角蛋白基药物载体的发展及应用探讨

从毛发中提取角蛋白，开发具有独特功能的角蛋白基药物载体材料，提高药物的活性和生物利用率，既能够增加毛发的利用价值，又能够实现节能减排，符合可持续发展战略要求。对毛发中提取角蛋白进行二硫键重建、自由基聚合、多糖改性和烷基化等改性处理，赋予角蛋白基药物载体优异地功能特性，进一步拓宽其作为角蛋白基药物载体的应用范围。角蛋白基药物载体可被加工成纳米粒子、纤维支架、水凝胶等各种形式用于药物的递送。作为一种高硫含量且具有良好细胞相容性的结构蛋白，角蛋白基药物载体在组织工程、再生医学等领域扮演着重要的角色。     

Preparations and properties of thermosensitive terpolymers of N‐isopropylacrylamide,sodium 2‐acrylamido‐2‐methyl‐propanesuphonate,and N‐tert‐butylacrylamide

Terpolymers based on N‐isopropylacrylamide, sodium 2‐acrylamido‐2‐methyl‐propanesulfonate, and N‐tert‐butylacrylamide were synthesized by free‐radical copolymerization with 2,2′‐azobisisobutyronitrile as an initiator. The lower critical solution temperatures (LCSTs) of the linear polymer aqueous solutions were determined by the measurement of the transmittance on UV at different temperatures. The influence of the polymer concentration, polymer composition, and ionic strength on the LCSTs of the linear polymers was investigated. The LCST decreased with increases in the hydrophobic monomer N‐tert‐butylacrylamide, polymer concentration, and ionic strength. The phase transition became sharp when the polymer concentration and ionic strength increased. Meanwhile, the crosslinked hydrogels were prepared with the same recipe used for the linear terpolymers, but a crosslinker was added to the reaction system. The swelling ratios of the hydrogels at various temperatures and salt solutions were determined. The hydrogels possessed both high swelling ratios and thermosensitivity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis of tetramethyl-p-silphenylenesiloxanedimethylsiloxane triblock copolymer by employing living anionic polymerization

Dimethylsiloxane-tetramethyl-p-silphenylenesiloxane-dimethylsiloxane (DMS-TMPS-DMS) triblock copolymer was synthesized by employing living anionic polymerization of hexamethylcyclotrisiloxane (D₃). Two synthetic methods were carried out for the polymerization. One of those methods was the anionic polymerization of D₃ initiated at the silanolate anion which was prepared from the terminal hydroxyl group of silanol-terminated TMPS prepolymer by reaction with n-butyllithium (method 1). The other was the coupling reaction of vinyl-terminated TMPS prepolymer with hydrosilyl-terminated DMS prepolymer obtained from the anionic polymerization of D₃ by using diphenylmethylsilanolate anion as initiator (method 2). In method 1, DMS contents of the copolymers ranged from 25.8 to 72.5 wt% and the values agreed with the ratio of D₃ to TMPS prepolymer. The weight-average molecular weights ranged from 1.36×10⁴ to 19.4×10⁴ and were close to the predicted values calculated from the $\text{M}\text{?}{}_{\mathrm{v}}$ of the TMPS prepolymer and the amount of D₃ added. In the case of method 2, weight-average molecular weights ranged from 19.5×10⁴ to 24.2×10⁴. The high molecular weight copolymer could thus be obtained by method 2. Intrinsic viscosity values of the triblock copolymers agreed with calculated values obtained by considering the copolymer as a binary mixture of these homopolymers. Differential scanning calorimetry and thermogravimetry were carried out on the triblock copolymers. The equilibrium melting temperatures of each of the copolymers were very close to that of poly-TMPS (160°C). The glass transition temperature and heat of fusion were decreased as the DMS content was increased. The thermogravimetric curves for the copolymers indicated that the thermal stability of the triblock copolymer was intermediate between the DMS and TMPS homopolymers.     

High temperature polymerization of propylene catalyzed by MgCl2‐supported Ziegler–Natta catalyst with various cocatalysts

Four cocatalysts, referred to as ethylaluminoxanes, were synthesized by the reaction between triethylaluminium (AIEt₃) and water under various molar ratios of H₂O/Al at ?78°C. Aluminoxanes were used as cocatalysts for a MgCl₂‐supported Ziegler–Natta catalyst for propylene polymerization at temperatures ranging from 70 to 100°C. When the polymerization was activated by AlEt₃, the activity as well as the molecular weight and isotacticity of the resulting polymer gradually dropped as the temperature varied from 70 to 100°C. When ethylaluminoxane was employed as the cocatalyst, good activity and high molecular weight and isotacticity were obtained at 100°C. Furthermore, when the cocatalyst varied from AlEt₃ to ethylaluminoxane, the atactic fraction and polymer fraction with moderate isotacticity decreased and the high isotactic fraction slightly increased, which indicated that the variation of the cocatalyst significantly affects the isospecificity of active sites. It was suggested that the reactivity of the Al‐Et group and the size of the cocatalyst were correlated to the performance of the Ziegler–Natta catalyst at different temperatures. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1978–1982, 2006     

