α-苯甲胺基-β-(3-吲哚基)-丙酸甲酯的合成

以L-色氨酸为原料经过4步得到α-苯甲胺基-β-(3-吲哚基)-丙酸甲酯,它是一种具有潜在的抗肿瘤活性的吲哚二酮哌嗪化合物的中间体,首先通过“酰氯法”合成L-色氨酸甲酯盐酸盐,再脱去盐酸,与苯甲醛发生缩合反应形成希夫碱,最后选择性还原,得目的产物,得率54.9%.     

Preparation and Properties of Polylactic Acid (PLA)/Silica Nanocomposites

Surface-modified silica was incorporated into bio-based polylactic acid (PLA) to improve its performance. The modification by aminosilane on the silica was confirmed through FTIR (Fourier transform infrared) spectra. Following the aminosilane modification, polyethylene glycol methyl ether (PEGME) was grafted, via the aminosilane, on the silica to form the desired surface-modified silica (PEGME-silica). The grafting percentage of polyethylene glycol methyl ether was about 6.9 wt%. Unmodified silica, having underwent a similar treatment to maintain the same thermal history but without adding silane and PEGME, was also prepared. The PEGME-silica system had slightly higher tensile strength than the unmodified silica system, with a rheological study showing an enhanced polymer matrix-dispersed silica interaction and better dispersion in morphology observations being proposed as the cause. The dynamic storage modulus in the terminal zone was reduced for large amounts of highly dispersed surface-modified silica in comparison with unmodified silica. Tan δ decreased significantly with increasing unmodified silica contents in the low frequency region, resulting in solid-like behaviors. On the other hand, there was only a limited decrement for modified silica-filled samples in the corresponding ranges, especially for low dosages of the modified silica. The shear thinning phenomenon appeared to be more pronounced for unmodified silica at high silica content, but not for modified silica. To the best of our knowledge, this is the first report of the effect of polyethylene glycol methyl ether (PEGME)-modified nanosilica on the properties of PLA/silica nanocomposites prepared under a melt mixing process to illustrate the significance of surface modification via Cole–Cole plots.     

Thiolated polyethylene oxide as a non-fouling element for nano-patterned bio-devices

This work describes the synthesis of a thiolated polyethylene oxide that self-assembles on gold to create a non-fouling surface. Thiolated polyethylene oxide was synthesised by reacting 16-mercaptohexadecanoic acid with polyethylene glycol mono methyl ether. The coverage of the thiolated polyethylene oxide on gold was studied by cyclic voltammetry, and the modified surfaces were characterised by X-ray photoelectron spectroscopy and ellipsometry. Protein resistance was assessed using quartz crystal microbalance. Results showed a non-fouling character produced by the thiolated polyethylene oxide. The synthesised product was used as the passivation layer on nano-patterned surfaces consisting of arrayed nano-spots, fabricated by plasma based colloidal lithography. The specific adsorption of anti-bovine serum albumin in the mercaptohexadecanoic acid spots was verified by atomic force microscopy.     

Blood Compatibility of Multilayered Polyelectrolyte Films Containing Immobilized Gold Nanoparticles

Surface material functionalization including layer‐by‐layer (LbL) polyelectrolyte films with incorporated nanoparticles is a growing field with a wide range of biomedical applications: drug reservoirs, medical devices, or tissue engineering. In parallel, gold nanoparticles (AuNPs) can be grafted by drugs and sensitive molecules using simple protocols. This study shows that AuNP behavior is modified when they are entrapped into three partner LbL films in comparison to the colloidal solution. A polycationic (polyallylamine hydrochloride (PAH)) and a polyanionic (polyacrylic acid (PAA)) polymer is used to build films based on three cycles ((PAH/AuNP/PAA)₃). To investigate the interaction with biomolecules and cells, three different films are developed changing the outer layer (either PAH or AuNP or PAA) with the same number of AuNP deposit. The best biocompatibility is observed with a polyacrylic acid outer layer. Due to the high capacity of drug grafting on gold nanoparticles, the results seem promising for the development of nanostructured biomedical devices.     

Chemical modification of porous and corrugated silicon surfaces in polyacrylic acid solutions

The chemical modification of porous silicon (PS) surfaces makes it possible to eliminate weak silicon-hydrogen bonds and prevent the formation of Si-O and Si-OH groups deep in pores and on a corrugated silicon surface. Hence, the effect of PS aging is not observed during its storage in air, and the porous layer??s composition is stable. Surfaces have been modified in polyacrylic acid solutions. The surface composition is analyzed on the basis of X-ray absorption spectra, and the morphology is investigated via scanning electron microscopy. It has been ascertained that the composition and morphology of a surface treated in polyacrylic acid solutions depend on the PS preparation method.     

