Synthesis and biological activity of phthalimide‐based polymers containing 5‐fluorouracil

The attachment of anticancer agents to polymers is a promising approach towards reducing the toxic side‐effects and retaining the potent antitumour activity of these agents. A new tetrahydrophthalimido monomer containing 5‐fluorouracil (ETPFU) and its homopolymer and copolymers with acrylic acid (AA) and with vinyl acetate (VAc) have been synthesized and spectroscopically characterized. The ETPFU contents in poly(ETPFU‐co‐AA) and poly(ETPFU‐co‐VAc) obtained by elemental analysis were 21 mol% and 20 mol%, respectively. The average molecular weights of the polymers determined by gel permeation chromatography were as follows: M_n = 8900 g mol^?1, M_w = 13 300 g mol^?1, M_w/M_n = 1.5 for poly(ETPFU); M_n = 13 500 g mol^?1, M_w = 16 600 g mol^?1, M_w/M_n = 1.2 for poly(ETPFU‐co‐AA); M_n = 8300 g mol^?1, M_w = 11 600 g mol^?1, M_w/M_n = 1.4 poly(ETPFU‐co‐VAc). The in vitro cytotoxicity of the compounds against FM3A and U937 cancer cell lines increased in the following order: ETPFU > 5‐FU > poly(ETPFU) > poly(ETPFU‐co‐AA) > poly(ETPFU‐co‐VAc). The in vivo antitumour activities of all the polymers in Balb/C mice bearing the sarcoma 180 tumour cell line were greater than those of 5‐FU and monomer at the highest dose (800 mg kg^?1). © 2002 Society of Chemical Industry     

Structure and properties of poly(ethylene‐co‐chlorotrifluoroethylene) and polyvinylidene fluoride exposed to water,hydrochloric acid,hydrobromic acid and tetrachloroethylene

The transport of water, hydrochloric acid, hydrobromic acid and tetrachloroethylene in an poly(ethylene‐co‐chlorotrifluoroethylene) and polyvinylidene fluoride were studied at 70°C by the sorption/desorption technique. The effects on the structure and mechanical properties were studied using size‐exclusion chromatography, infrared spectroscopy, differential scanning calorimetry and tensile testing. Solute concentrations in the polymers indicated that both the water and HCl/HBr components diffused into the polymers on exposure to acid solutions. The calculated water contents of the diffusing acids generally differed from the water content in the solution. The ratio of water content in the diffusing acid to that in the surrounding acid solution was generally a function of the relative vapor activity of water and HCl/HBr. It was possible to describe the 35%HCl and 47%HBr desorption data using a two component model. It was here assumed that the water and HCl/HBr diffused separately, each having its own constant diffusion coefficient. The water diffusivity was obtained from the pure water system, and this allowed the HCl/HBr diffusivity to be calculated. It was found that the diffusivity decreased, in a non‐simple way, as a function of solute size. The exposure to solute did not lower the molar mass of the polyvinylidene fluoride. Differential scanning calorimetry indicated the development of low‐melting point polyvinylidene fluoride crystals during the exposure to all solutes. This seemed to be a consequence of the long‐term exposure (175 to 376 days) at 70°C. The long‐term exposure stiffened several of the polyvinylidene fluoride resins and occasionally made them less ductile. The poly(ethylene‐co‐chlorotrifluoroethylene) also became stiffer, but it was otherwise unaffected as far as observation by the other available techniques was concerned.     

