Complex macromolecular architecture design via cyclodextrin host/guest complexes

The design of complex macromolecular architectures has driven macromolecular engineering over the past decades. The introduction of supramolecular chemistry into polymer chemistry provides novel opportunities for the generation of macromolecular architecture with specific functions. Cyclodextrins are attractive design elements as they form supramolecular inclusion complexes with hydrophobic guest molecules in aqueous solution affording the possibility to combine a large variety of building blocks to form novel macromolecular architectures. In the present critical review, the design of a broad range of macromolecular architectures driven by cyclodextrin host/guest chemistry is discussed, including supramolecular block copolymers, polymer brushes, star and branched polymers.     

以TEA和PAA为分散剂的水基流延SDC

分别以三乙醇胺(TEA)和聚丙烯酸(PAA)为分散剂,用水基流延法制备Sm2O3掺杂的CeO2(Ce0.8Sm0.2O1.9,SDC)陶瓷,研究了pH值对SDCζ电位的影响,分析了SDC生坯的物理性能。TEA和PAA分散的SDC,最大ζ电位绝对值分别为62 mV和49 mV,TEA分散的生坯在基板上铺展得更好,外观更均一,显微结构更均匀、致密,TEA和PAA分散的生坯,相对密度分别为51.7%和46.2%,极限抗拉强度分别为1.25 MPa和1.06 MPa。TEA是SDC陶瓷较好的水基流延分散剂。     

Morphology of multilayers assembled by electrostatic attraction of oppositely charged model polyelectrolytes

Alternating multilayers assembled stepwise with two prototype polyelectrolytes, i.e. poly(allylamine) hydrochloride (PAA) and poly(vinyl sulfate) potassium salt (PVS), have been examined by means of reflection–absorption infrared (RAIR) spectroscopy and atomic force microscopy (AFM). The growth step revealed by the RAIR spectroscopy was in good agreement with the ellipsometric data. The RAIR spectral data revealed that both macromolecules were randomly oriented in the (PVS/PAA) composite system without any preferential alignment. The atomic force microscopy measurements showed that the morphology of the (PVS/PAA) multilayers prepared in the absence of NaCl were quite homogeneous in agreement with a recent report. However, the morphology of the multilayers prepared in the presence of NaCl was observed to be significantly heterogeneous; the morphology was gradually roughened upon an increase in the number of bilayers. The highly coiled, compact macromolecules present in a NaCl solution seemed preferentially to anchor on the oppositely charged, aggregated surface sites without spreading over the interfacial region. Nonetheless, the morphology of the surface of the (PVS/PAA) system was hardly subjected to change once a stable film had been assembled, regardless of the presence of NaCl.     

Formation of ZnS nanorods entrapped in polyacrylic acid (PAA) film

A simplistic approach for synthesis of zinc sulphide (ZnS) nanorods is reported. The synthesis of ZnS nanoparticles involved mixing of zinc acetate, sodium sulphide and acrylic acid in appropriate ratio at proper conditions, which formed the core. These nanoparticles were trapped in PAA by in-situ polymerization of acrylic acid and carefully casted into the film which resulted into entrapped nanorods in the polymer matrix. The nanoparticles as well as nanorods entrapped in PAA were characterized using high resolution scanning electron microscopy (SEM) for morphological investigations; energy dispersive X-ray analysis (EDAX) for composition and its crystalinity was checked using X-ray diffraction (XRD). The length of nanorods was in the range of 2–4 μm and thickness between 50–200 nm.     

Absorption of carbon dioxide into aqueous PAA solution containing diethanolamine

Carbon dioxide was absorbed into aqueous polyacrylamide (PAA) solution containing diethanolamine (DEA) of 0–2 kmol/m³ in a flat-stirred vessel with the impeller of 0.034 m and agitation speed of 50 rpm at 25 °C and 0.101 MPa to measure the absorption rate of CO₂. The volumetric liquid-side mass transfer coefficient (k_La) was obtained from the dimensionless empirical correlation formula presenting the rheological behavior of aqueous PAA solution. PAA with elastic property of non-Newtonian liquid made the rate of chemical absorption of CO₂ accelerate compared with Newtonian liquid based on the same viscosity of the solution. The estimated value of the absorption rate of CO₂ was obtained from the model based on the film theory accompanied by chemical reaction and compared with the measured value.     

