Application of Ultrasonic Attenuation Measurements in the Studies on Macromolecular Conformational Behaviors

——Phase Behavior of the Aqueous Solution of Poly(vinyl methyl ether) Sensitive to Temperature and the Modification of the Behavior by Using Poly(acrylic acid) The phase behavior of the aqueous solution of poly(vinyl methyl ether) (PVME) sensitive to temperature and the modification of the behavior by using poly(acrylic acid) (PAA) have been studied by ultrasonic attenuation measurements and fluorescence probe techniques. It has been observed that PVME solution is transparent at room temperature and becomes turbid upon heating. The solution turns clear again as soon as the temperature is decreased to room temperature. The heating and cooling process can be repeated for many times. The phase behavior of the solution sensitive to temperature is attributed to the conformational changes of the polymer. PVME may adopt an open coil conformation at room temperature. With this conformation, the polymer is well miscible with the solvent, water, and thereby the system is a real solution. The polymer may adopt a compact coil conformation when the temperature is higher than a specific value, which is called the LCST (the lower critical solution temperature) of PVME. In this case, the polymer tangles to each other and forms various aggregates, which can scatter incident light and ultrasonic waves greatly, resulting in the phase separation. Introduction of PAA decreases the temperature sensitivity of the phase behavior of the polymer. The nature of the inhibition is attributed to the complexation of PAA with PVME and the strong hydrophilicity of PAA. Results from fluorescence probe studies are in accordance with those from ultrasonic attenuation measurements, indicating again that the ultrasonic attenuation method can be successfully used for the qualitative studies of polymer conformations and complexation between polymers.     

聚合物PVP与表面活性剂AOT相互作用的介观模拟

用耗散颗粒动力学模拟(DPD)方法研究了聚乙烯吡咯烷酮(PVP)与2-乙基己基琥珀酸酯磺酸钠(AOT)之间的相互作用.在三维模拟格子中,聚合物链均方末端距〈r²〉随着表面活性剂浓度的增加呈现一种首先减小,接着增加,然后又减小的趋势.构型和结构分析表明,AOT的加入能够引起聚合物链的二面角分布发生改变,这意味着AOT与PVP产生了相互作用.同时表面活性剂/聚合物体系的聚集形态也可以在DPD三维模拟格子中直观显现出来.     

喷墨打印技术制备聚合物太阳能电池的研究进展

聚合物太阳能电池具有成本低、质量轻、容易制备大尺寸器件等优势,是太阳能电池研究中最为活跃的领域之一。喷墨打印技术作为新的成膜技术,具有材料利用率高、快速、可柔性加工等优点,已被用于聚合物太阳能电池的制备,发展潜力巨大。综述了聚合物太阳能电池、喷墨打印技术和喷墨打印技术制备聚合物太阳能电池的研究进展,同时对聚合物太阳能电...     

Real-time analysis of enzymatic surface-initiated polymerization using surface plasmon resonance (SPR)

The kinetics of enzymatic surface-initiated polymerization of PHB on gold surface has been examined by SPR and the resultant polymer layers characterized by AFM and FT-IR spectrometry. The immobilized enzyme catalyzed surface-initiated polymerization of 3HB-CoA, resulting in the formation of a polymer brush on the surface. The rate of polymer growth from the surface was monitored by SPR in real-time. Polymer growth as measured by the increase in the resonance angle showed no apparent lag phase during the polymerization reaction. SPR analysis also revealed that the thickness of the polymer film could be controlled by varying the initial enzyme density on the surface. The average thicknesses of the PHB film after polymerization reaction were 95, 45 and 15 nm for the surfaces that were treated with 0.5, 0.3 and 0.1*10(-6) M of enzyme, respectively. The binding of PHA synthase at different concentration to the mixed SAMs and subsequent polymerization.     

Application of Ultrasonic Attenuation Measurements in the Studies on Macromolecular Conformational Behaviors——Phase Behavior of the Aqueous Solution of Poly(vinyl methyl ether) Sensitive to Temperature and the Modification of the Behavior by Using Pol

Introduction Studies on the conformational and aggregation be-haviors of macromolecules in aqueous solution and at solid/liquid interfaces have been highlighted in colloid and interface science since the early 1990s.1-3 It was mentioned in the first part of this series of studies that development of new methods, which are characterized by being in time and non-destructive and can be used for monitoring the conformational and aggregation be-havior of macromolecules, is of critical importance fo…     

Building up polymer architectures on graphene oxide sheet surfaces through sequential atom transfer radical polymerization

