单溴四苯基卟啉吸附在AgCl溶胶表面性质研究

合成了单溴四苯基卟啉—— 5 - (邻溴苯基 ) - 1 0 ,1 5 ,2 0 -三苯基卟啉 (H2 L) ,用元素分析 ,红外光谱、电子吸收光谱和氢核磁共振谱确定了其组成和结构。研究了 H2 L在醋酸中电子吸收光谱和在 Ag Cl溶胶上的表面化学反应。结果表明 ,单邻溴四苯基卟啉在冰醋酸中以二酸形式 H4 L2 + 和游离碱 H2 L形式存在 ,二者之间存在着电离平衡 :H4 L2 + =H2 L+2 H+ ;当 p H=7.0～ 1 1 .0时 ,H2 L在Ag Cl溶胶表面发生配位反应生成 Ag( ) L,并且溶液的 p H增大 ,配位反应的速率增大。     

Molecular species of 1-O-alk-1′-enyl-2-acyl-, 1-O-alkyl-2-acyl- and 1,2-diacyl glycerophospholipids in Japanese oysterCrassostrea gigas (Thunberg)

Molecular species of 1-O-alk-1′-enyl-2-acyl-, 1-O-alkyl-2-acyl-, and 1,2-diacyl-sn-glycero-3-phosphoethanolamine (EPL) andsn-glycero-3-phosphocholine (CPL) of Japanese oysterCrassostrea gigas were analyzed by selectedion monitoring gas chromatography/mass spectrometry using electron impact ionization. The characteristic fragment ions, [RCH=CH+56]⁺ due to the alkenyl residue in thesn-1 position and [RCO+74]⁺ due to the acyl residue in thesn-2 position of alkenylacylglycerols, [R+130]⁺ due to the alkyl residue in thesn-1 position and [RCO+74]⁺ due to the acyl residue in thesn-2 position of alkylacylglycerols, [RCO+74]⁺ due to the acyl residues in thesn-1 and/orsn-2 positions of diacylglycerols, and [M−57]⁺ being indicative of the corresponding molecular weight, were used for structural assignments. For alkenylacyl EPL and CPL, 19 and 16 molecular species were determined, respectively. Two molecular species, 18∶0alkenyl-22∶6n−3 and 18∶0-alkenyl-22∶2-non-methylene interrupted diene (NMID), amounted to 53.2% and 47.9%, respectively. The alkylacyl EPL and CPL consisted of 16 and 20 molecular species, respectively, and the prominent components were 18∶0alkyl-22∶2NMID, 20∶1alkyl-20∶1n−11 (27.4%) and 20∶1alkyl-20∶2NMID (16.3%) in the former, and 16∶0alkyl-20∶5n−3 (23.0%) and 16∶0alkyl-22∶6n−3 (21.6%) in the latter. For the diacyl EPL and CPL, 14 and 51 molecular species were determined, respectively. The major molecular species were 18∶0–20∶5n−3 (37.4%), 16∶0–20∶5n−3 (14.2%) and 18∶1n−7–22∶2NMID (13.2%) in the former, and 16∶0–20∶5n−3 (33.4%) and 16∶0–22∶6n−3 (22.3%) in the latter. It was found that there were significant differences in the molecular species between the alkylacyl and diacyl EPL and the alkylacyl and diacyl CPL; the number of molecular species was larger in CPL than in EPL, while the number of total carbons and double bonds of the major molecular species were larger in the EPL than in the CPL. Alkenylacyl EPL were similar to alkenylacyl CPL in molecular species composition.     

Effect of thermal history on mechanical properties of polyetheretherketone below the glass transition temperature

Tensile properties of polyethertherketone (PEEK) have been studied at 125, 25, and ?100°C for thin films prepared with different thermal histories. Initial morphology was controlled by rate of cooling from the melt. Amorphous films resulted from quenching the melt, while semicrystalline films were obtained by cooling the melt at different rates, or by crystallization of the rubbery amorphous state. The films were characterized using density, X-ray scattering, differential scanning calorimetry, and infrared spectroscopy. Scanning electron microscopy was used to examine fracture surfaces. Degree of crystallinity and rate of cooling from the melt affected the tensile properties at all test temperatures. For films with nearly the same degree of crystallinity, those which were more slowly cooled from the melt fractured at the lowest strain. The amorphous films were most tough, drawing to 233% at ?100°C and to over 500% at 125°C. Films crystallized from the rubbery amorphous state had stress–strain behavior intermediate between that of the amorphous and melt-crystallized films at all test temperatures. Density measurements on the drawn material indicate that void formation occurs simultaneously with the formation of fibrillar crystals. Necking resulted in density increases for amorphous films, and density decreases for the semicrystalline films.     

