Syntheses and biological activities of polymers containing methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid or 5‐fluorouracil

A series of novel copolymers, poly(methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid‐co‐exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalic acid) [poly(MTCA‐co‐ETAc)], poly(methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid‐co‐hydrogenethyl‐exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalate) [poly(MTCA‐co‐HEET)], and poly(methacryloyl‐2‐oxy‐1,2,3‐propanetricarboxylic acid‐co‐α‐ethoxy‐exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthaloyl‐5‐fluorouracil) [poly(MTCA‐co‐EETFU)], were prepared from corresponding monomers by photopolymerizations at 25°C for 48 h. The polymers were identified by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopies. The number‐average molecular weights of the fractionated polymers determined by GPC were in the range from 9400 to 14,900 and polydispersity indices were 1.2–1.4. The in vitro IC₅₀ values of polymers against mouse mammary carcinoma (FM3A), mouse leukemia (P388), and human histiocytic lymphoma (U937) as cancer cell lines and mouse liver cells (AC2F) as a normal cell line were much higher compared to that of 5‐fluorouracil (5‐FU). The in vivo antitumor activities of monomers and polymers against mice bearing sarcoma 180 tumor cell line were better than those of 5‐FU. The inhibition of DNA replication and antiangiogenesis activities of MTCA and copolymers were better compared to those of 5‐FU. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 57–64, 2004     

一种新的基于最大边缘准则的监督流形学习方法

在深入研究局部样条嵌入算法(LSE)的基础上,引入明确的线性映射关系,构建平移缩放模型和正交化特征子空间,提出了一种正交局部样条判别投影算法(O-LSDP),有效解决了原始LSE算法存在的两个主要问题:样本外点学习问题和无监督模式学习问题。该算法能够应用于模式分类问题并显著改善算法的分类识别能力。在标准人脸数据库上进行的实验比较分析验证了该算法的有效性与可行性。     

Web交互模型的形式化验证研究

Web交互模型的形式化验证是对Web事件属性进行校验的十分可信的方法。通过一系列的系统模型建立、系统行为分析以及对于模型中关心属性的相关验证,能够让交互模型在设计阶段就能使形式化模型暴露出其所存在的缺陷,而不至于让缺陷保留到编码阶段或者更后面才能被真正地暴露出来,这样使系统模型的生存能力更加强大,同时避免了因后期缺陷暴露而出现的大代价修复。通过对Web系统的交互应用服务的过程模型化的体系进行研究,通过模型本身具有的属性进行相关正确性的校验,主要通过使用数学推理实现系统逻辑上的服务交互进程,从而进行过程的推演,并对系统服务的正确性进行过程的形式化验证,从而使系统服务模块的属性正确性可以通过逻辑上的演进来发现服务问题的存在,而不再是系统通过编码实现后才发现。对Web交互模型的形式化验证是基于IMWSC模型语义形成的IMWSC模型的验证机制。     

具有不同代理群的多代理多签名方案

目前在大多数多代理多签名(multi-proxy multi-signature,MPMS)方案中,所有的原始签名人指定同一个代理群生成代理签名。然而在很多实际应用中,每个原始签名人经常需要在自己所在的组织中选择代理群,从而导致各个原始签名人需要选择不同的代理群,代表自己生成代理签名。现有的多代理多签名方案中还没有考虑这方面的需求。提出一个可以指定不同代理群的MPMS方案。在该方案中,可以指定一个多人的验证群合作验证最终签名的合法性。为证明方案的安全性,对现有的安全模型进行改进,在计算Diffie-Hellman假设的基础上,验证所提方案是安全的。与已有方案相比,本方案更加安全和有效。     

Thermal properties measurements of renatured gelatin using conventional and temperature modulated differential scanning calorimetry

The thermal properties of amorphous gelatin films and gelatin films with renatured structural order were measured by using conventional and temperature modulated differential scanning calorimetry (DSC). Different amounts of gelatin structural order associated with a melting enthalpic change in the DSC measurement were prepared based on different gelatin drying conditions. Two consecutive heating and cooling DSC measurements on the gelatin films showed that there was no change in the glass‐transition temperature (T_g) for the amorphous gelatin but there was a decrease in the T_g for the structural gelatin on the second DSC scan. This decrease was attributed to the plasticizing effect from the release of originally hydrogen‐bonded water associated with the structural gelatin. In addition, a reversing endotherm observed upon melting of the structural gelatin during a temperature modulated DSC measurement indicated that the transition of bound water to free water occurred as the partial triple‐helix gelatin melted. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1795–1801, 2006     

Effects of melt‐extension and annealing on row‐nucleated lamellar crystalline structure of HDPE films

The row‐nucleated lamellar crystalline structure of high‐density polyethylene (HDPE) films was prepared by applying elongation stress to HDPE melt during T‐die cast film extrusion and subsequently annealing the extruded films. This unusual crystalline structure was analyzed in terms of lamellar crystalline orientation, long‐period lamellar spacing, crystallite size, and degree of crystallinity. The contribution of melt‐extension represented by draw‐down‐ratio (DDR) to the overall orientation was found to be most noticeable than other processing variables. Meanwhile, the long‐period lamellar spacing, the crystallite size, and the degree of crystallinity were influenced predominantly by the annealing temperature. Finally, the processing (melt extension and annealing temperature) – structure (lamellar crystalline structure) – property (hard elasticity) relationship of HDPE films was investigated. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3326–3333, 2007     