The reactivity between the active species of atom transfer radical addition and the unsaturated groups of graphene oxides (GOs) has been demonstrated in this work. The reaction and the sequential surface‐initiated atom transfer radical polymerization provide a convenient approach to anchor various polymer chains and to buildup various polymer architectures, such as linear polymer, V‐shape block polymer, multibonded polymer layer, and hierarchical brush‐on‐layer polymer, on GO sheet surfaces. The chemical structures and morphology of the polymer‐modified GOs have been characterized with Fourier transform infrared spectroscopy, Raman spectroscopy, X‐ray photoelectron spectroscopy, and atomic force microscopy. After organomodification, the GOs exhibit a good dispersion ability in organic solvent over 80 days, amphiphilic characteristics, and temperature‐responsive properties. Reduction of the GOs has been performed to result in graphene‐like materials showing certain extent of electron conductivities. An effective approach to synthesize GO/polymer hybrid materials possessing various polymer architectures and attractive properties has been developed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1588–1596     

Biodegradation behavior of polycaprolactone/rice husk ecocomposites in simulated soil medium

In this study, novel ecocomposites based on degradable polymer, polycaprolactone (PCL) and natural lignocellulosic material, rice husk (RH) have been prepared. The crystallization behavior of these ecocomposites was first studied by using differential scanning calorimetry (DSC). The method of soil suspension system (i.e. simulated soil medium) was utilized to investigate the biodegradation behavior of the PCL/RH ecocomposites, and quantitative analysis on the degradation behavior of the two components (i.e. PCL and RH) has been achieved by a modified TGA method. Results demonstrate that the incorporation of RH fillers can inhibit the crystallization of PCL phase to some extent. Furthermore, the presence of RH fillers can accelerate the degradation of the PCL matrix in the ecocomposites, and this acceleration effect becomes more pronounced with the increase of RH content, which has been explained in terms of the depressed crystallinity of the polymer matrix, improved hydrophilicity and depolymerase-binding capacity of the substrate.     

Influence of the Nanoscale Morphology on the Photovoltaic Properties of Fullerene/MEH-PPV Composites

The relation between morphology and photoelectric properties of PPV derivatives/fullerene composites forming bulk heterojunction solar cells has been investigated. The solvent used to spin cast the photoactive layers has a main influence on the quenching of the MEH-PPV fluorescence, which could be attributed to different dispersion abilities of C₆₀ in the polymer layer shown by AFM microscopy. Formation of large fullerene aggregates is observed at fullerene concentrations of the order of 10% leading to phase separation for composite layers processed in THF, whereas more dispersed distributions of fullerenes are observed in an aromatic solvent like ODCB which accounts for a more efficient luminescence quenching with increasing filler concentrations. However the improvement of the dissociation of photogenerated charge pairs is counterbalanced by a less efficient charge transport in the composite shown by lower short circuit currents probably due to unfavorable polymer chain arrangement in ODCB. Thin film processing conditions have been modified by the preparation of blends of solutions of the polymer in THF and fullerene in ODCB. The resulting spin casted layers show improved morphologies implying better dispersion of the fullerenes and increased short circuit currents. The improvement of the photovoltaic properties of the MEH-PPV/C₆₀ composites has been attributed to the nanosized fullerene domains formed upon phase separation.     

漆酶催化对苯基苯酚的聚合

漆酶(EC 1．10．3．2)是一种氧化还原酶,可应用于催化氧化还原反应和高分子合成领域．聚酚类物质由于具有丌电子共轭结构,通过掺杂可以表现出一定的导电性,而有机导电聚合物是一类有着广泛应用前景的功能材料．此外这类物质还具有较高的三阶非线性系数,是一类重要的有机非线性光学材料,是激光技术的重要物质基础之一．而取代苯酚类物质由于其结构的特殊性,一般很难用化学方法使其聚合．有报道用辣     

聚苯乙炔/碳纳米管复合材料的导电性能研究

本文以无水A lC l3作催化剂合成聚苯乙炔(PPA),用H2SO4对其进行磺化改性,采用其混法制得了PPA/碳纳米管(CNTs)及磺化PPA/CNTs复合材料,对二者的常温电导率及变温电导率进行了测试。结果表明:磺化PPA的电导率较PPA的提高了3个数量级;随着CMTs含量增加,复合材料的电导率升高;PPA/CNTs导电的阈值是3%,达极限电导率(0.04S/m)所需CNTs含量为25%,而磺化PPA/CNTs导电的阈值是2%,达极限电导率所需CNTs(0.14 s/m)含量为25%。并分析了温度变化对复合材料电阻变化的影响因素。     

IN AQUA SYNTHESIS OF A HIGH MOLECULAR WEIGHT ARYLETHYNYLENE POLYMER EXHIBITING REVERSIBLE HYDROGEL PROPERTIES

ABSTRACT

A high molecular weight poly(aryleneethynylene) (M_w ～ 60,000) is prepared by the palladium catalyzed copolymerization of 3,5-diiodobenzoic acid and acetylene gas in a basic aqueous medium. The polymer has a “zig-zag”, fully conjugated backbone. The polymer has been characterized by a variety of methods and exhibits high thermal stability. Furthermore, the polymer is readily soluble in aqueous base and is reversibly switchable from the solution state to a hydrogel state, in water, by changing the pH of the solvent.     