网络化雷达协同抗欺骗式干扰技术研究进展

网络化雷达在战场上可以构成全方位、立体化、多层次的战斗体系,因 此对欺骗式干扰对抗具有很大的优越性。本文首先简要介绍了网络化雷达概念,并分析了其 抗干扰优势。根据网络化雷达融合结构不同,将现有协同抗干扰方法分为数据级融合抗欺骗 式干扰和信号级融合抗欺骗式干扰两大类,其中,数据级融合方法进一步分类为点迹关联和 航迹关联两类。本文对各类方法进行了详细介绍,在此基础上,比较分析了数据级融合和信 号级融合两类方法的抗干扰性能及算法复杂度,为抗干扰措施的选择提供依据。最后,针对 现有方法中存在的问题,对网络化雷达协同抗欺骗式干扰的发展趋势进行展望,指出下一步 的研究方向。     

Methods to determine solubility parameters of polymers using inverse gas chromatography

Experimental values of the Flory–Huggins parameter, χ, between polymers and solvents, are frequently used to determine the solubility parameters of the polymers. A method using nonlinear curve fitting of RTχ/V was compared to the linear regression method commonly used. It was found that the formulas for the solubility parameter were the same, but the linear method produced a slightly different entropy term. The nonlinear method gave a lower correlation coefficient and wider confidence intervals and was more effective at distinguishing systems than the linear model. The effect of the deviation of probes in the solubility parameter model is discussed. Using probes with low solubility parameters to measure the polymer solubility parameter gave wider confidence intervals. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2894–2902, 2004     

Crosslinking of cotton cellulose in the presence of alkyl diallyl ammonium salts. I. Physical properties and agent distribution

We used three kinds of alkyl diallyl ammonium salts (methyl, ethyl, and propyl) in combination with dimethyloldihydroxyethyleneurea (DMDHEU) as crosslinking agents. The nitrogen content, dry crease recovery angle (DCRA), moisture regain, and wicking height for the DMDHEU/alkyl diallyl ammonium salts were in the order of ? CH₃ > ? C₂H₅ > ? C₃H₇, but the wet crease recovery angle (WCRA) and tensile strength retention (TSR) were in the opposite order at the same resin concentration. For the same DCRA and TSR, the WCRA values for only DMDHEU were lower than those for DMDHEU/alkyl diallyl ammonium salts, and the WCRA values for DMDHEU/alkyl diallyl ammonium salts were in the order of ? C₃H₇ > ? C₂H₅ > ? CH₃. Both the ? OH group of the cellulose and DMDHEU could react with the vinyl or epoxy groups of the alkyl diallyl ammonium salts during the pad–dry–cure process. The surface migration for DMDHEU/alkyl diallyl ammonium salts was in the order of ? CH₃ > ? C₂H₅ > ? C₃H₇. Fabrics treated with DMDHEU/alkyl diallyl ammonium salts showed good antibacterial properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1662–1669, 2003     

Influence of grafted polypropylene on the mechanical properties of mineral‐filled polypropylene composites

The purpose of this work was to study how mineral fillers would behave in a polypropylene (PP) matrix when PP modified with maleic anhydride (MA) and/or itaconic acid (IA) was used as a coupling agent in the preparation of mineral‐filled PP composites. The composites were characterized with tensile mechanical measurements and morphological analysis. The optimum amount of the coupling agent to be used to obtain composites with improved mechanical properties was established. The results indicated that these coupling agents enhanced the tensile strength of the composites significantly, and the extent of the coupling effect depended on the nature of the interface that formed. The incorporation of coupling agents enhanced the resistance to deformation of the composite. The behavior of IA‐modified PP as a coupling agent was similar to that of a commercial MA‐modified PP for the filled PP composites. Evidence of improved interfacial bonding was revealed by scanning electron microscopy studies, which examined the surfaces of fractured tensile test specimens; their microstructures confirmed the mechanical results with respect to the observed homogeneous or optimized dispersion of the mineral‐filler phase in these composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2343–2350, 2007     

Modification of leather properties by grafting. I. Effect of monomer chain on the physico‐mechanical properties of grafted leather