Novel nitrogen‐containing epoxy resin. II. Cure kinetics by differential scanning calorimetry

The isothermal and nonisothermal cure behaviors of a novel nitrogen‐containing epoxy resin (XT resin) were studied by differential scanning calorimetry (DSC). Various kinetic parameters and details of cure process were obtained based on the Avrami theory. The results indicated that Avrami method is suitable for calculating the kinetic parameters up to the gel point at least. The apparent activation energy (E_a) for isothermal cure process was in agreement with that for nonisothermal cure process. E_a value in the early stage (78.5–81.0 KJ mol^?1) was about three times than that in the later stage (23.3–26.5 KJ mol^?1). The kinetic results from Avrami theory may present a combined effect of all factors, and which is helpful to understand the cure technique for XT–DDS system. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3483–3489, 2006     

基于神经网络和过程机理的热流体系统仿真

构建了一种基于复合神经网络和过程机理特性的热流体系统仿真模型 .该模型在形式上为一种复合人工神经网络模型 ,保证了模型具有十分理想的仿真速度 ;在网络模型设计上较好地考虑了系统输入与输出间的物理基础 ,网络模型在一定程度上由常规的黑箱模型转化为“灰箱模型” ,网络的训练除了具有常规的输入、输出间的纯数值映射关系学习功能之外较好地体现了对象输入与输出间的物理机理学习 ,保证了网络模型具有良好的联想能力、外推能力和时间递推能力 .     

Isothermal crystallization kinetics and morphology development of isotactic polypropylene blends with atactic polypropylene

The crystallization kinetics and morphology development of pure isotactic polypropylene (iPP) homopolymer and iPP blended with atactic polypropylene (aPP) at different aPP contents and the isothermal crystallization temperatures were studied with differential scanning calorimetry, wide‐angle X‐ray diffraction, and polarized optical microscopy. The spherulitic morphologies of pure iPP and larger amounts of aPP for iPP blends showed the negative spherulite, whereas that of smaller amounts of aPP for the iPP blends showed a combination of positive and negative spherulites. This indicated that the morphology transition of the spherulite may have been due to changes the crystal forms of iPP in the iPP blends during crystallization. Therefore, with smaller amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends increased with increasing aPP and presented a lower degree of perfection of the γ form coexisting with the α form of iPP during crystallization. However, with larger amounts of aPP, the spherulitic density and overall crystallinity of the iPP blends decreased and reduced the γ‐form crystals with increasing aPP. These results indicate that the aPP molecules hindered the nucleation rate and promoted the molecular motion and growth rate of iPP with smaller amounts of aPP and hindered both the nucleation rate and growth rate of iPP with larger amounts of aPP during isothermal crystallization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1093–1104, 2007     

Self-assembly of C60 containing poly(methyl methacrylate) in ethyl acetate/decalin mixtures solvent

[60]Fullerene (C₆₀) was mono-substituted with well-defined poly(methyl methacrylate) (PMMA-b-C₆₀) using the atom transfer radical polymerization (ATRP) technique. The self-assembly behaviors of PMMA-b-C₆₀ in ethyl acetate (EA) and decalin mixtures were studied using laser light scattering (LLS) and transmission electron microscopy (TEM). Homogeneous solutions of PMMA-b-C₆₀ can be obtained in the solvent mixtures containing more than 40 wt% EA, where the molar ratio of decalin to EA is close to 1. For each solvent mixture, unimers coexist with micelles and large aggregates. The sizes of PMMA-b-C₆₀ micelles and aggregates are independent of polymer concentration, confirming that they are produced via the closed association mechanism. For the various solvent mixtures, the weight-averaged molecular weights, M_w of the PMMA-b-C₆₀ aggregates range from 4.1×10⁷ to 12.5×10⁷ g/mol. The hydrodynamic radii of the large aggregate, R_h, vary from 90 to 136 nm, while the z-averaged radii of gyration, R_g, range from 210 to 311 nm. The R_g/R_h value for each solvent mixture is ∼2.3, which is independent of decalin contents in the mixed solvents. The morphological study using the transmission electron microscope suggests that the large aggregates are composed of porous large compound micelles (LCM) in solution.     