Polyolefins: The most promising large-volume materials for the 21st century

Polyolefins (POs) constitute an extremely interesting family of materials. They include large-volume materials such as polyethylene and polypropylene and specialty materials. Outstanding scientific and technology developments have led to the most aggressive, endless, always increasing, successful growth speed of any family of large-volume materials. For those of us who have lived through the entire PO adventure, from its problematic beginnings to the eventual successful developments of the last 25 years, it has been a quite unforeseeable and unexpected story not shared by the majority. The main reason for such behavior and the present situation is the inherent complexity of their catalytic systems, which are difficult to understand and manage, along with all the consequences in terms of the process versatility, the reliability and cost, the lack of product properties, and the possibility of new material creation and commercial availability. After the early commercial disappointments of the 1960s and early 1970s, the deep commitment of the industry in research and development, mostly aimed at an understanding of the catalysis and its improvement and management, created the basis for and led to the generation of new, elegant, and versatile processes and, most importantly, to the generation of new products and properties. It activated that dynamic and aggressive growth that, since the late 1970s, has characterized the entire PO market and still, at the beginning of the third millennium, is not showing any sign of decline. An attempt to provide a rational explanation for such a unique case of technological and commercial success in the history of materials has led us to the following conclusions. First, dramatic improvements in the polymer properties and the generation of new materials have been the key reasons for their commercial success and continuous market expansion. Second, the tremendous and dynamic development of new, elegant, and versatile technologies has been and is the fundamental prerequisite for the generation of that rich world of new properties and materials. Third, the strategic management of the technological background and potential for the creation of new properties and new applications has been and is the basis for the fast and successful market expansion. The key technological driving force has been the understanding and management of the catalytic system. The early generations of chromium-based and Ziegler–Natta catalysts, after a difficult beginning, have progressively accelerated in their development toward new revolutionary generations with outstanding potential in terms of the creation of new polymer properties. The most recent families of single-site catalysts, together with the still largely unexploited potential of the previous Ziegler–Natta, chromium, and vanadium catalysts, are showing the ability to guarantee the continued support and fueling of the expansion for several further decades. The development philosophy will always be more tuned toward the creation of low-cost, low-environmental-impact polymers and processes, with a minimum amount of constraints. Today, at the beginning of the new century, we see the PO future as still very bright because of the huge, unexploited potential of already existing and emerging technologies. The PO adventure continues and is still exciting like it was 50 years ago. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 396–415, 2004     

Synthesis and characterization of PISOZ-PDMS-PISOZ triblock polymer vesicles

In this project, we synthesized poly(2-isopropyl-2-oxazoline)-block- poly(dimethyl-siloxane)-block-poly(2-isopropyl-2-oxazoline) (PISOZ-PDMS-PISOZ) triblock polymer, which has been prepared as vesicles. The triblock polymer was characterized by ¹H-NMR, F-NMR, LS and TEM. The size of the empty vesicle is about 60 nm. When curcumin was encapsulated into PISOZ-PDMS-PISOZ triblock polymer, formed well defined vesicles in a size about 70 nm.     

Study of the self‐diffusion of poly(ethylene glycol)s in poly(vinyl alcohol) aqueous systems

We have measured the self‐diffusion coefficients of a series of oligo‐ and poly(ethylene glycol)s with molecular weights ranging from 150 to 10,000, in aqueous solutions and gels of poly(vinyl alcohol) (PVA), using the pulsed‐gradient spin‐echo NMR techniques. The PVA concentrations varied from 0 to 0.38 g/mL which ranged from dilute solutions to polymer gels. Effects of the diffusant size and polymer concentration on the self‐diffusion coefficients have been investigated. The temperature dependence of the self‐diffusion coefficients has also been studied for poly(ethylene glycol)s with molecular weights of 600 and 2,000. Several theoretical models based on different physical concepts are used to fit the experimental data. The suitability of these models in the interpretation of the self‐diffusion data is discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2396–2403, 1999     

Superparamagnetic lysozyme surface-imprinted polymer prepared by atom transfer radical polymerization and its application for protein separation

Molecular imprinting as a promising and facile separation technique has received much attention because of their high selectivity for target molecules. In this study, the superparamagnetic lysozyme surface-imprinted polymer was prepared by a novel fabricating protocol, the grafting of the imprinted polymer on magnetic particles in aqueous media was done by atom transfer radical polymerization (ATRP), and the properties of the imprinted polymer were characterized in detail. Its high selective adsorption and recognition to lysozyme demonstrated the separation ability of the magnetic imprinted material to template molecule, and it has been used for quick and direct separation of lysozyme from the mixture of standard proteins and real egg white samples under an external magnetic field. Furthermore, the elution of lysozyme from the imprinted material was achieved by PEG/sulphate aqueous two-phase system, which caused lysozyme not only desorption from the imprinted materials but also redistribution in the top and bottom phase of aqueous two-phase system. The aqueous two-phase system exhibited some of the extraction and enrichment effect to desorbed lysozyme. Our results showed that ATRP is a promising method for the protein molecularly imprinted polymer preparation.     