Although leather has a number of desirable properties such as thermal stability and fire retardancey, in addition to high toughness, it has a few drawbacks such as weight, high water absorption, poor soil and rot resistance, and nonuniformity. If these defects are overcome, leather's usefulness would be further enhanced and its competitive position with respect to synthetics would increase. This study reports the physical and mechanical properties of buffalo leather after chemical graft copolymerization with ethyl acrylate, butyl acrylate, and 2‐ethyl hexyl acrylate using benzoyl peroxide as an initiator. The optimum conditions for grafting (e.g., monomer and initiator concentrations, temperature and time of grafting, and solvent leather ratio) were extensively investigated. The study achieved outstanding properties for buffalo leather in reduction of water uptake after grafting, especially on using 2‐ethyl hexyl acrylate and butyl acrylate monomers. FT‐IR and solid ¹³C‐NMR for leather before and after grafting confirmed the grafting process.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1478–1483, 2003     

Photoluminiscent Manganese Nanoparticles from Solid State Polyphosphazenes Organometallic Derivatives

Pyrolysis in air at 800°C of [{NP(OC₁₂H₁₀)}_0.6{NP(OC₆H₄PPh₂·(π-CH₃C₅H₄)−Mn(CO)₂)₂}_0.4] _n (1) in the solid state affords product 2 containing nanoclusters of Mn₂P₂O₇ with sizes ranging from 50 to 90 nm and averaging about 74 nm. The egg-shape of the unpyrolyzed organometallic polymer is retained but with increased particle size after pyrolysis. The pyrolytic material shows near-infrared photoluminescence attributed to the emission of tetrahedral Mn²⁺ embedded in a matrix of Mn₂P₂O₇. The solid-state pyrolysis of organometallic derivatives of polyphosphazenes may be a useful and general route to nano-structured Mn₂P₂O₇. An erratum to this article can be found at     

Optimal reaction conditions for the minimization of energy consumption and by‐product formation in a poly(ethylene terephthalate) process

We determined the optimal reaction conditions to minimize the energy cost and the quantities of by‐products for a poly(ethylene terephthalate) process by using the iterative dynamic programming (IDP) algorithm. Here, we employed a sequence of three reactor models: the semibatch transesterification reactor model, the semibatch prepolymerization reactor model, and the rotating‐disc‐type polycondensation reactor model. We selectively chose or developed the reactor models by incorporating experimentally verified kinetic models reported in the literature. We established the model for the entire reactor system by connecting the three reactor models in series and by resolving some joint problems arising when different types of reactor models were interconnected. On the basis of the simulation results of the reactor system, we scrutinized the cause and effect between the reaction conditions and the final quality of the polymer product. Here, we set up the optimization strategy by using IDP on the basis of the integrated reactor model, and the process variables with significant influence on the properties of polymer were selected as control variables with the help of a simulation study. With this method, we could refine the reaction conditions at the end of each iteration step by contracting the spectra of control regions, and the iteration process finally stopped when the profile of the optimal trajectory converged. We also took the constraints on the control variables into account to guarantee polymer quality and to suppress side reactions. Constituting six different strategies by setting weighting vectors differently, we examined the differences in optimal trajectories, the trend of optimality, and the quality of the final polymer product. For each of the strategies, we conducted the optimization to examine whether the number‐average degree of polymerization approached the desired value. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 993–1008, 2002     

Adsorption mode of ethyl pyruvate on platinum: an in situ XANES study

The adsorption of ethyl pyruvate on Pt(111) has been studied by in situ XANES measurements in the presence and absence of hydrogen. Depending on the hydrogen and ethyl pyruvate pressure, the C and O K‐edge spectra exhibit distinctly different angular dependence. Without hydrogen ethyl pyruvate is oriented preferentially perpendicular to the surface, indicating bonding via the O lone pairs. In the presence of hydrogen the mean orientation is more tilted towards the surface. Likely, ethyl pyruvate also interacts with Pt via its π system under these conditions. The observed angle‐dependent shift of the energy of the π* and σ* resonances indicates the coexistence of differently adsorbed ethyl pyruvate species. The experimental findings demonstrate the importance of the in situ approach for unraveling the adsorption mode of ethyl pyruvate in the enantioselective hydrogenation over cinchona‐alkaloid‐modified Pt. This revised version was published online in July 2006 with corrections to the Cover Date.