. 本文提出了这个间隔定时器的一种可能的数学模型. 模型的特点是大聚合物, 快速交换, 不同磷酸化位点有不同功能. 模拟结果基本与实验相符, 符合PER-TIM间隔定时器的主要时间特征并重现了per^L 变异细胞系中定时器的特点, 以及PER和TIM蛋白进入细胞核的三种不同类型的过程.     

Fluctuations in apparent mass at the bottom of granular columns due to different arrangements

We report the fluctuations in apparent mass at the bottom of granular columns due to various configurations. It is found that the fluctuations decrease with the increase in the ratio of diameters of silo to grain. For the arrangement of different grain layers in a column, the higher fluctuations appear when the larger grains are stacked at the bottom layer while reversing the order of grain-layers leads to smaller fluctuations. We attribute this behavior to the randomness in the direction of frictional forces between the grains and the confining wall. Moreover, due to polydisperse media, the development of inhomogeneous force transmission in grains may cause this to happen.     

A strategy for synthesis of ion‐bonded amphiphilic miktoarm star copolymers via supramolecular macro‐RAFT agent

Amphiphilic supramolecular miktoarm star copolymers linked by ionic bonds with controlled molecular weight and low polydispersity have been successfully synthesized via reversible addition‐fragmentation chain transfer (RAFT) polymerization using an ion‐bonded macromolecular RAFT agent (macro‐RAFT agent). Firstly, a new tetrafunctional initiator, dimethyl 4,6‐bis(bromomethyl)‐isophthalate, was synthesized and used as an initiator for atom transfer radical polymerization (ATRP) of styrene to form polystyrene (PSt) containing two ester groups at the middle of polymer chain. Then, the ester groups were converted into tertiary amino groups and the ion‐bonded supramolecular macro‐RAFT agent was obtained through the interaction between the tertiary amino group and 2‐dodecylsulfanylthiocarbonylsulfanyl‐2‐methyl propionic acid (DMP). Finally, ion‐bonded amphiphilic miktoarm star copolymer, (PSt)₂‐poly(N‐isopropyl‐acrylamide)₂, was prepared by RAFT polymerization of N‐isopropylacrylamide (NIPAM) in the presence of the supramolecular macro‐RAFT agent. The polymerization kinetics was investigated and the molecular weight and the architecture of the resulting star polymers were characterized by means of ¹H‐NMR, FTIR, and GPC techniques. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5805–5815, 2008     

Mechanical properties of jammed packings of frictionless spheres under an applied shear stress

By minimizing a thermodynamic-like potential, we unbiasedly sample the potential energy landscape of soft and frictionless spheres under a constant shear stress. We obtain zero-temperature jammed states under desired shear stresses and investigate their mechanical properties as a function of the shear stress. As a comparison, we also obtain the jammed states from the quasistatic-shear sampling in which the shear stress is not well-controlled. Although the yield stresses determined by both samplings show the same power-law scaling with the compression from the jamming transition point J at zero temperature and shear stress, for finite size systems the quasistatic-shear sampling leads to a lower yield stress and a higher critical volume fraction at point J. The shear modulus of the jammed solids decreases with increasing shear stress. However, the shear modulus does not decay to zero at yielding. This discontinuous change of the shear modulus implies the discontinuous nature of the unjamming transition under nonzero shear stress, which is further verified by the observation of a discontinuous jump in the pressure from the jammed solids to the shear flows. The pressure jump decreases upon decompression and approaches zero at the critical-like point J, in analogy with the well-known phase transitions under an external field. The analysis of the force networks in the jammed solids reveals that the force distribution is more sensitive to the increase of the shear stress near point J. The force network anisotropy increases with increasing shear stress. The weak particle contacts near the average force and under large shear stresses it exhibit an asymmetric angle distribution.