可紫外光交联氟代聚芳醚的合成及性能研究

以丙酮酸、苯甲醚为原料合成了1,1-双(4-甲氧基苯基)(BMPE)乙烯单体,并通过去甲基反应得到了含可交联基团的二酚单体1,1-双(4-羟基苯基)乙烯(BHPE),并且用核磁共振、飞行质谱及元素分析表征了单体的结构,DSC测试了单体的熔点.并将BHPE与全氟联苯(DFBP)在氟化钾和氢化钙的催化作用低温下进行缩聚反应,得到了一种可紫外辐照交联的氟代聚芳醚.通过核磁共振证明了所合成的单体以及聚合物的结构,凝胶渗透色谱(GPC)测定了聚合物的分子量.傅立叶变换红外光谱分析了聚合物紫外辐照下的交联反应.所合成的氟代聚芳醚在室温下可溶于氯仿、四氢呋喃等有机溶剂,紫外交联后不溶于任何有机溶剂.且合成的聚合物具有良好的热稳定性能(玻璃化转变温度为160℃,交联后的5%热失重为465℃).     

Evaluation of asymmetrical structure dialysis membrane by tortuous capillary pore diffusion model

The tortuous capillary pore diffusion model (TCPDM) has been used for estimating diffusive and pure water permeability from simple structure parameters such as pore diameter, surface porosity, wall thickness and tortuosity. The validity of this model for evaluation of homogeneous membrane has been already confirmed. Recently, there is a trend toward the use of asymmetrical dialysis membranes made of synthetic polymer such as poly(acrylonitrile) (PAN), polysulfone (PS) and a polyethersulfone polyarylate (PEPA) blend polymer. The purpose of the present study is to apply the TCPDM to evaluation of commercially available hollow-fiber dialysis membranes with asymmetrical structures by simplifying them to a double-layer membrane. The TCPDM is capable of estimating pore tortuosity of asymmetrical dialysis membranes having skin and supporting layers from data on membrane thickness, pore diameter, pure water permeability and water content. Values for diffusive permeability obtained by the TCPDM are in a good agreement with experimental data. This TCPDM model is useful for evaluation of not only homogeneous membrane but also asymmetrical membrane.     

Self-assembly of monodisperse polymer microspheres from PPQ-b-PEG rod-coil block copolymers inselective solvents

Self-assembly of macromolecules is a new fastdeveloping research field in recent years. So far it hasbeen known that many different forms and orderedfunctional nanometer materials, nanometer structurematerials and ordered porous materials are obtained bys…     

Viscometric behaviour of polymer blends based on poly (vinylidene fluoride)

The viscosity behaviour of dilute dimethylformamide solutions of poly(vinylidene fluoride)-poly (methyl methacrylate) and poly(vinylidene fluoride)-polystyrene has been studied at 25°C. The polymer concentration ranges are such that neither phase separation nor microgel formation occurs, although we are very close to theta conditions. The intrinsic viscosity and viscosity interaction parameter of the ternary mixtures have been calculated. The estimation of the compatibility of the above polymer pairs has been studied based on: a) specific viscosities; b) viscosity interaction parameters, according to Krigbaum and Wall formalism, and c) viscosity interaction parameters of a system formed by a dilute probe polymer in the presence of a matrix polymer and a small molecule solvent.     

新型鳞片状聚合物修饰硅胶填料固定化酶的制备及其在蛋白质组鉴定中的应用

利用原子转移自由基聚合法制备了鳞片状聚合物修饰的硅胶填料,将其作为一种新型的固定化酶载体,实现了蛋白酶的高密度固定,从而明显缩短了复杂蛋白质样品的酶解时间。使用标准蛋白质对固定化酶的酶解效率进行了考察,结果表明: 鳞片状聚合物修饰的新型固定化酶硅胶填料具有较高的酶解效率,酶解标准蛋白质1 min后,鉴定到肽段的氨基酸序列覆盖率可达95%以上。将该固定化酶硅胶填料成功应用于大肠杆菌全蛋白质的酶解,从2 min酶解肽段的混合物中鉴定到的蛋白质数量超过同样条件下溶液酶解12 h的结果。另外,该固定化酶硅胶填料可以重复使用,其酶解效率具有良好的稳定性和重现性;该固定化酶具有较好的样品回收率,因而可以应用于蛋白质组学研究中。