Poly(p-tert-butoxycarbonyloxystyrene): a convenient precursor to p-hydroxystyrene resins

An efficient synthetic route to pure, high molecular weight poly(p-hydroxystyrene) is reported. The route involves synthesis of a new monomer, p-tert-butoxycarbonyloxystyrene, polymerization by radical initiation or by cationic initiation in liquid SO₂, followed by thermolysis or acidolysis of the tert-butoxycarbonyl protecting group. Porous, crosslinked resin beads containing the nucleophilic, phenol pendant group have been prepared in a similar fashion from the precursor terpolymer of p-tert-butoxycarbonyloxystyrene, styrene and divinylbenzene. The utility of this resin for solid-phase synthesis has been demonstrated.     

高聚合度聚氯乙烯的加工性能

本文对高聚合度聚氯乙烯(H-PVC)的发展及其优异的物理机械性能作了简要介绍;着重分析了H-PVC的加工性能和表征方法,并讨论了分子特性和颗料特性及加工组成、加工条件对加工性能的影响,提出了改进H-PVC加工性能的方法。     

Configurational statistics of copolymers prepared by complex-radical polymerization

Radical copolymerization is considered theoretically taking into account the effect of complexing on the configurational statistics of macromolecules formed. Akinetic model has been developed that considers, apart from the ordinary addition of single monomer units to a propagating chain, the possible addition of monomer unit pairs along with a complexing agent in the form of a ternary complex. Within the framework of this model, the problem of calculating the probabilities of formation of any sequences of monomer units (taking into account their microtacticity) in a macromolecule has been rigorously solved as well as the problem of finding the composition distribution of the copolymer formed. It has been shown that this distribution is described by a conventional Gauss law and the appropriate parameters are given. Possible generalizations of the suggested approach are indicated.     

MACROPROCESS OF PARTICLE FORMATION IN SUSPENSION POLYMERIZATION OF STYRENE WITH INORGANIC STABILIZER SYSTEM

The macroprocess of particle formation from suspension droplets of styrene in a pdymerizationsystem was investigated.Inorganic hydroxyapatite or its mixture with polyvinyl alcohol as thepolymerization system was used.Those items such as the effects of the Weight fraction of dispersed-phase,the amount of the inorganic stabilizer and the agitation speed on the breakup and coalescence of thetransient dispersed drops etc.Were examined.Results showd that the dynamic behavior of the transi-ent polymer droplets changed in the presence of the suspension stabilizer during the reaction.     

Synthesis and characterization of copolythiophene

Copolythiophenes (Co‐PTs), poly(3‐hexylthiophene‐co‐3‐thiophene carboxylic acid) (P3HT‐TCa), poly(3‐hexyloxylthiophene‐co‐3‐thiophene carboxylic acid) (P3HOT‐TCa), and poly(3‐phenylthiophene‐co‐3‐thiophene carboxylic acid) (P3PhT‐TCa), were synthesized by chemical oxidized polymerization to investigate the effect of copolymerization on the properties of polythiophenes (PTs). Gel permeation chromatography showed that the molecular weight (MW) of Co‐PT was lower than that of homopolythiophene. Fourier transform infrared (FTIR) spectra indicated that the copolymerization was successful between the monomers. The λ_max of Co‐PTs gave a “blue shift” in ultraviolet‐visible (UV‐VIS) spectra. Photoluminescence (PL) spectra showed that the PL intensity of Co‐PT became weaker than that of homopolythiophene and the disappearance of PL had been observed in P3HOT‐TCa. The thermal stability of Co‐PT was influenced by the carboxyl for its low decomposition temperature. Furthermore, the copolymerization between multi‐wall carbon nanotube containing thiophene ring (MWNT‐Th) and 3‐hexyloxylthiphene could also take place successfully. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Apparatus and procedure for measuring release rates from formulations of lepidopteran semiochemicals

An apparatus was developed wherein a vacuum source was used to pull air across a controlled-release-formulation dispenser or a planchet containing a known quantity of a semiochemical and into a collector filled with a polymeric adsorbent. After a set time, the semiochemical was eluted with solvent and was quantified by gas-liquid chromatography (GLC). High percentages of known quantities of the lepidopteran semiochemicals (Z)-7-dodecen-l -ol acetate (Z7DDA), boiling point (bp) 275 ° C/1 atm, (Z)-9-tetradecen-1-ol formate (Z9TDF), bp 289 °C/1 atm, and (Z,Z)-3,13-octadecadien-1-ol acetate (ZZODDA), bp 490 °C/1 atm, were recovered. The semiochemicals did not oxidize and were recovered quantitatively from the adsorbent. The release rates of Z9TDF from a controlled-release dispenser were found to be directly proportional to the airflow rates. Release rate measurements on the Z9TDF dispensers were made for the purpose of estimating the method's precision. The method was shown to give internally consistent results by measurements on another Z9TDF formulation. The accuracy of the method is discussed.Mention of a commercial or proprietary product in this paper does not constitute an endorsement by the USDA.