PVA/PAA复合膜电响应特性的研究

通过研究PVA/PAA复合膜红外光谱特性,扫描电镜分析,及电场作用下膜通量的变化,阐明了PVA/PAA复合膜的电响应特性和规律。研究结果表明:制备的PVA/PAA复合膜中PVA与戊二醛已经发生交联反应形成酯键;-COOH基团的离子化是产生电响应的必要条件。随着PAA含量的增加,膜通量也明显的增加,表明体系中离子基团的数量(浓度)能够强烈影响PVA复合膜的直流电响应性;随着电场强度的增大,膜通量增加;在离子强度小于0.01mol/L时,膜通量随离子强度的增加而增加,但当离子强度大于0.01mol/L时,膜通量则呈现下降的趋势。在实验条件下,比较理想电响应条件为PVA∶PAA=1∶1,溶液离子强度为0.01mol/L。     

Covalent immobilization of α‐amylase onto thermally crosslinked electrospun PVA/PAA nanofibrous hybrid membranes

Poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) nanofibers with the fiber diameter of 100–150 nanometers were fabricated by electrospinning. PVA/PAA nanofibers were crosslinked by heat‐induced esterification and resulting nanofiber mats insoluble in water. α‐Amylase was covalently immobilized onto the PVA/PAA nanofiber surfaces via the activation of amine groups in the presence of 1,1′‐carbonyldiimidazole. The immobilized α‐amylase has more resistance to temperature inactivation than that of the free form and showed maximum activity at 50°C. pH‐dependent activities of the free and immobilized enzymes were also investigated, and it was found that the pH of maximum activity for the free enzyme was 6.5, while for the optimal pH of the immobilized enzyme was 6.0. Reuse studies demonstrated that the immobilized enzyme could reuse 15 times while retaining 81.7% of its activity. Free enzyme lost its activity completely within 15 days. Immobilized enzyme lost only 17.1% of its activity in 30 days. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of biocompatible multi‐walled carbon nanotubes as potential tracers for sentinel lymph nodes

Carbon nanotubes (CNTs) are capable of traversing cellular membranes by endocytosis and are therefore promising materials for use in imaging and drug delivery. Unfortunately, pristine CNTs are practically insoluble and tend to accumulate inside cells, organs and tissues. To overcome the poor dispersibility and toxicity of pristine CNTs, hydrophilic functionalization of CNTs has been intensively investigated. Water‐soluble multi‐walled carbon nanotubes (MWCNTs) were prepared by in situ polymerization of acrylic acid in a poor solvent for poly(acrylic acid) (PAA). The solvent type influenced the grafted density and chain length of PAA. MWCNTs with a high grafted density of PAA (22 wt%) could be well dispersed in water, NaCl aqueous solution (0.9 wt%) and cell culture media. The in vitro cytotoxicity of these MWCNTs for endothelial cells is reasonably low even at high concentration of PAA‐g‐MWCNT (70 µg mL^?1). The experimental results show that the biocompatibility of these MWCNTs is sufficient for biological applications. PAA‐g‐MWCNTs were successfully utilized for lymph node tracing. Experimental results suggest that PAA‐g‐MWCNTs have potential to be used as a vital staining dye, which may simplify the identification of lymph nodes during surgery. Copyright © 2009 Society of Chemical Industry     

含偶氮侧链聚酰胺酸合成及其三阶非线性光学性能

选取苯代三聚氰胺(BGA)和均苯四酸二酐(PMDA)为单体进行微波辐射溶液聚合反应,所得聚酰胺酸(PAA)通过重氮偶合反应引入含偶氮键的侧链,并且通过二次偶合进一步增加偶氮侧链的长度,从而合成新的具有三阶非线性光学活性的侧链型聚合物。通过红外、紫外、元素分析、拉曼等测试方法对接枝聚合物的结构进行了表征。通过简并四波混频飞秒激光系统对各个接枝聚合物的三阶非线性极化率系数进行了测定,考察了含取代基的偶氮侧链的引入对聚合物主链三阶非线性的影响,并考察了侧链上偶氮键的共轭长度对主链三阶非线性的影响。结果表明,侧链上偶氮基团的引入及其长度对提高聚合物主链三阶非线性都具有一定的影响。     

聚6-氨基己酸-β-丙氨酸的合成及降解行为研究

采用熔融缩聚法制备了一种新型可降解的6-氨基己酸(6N)和β-丙氨酸(βA)的二元共聚物(PAA),并研究了该共聚物的性能。采用红外光谱分析(FT-IR)、X射线衍射分析(XRD)、差示扫描量热分析(DSC)、热重分析(TGA)等手段对其结构进行了表征,结果表明,所合成的材料是2种单体的聚酰胺共聚物;随β-丙氨酸含量的增加,共聚物的结晶度、熔融温度呈先减小后增大的趋势,而分解温度呈依次减小的趋势,当共聚物中2种单体摩尔比为1∶1时,其为无定形共聚物。共聚物在去离子水中的降解实验结果表明,材料具有良好的降解性能;不同单体比例合成的共聚物中,共聚物的降解速率与共聚物的结晶度成反比,当聚合物中2种单体摩尔比为1∶1时,聚合物的降解速度最快,2周后几乎完全降解;整个降解过程中,降解液的pH值都维持在相对稳定的水平。在环保方面,该材料可望有良好的应用前景。