Optical Properties of Silver Nanoclusters Synthesized in Surface-Grafted Polyacrylic Acid at Different Grafting Densities

Optics and Spectroscopy - Fluorescent silver nanoclusters immobilized on a plastic substrate are obtained by photoinduced template synthesis using polyacrylic acid chemically grafted to the...     

聚丙烯酸酯玻璃化转移温度QSPR的研究

对聚丙烯酸酯的定量构性关系(QSPR)研究具有重要意义。采用分子电性作用失量(MEIV)表征聚丙烯酸酯的分子结构,运用多元线性回归(MLR)建立定量结构玻璃化转移温度相关(QSPR)模型,同时采用逐步回归结合统计检测筛选模型变量,建立了22个聚丙烯酸酯玻璃化转移温度（Tg）与其结构间的多元线性回归方程。另外采用内部及外部双重验证的办法深入分析和检验模型的稳定性。建模的复相关系数(Rcum)、留一法(LOO)交互校验复相关系数(Qcum)和外部样本校验复相关系数(Qext)分别为0.982、0.971和0.922。表明用MEIV对聚丙烯酸酯分子结构信息表达较好,所建QSPR模型的稳定性和预测能力良好。     

Surface modification of ultra high molecular weight polyethylene fibers via the sequential photoinduced graft polymerization

In this study, a sequential photoinduced graft polymerization process was proposed to improve the poor interfacial bonding property of ultra high molecular weight polyethylene (UHMWPE) fibers. The polymerization was initiated by dormant semipinacol (SP) groups and carried out in a thin liquid layer. Methacrylic acid (MAA) and acryl amide (AM) were grafted stepwise onto the surface of UHMWPE fibers. Attenuated total reflectance infrared spectroscopy (ATR-IR) and thermo gravimetric analysis (TGA) confirmed the grafting. The analysis result of pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) indicated the structure of grafted chains. Scanning electron microscopy (SEM) images and atomic force microscopy (AFM) images revealed the apparent morphology changing, and the grafted layers were observed. Interfacial shear stress (IFSS) test of the modified fibers showed an extensively improved interfacial bonding property. The active groups grafted onto the fibers would supply enough anchor points for the chemical bonding with various resins or further reactions.     

Influence of Compatibilizer-Type and Processing Approach on the Dispersion of OMMT in High-Density Polyethylene Matrix

High-density polyethylene/organoclay nanocomposites were prepared via melt intercalation in an internal mixer using both a direct mixing and master batching method. Two types of maleic anhydride grafted polyethylene, high-density polyethylene grafted maleic anhydride, and linear low-density polyethylene grafted maleic anhydride, (HDPE-g-MA, LLDPE-g-MA) were used as compatibilizers to enhance the dispersibility of nanoclay in HDPE. Dispersion of organoclay in the nanocomposites was characterized by using X-ray diffraction (XRD), transmission electron microscopy (TEM), and rheological mechanical spectroscopy (RMS). Effects of clay content and degree of clay dispersion on the rheological and tensile properties were also investigated. Furthermore, the effect of order of mixing on the dispersion and distribution of the clay layers was studied. The obtained results showed that organoclay in the nanocomposites were dispersed homogeneously and exfoliated better when HDPE-g-MA and the direct mixing route were used. Although in the master batching method clay intercalated better, clay layers chiefly remain in compatibilizer rich areas. On the other hand, direct mixing was observed to lead to clay particles being dispersed in the HDPE matrix or at the interface of the matrix and compatibilizer and, consequently, better improvement in the tensile modulus was achieved. It was determined that the compatibilizer with the higher miscibility with the matrix was the key factor for achieving better exfoliation of clay sheets.     