Preparation and characterization by radiation of hydrogels of PVA and PVP containing Aloe vera

In these studies, hydrogels for wound dressing were made from a mixture of Aloe vera, poly(vinyl alcohol) (PVA) and poly(N‐vinylpyrrolidone) (PVP) by freeze‐thaw, gamma‐ray irradiation, or a two‐step process of freeze‐thaw and gamma‐ray irradiation. Physical properties, such as gelation, water absorptivity, gel strength and degree of water evaporation were examined to evaluate the applicability of these hydrogels to wound dressing. The PVA:PVP ratio was 6:4, and the dry weight of Aloe vera was in the range of 0.4‐1.2 wt %. The solid concentration of PVA/PVP/Aloe vera solution was 15 wt %. Mixtures of PVA/PVP/Aloe vera were exposed to gamma irradiation doses of 25, 35 and 50 kGy to evaluate the effect of irradiation dose on the physical properties of the hydrogels. Gel content and gel strength increased as the concentration of Aloe vera in PVA/PVP/Aloe vera decreased and as irradiation dose increased and freeze‐thaw was repeated. Swelling degree was inversely proportional to gel content and gel strength. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1612–1618, 2004     

Durable antimicrobial treatment of cotton fabrics using N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride and polycarboxylic acids

N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride (HTCC), a water‐soluble chitosan quaternary ammonium derivative, was used as an antimicrobial agent for cotton fabrics. HTCC has a lower minimum inhibition concentration (MIC) against Staphylococcus aureus, Klebsiella pneumoniae, and Escherichia coli compared to that of chitosan; however, the imparted antimicrobial activity is lost on laundering. Thus crosslinking agents were utilized to obtain a durable antimicrobial treatment by immobilizing HTCC. Several crosslinkers such as dimethyloldihydroxyethylene urea (DMDHEU), butanetetracarboxylic acid (BTCA), and citric acid (CA) were used with HTCC to improve the laundering durability of HTCC treatment by covalent bond formation between the crosslinker, HTCC and cellulose. The polycarboxylic acid treatment was superior to the DMDHEU treatment in terms of prolonged antimicrobial activity of the treated cotton after successive laundering. Also, the cotton treated with HTCC and BTCA showed improved durable press properties without excessive deterioration in mechanical strength or whiteness when compared to the citric acid treatment. With the addition of only 0.1% HTCC to BTCA solutions, the treated fabrics showed durable antimicrobial activity up to 20 laundering cycles. The wrinkle recovery angle and strength retention of the treated fabrics were not adversely affected with the addition of HTCC. Therefore, BTCA can be used with HTCC in one bath to impart durability of antimicrobial activity along with durable press properties to cotton fabric. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1567–1572, 2003     

Preparation and characterizations of interpenetrating polymer network hydrogels of poly(ethylene oxide) and poly(methyl methacrylate)

Interpenetrating polymer network (IPN) hydrogels based on poly(ethylene oxide) and poly(methyl methacrylate) were prepared by radical polymerization using 2,2‐dimethyl‐2‐phenylacetophenone and ethylene glycol dimethacrylate as initiators and crosslinkers, respectively. The IPN hydrogels were analyzed for sorption behavior at 25°C and at a relative humidity of 95% using dynamic vapor sorption. The IPN hydrogels exhibited a relatively high equilibrium water content in the range of 13–68%. The state of water in the swollen IPN hydrogels was investigated using differential scanning calorimetry. The free water in the hydrogels increased as the hydrophilic content increased. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 258–262, 2003