Preparation and characterization of modified starch‐based plastic film reinforced with short pulp fiber. II. Mechanical properties

Native corn starch‐ and hydroxypropylated starch (HPS‐) based plastic films were prepared using the short pulp fiber as the reinforcement and the glycerol as the plasticizer. The results of tensile test showed that the strain and stress at break and elastic modulus increased with pulp content. With glycerol content, the strain at break increased considerably, but the breaking stress and elastic modulus decreased. And the stress–strain curves showed that the brittleness problem of films was overcome by the pulp, glycerol, and water content. The hydroxypropyl starch films showed results similar to those of the native starch films. The results of the three‐point bending test showed that maximum deflection, flexural strength, and specific work increased with pulp content, but the flexural modulus was the highest at a pulp content of 20%. And with the glycerol content, the maximum deflection and specific work of rupture increased, but the bending elastic modulus decreased. The hydroxypropyl starch films showed results similar to those of native starch films as far as the maximum deflection and flexural strength were concerned, but the bending elastic modulus and specific work of the hydroxypropyl starch films were considerably lower than those of starch films. So it was concluded that the flexibility of films was improved by the hydroxypropylation. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2108–2117, 2003     

Toughness response of vinylester/epoxy‐based thermosets of interpenetrating network structure as a function of the epoxy resin formulation: Effects of the cyclohexylene linkage

Vinylester/epoxy (VE/EP)‐based thermosets of interpenetrating network (IPN) structures were produced by using a VE resin (bismethacryloxy derivative of a bisphenol A–type EP resin) with aliphatic (Al‐EP) and cycloaliphatic (Cal‐EP) EP resins. Curing of the EP resins occurred either with an aliphatic (Al‐Am) or cycloaliphatic diamine compound (Cal‐Am). Dynamic mechanical thermal analysis (DMTA) and atomic force microscopy (AFM) suggested the presence of an interpenetrating network (IPN) in the resulting thermosets. Fracture toughness (K_c) and fracture energy (G_c) were used as the toughness characterization parameters of the linear elastic fracture mechanics. Unexpectedly high K_c and G_c data were found for the systems containing cyclohexylene units in the EP network, such as VE/Al‐EP+Cal‐Am and VE/Cal‐EP+Al‐Am. This was attributed to the beneficial effects of the conformational changes of the cyclohexylene linkages (chair/boat), which were closely analogous to those in some thermoplastic copolyesters. The failure mode of the VE/EP thermoset combinations was studied in scanning electron microscopy (SEM) and discussed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2124–2131, 2003     

Effects of nano‐ and micro‐fillers and processing parameters on injection‐molded microcellular composites

The effects of submicron core‐shell rubber (CSR) particles, nanoclay fillers, and molding parameters on the mechanical properties and cell structure of injection‐molded microcellular polyamide‐6 (PA6) composites were studied. The experimental results of PA6 nanocomposites with 5.0 and 7.5 wt% nanoclay loadings and of CSR‐modified PA6 composites with 0.5 and 3.1 wt% CSR loadings were compared to their neat resin counterparts. This study found that nanoclay was more efficient in promoting a smaller cell size, larger cell density, and higher tensile strength for microcellular injection molding parts. A higher nanoclay loading led to more brittle behavior for microcellular parts. It was found that a proper amount of CSR particles could be added to the microcellular injection‐molded PA6 to reduce the cell size, increase the cell density, and enhance the toughness of the molded part. However, CSR particles were less effective cell nucleation agents as compared to nanoclay for producing desirable cell structures, and a higher CSR loading was found to have diminishing effects on the process and on the properties of the parts. POLYM. ENG. SCI., 45:773–788, 2005. © 2005 Society of Plastics Engineers     

Study on esterification of acrylic phenolic resin by maleic anhydride and photocrosslinking properties of the alkali‐soluble product

An alkali‐soluble, photocrosslinkable polymer was synthesized by esterification of OH groups of acrylic phenolic resin with maleic anhydride. The OH groups were formed by the ring‐opening reaction of epoxy groups of epoxy phenolic resin with acrylic acid. The esterification conditions were studied. The results showed that it is better to use tetramethyl ammonium bromide as catalyst than N,N‐dimethylbenzylamine. The conversion of maleic anhydride in acetone can reach about 80% at 56°C for 4 h. The purified product was characterized by IR, DSC, and TGA. The product containing acrylate and maleic acid monoester groups, above a certain content, can be dissolved in 1% Na₂CO₃ solution. The photocrosslinkable properties of the product were investigated through selection of photoinitiator, accelarator, crosslinkable diluent monomer, etc. The acrylate and maleic acid monoester group‐containing phenolic resin exhibited very good photocrosslinking behavior, since it contains double bonds from both acrylate groups and maleic acid monoester groups. The activity of photoinitiator decreases in the order: isopropylthioanthraquinone > benzoin ethyl ether (BE) > anthraquinone (AQ) > benzophenone > Michel ketone (MK) > 2,2‐diethoxyacetophenone. The combination of some photoinitiators showed synergistic effects. The order of increasing activity for the accelerator is as follows: MK > ethyl p‐(dimethylamino)benzoate > N,N‐dimethylaniline > triethanolamine. The optimum diluent monomer is trimethylolpropane trimethacrylate. The gel content of the mixture of the resin and trimethylolpropane trimethacrylate could reach 85% using the combined photoinitiators of BE and AQ under UV exposure for 120 s. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1607–1614, 2005