Three different low-temperature plasma-based methods for hydrophilicity improvement of polyethylene films at atmospheric pressure

Three different low-temperature plasma-based methods were used to improve the surface hydrophilicity of polyethy- lene （PE） films, and all the modification processes were carried out by employing an atmospheric pressure plasma jet （APPJ） system. （a） PE films were directly modified by APPJ using a gas mixture of He and 02. （b） Acrylic acid （AA） was introduced into the system and a polymer acrylic acid （PAA） coating was deposited onto the PE films. （c） AA was grafted onto the PE surface activated by plasma pre-treatment. It was found that the hydrophilicity of the PE films was significantly improved for all the three methods. However, the samples modified by Process （a） showed hydrophobicity recovery after a storage time of 20 days while no significant change was found in samples modified by Process （b） and Process （c）. The Fourier transform infrared spectroscopy （FTIR） results indicated that the most intensive C=O peak was detected on the PE surface modified by Process （c）. According to the X-ray photoelectron spectroscopy （XPS） analysis, the ratios of oxygen-containing polar groups for samples modified by Process （b） and Process （c） were higher than that modified by Process （a）.     

Jute fiber-reinforced chemically functionalized high density polyethylene (JF/CF-HDPE) composites with in situ fiber/matrix interfacial adhesion by Palsule Process

Jute fiber-reinforced chemically functionalized polyethylene high density (JF/CF-HDPE) composites have been processed, by Palsule process without using any compatibilizer and without any fiber modification, by using chemically functionalized maleic anhydride grafted polyethylene (MAPE) as matrix, in place of polyethylene. Fiber/matrix interfacial adhesion generated in situ, due to interactions between jute fiber and the maleic anhydride of the CF-HDPE matrix, has been established by Fourier transform infrared spectroscopy and scanning electron microscope micrographs. Mechanical properties of the JF/CF-HDPE composites developed with in situ fiber/matrix interfacial adhesion in this study have been found to be higher than those of the CF-HDPE matrix and increase with increasing amounts of jute fibers in the JF/CF-HDPE composites, and are better than properties of literature reported and laboratory processed jute fiber/polyethylene composites with and without MAPE compatibilizer. Measured tensile modulus of JF/CF-HDPE composites compares well with values predicted by rule of mixtures, inverse rule of mixture, Hrisch Model, Halpin-Tsai equations, Nielsen equations, and with Palsule equation. The feasibility of developing natural fiber/maleic anhydride grafted polyolefin composites by Palsule process without using any compatibilizer and without any fiber treatment is demonstrated.     

The application with tetramethyl pyrazine for antithrombogenicity improvement on silk fibroin surface

Chuanxiongqin (tetramethyl pyrazine, TMPZ) is an active ingredient of the Chinese herb and was used to improve the anticoagulant activity of silk fibroin (SF). The side methyl of TMPZ was oxidized, and then linked to polyacrylic acid (PAA) via an ester bond. The prepared conjugate was further mixed with SF solutions at different ratios to make blend films. The resulting products were characterized by FTIR, UV spectrometer and X-ray photoelectron spectroscopy (XPS). The in vitro antithrombogenicity were evaluated by the activated partial thromboplastin time (APTT) and the prothrombin time (PT). It was shown that blend films had longer coagulation time than the pure SF film.     

Surface modification of calcium carbonate: radical graft polymerization of vinyl monomers onto calcium carbonate surface initiated by azo groups introduced onto the surface

—The preparation of calcium carbonate modified by 12-hydroxystearate groups and the grafting of polymers onto the surface by the polymerization of vinyl monomers initiated by azo groups introduced onto the surface were investigated. The preparation of calcium carbonate modified by 12-hydroxystearate was achieved by the reaction of calcium chloride with sodium carbonate containing a small amount of sodium 12-hydroxystearate. The introduction of azo groups onto calcium carbonate was successfully achieved by the direct condensation of the carboxyl group of 4,4'-azobis(4-cyanopentanoic acid) with 12-hydroxystearate groups on the modified calcium carbonate using N,N'-dicyclohexylcarbodiimide as a condensing agent. It was found that the radical polymerization of vinyl monomers, such as methyl methacrylate (MMA), styrene, and N-vinylcarbazole (NVC), was initiated by azo groups introduced onto the surface, and the corresponding polymers were grafted onto the surface based on the propagation of polymer from the surface: the percentage of grafting of polyMMA, polystyrene, and polyNVC reached 5.7, 9.5 and 3.5%, respectively, at 70°C. The percentage of grafting was found to decrease with decreasing monomer concentration. The wettability of calcium carbonate surface was found to turn from hydrophilic to hydrophobic by the grafting of polymers.     

功能化石墨烯改性聚乙烯热力学特性的分子动力学模拟

聚乙烯绝缘材料在我国高压电缆中有着广泛的应用,为了提高其耐热稳定性和力学性能,利用石墨烯对聚乙烯进行掺杂改性,并基于分子动力学模拟的研究方法分别建立了低密度聚乙烯（LDPE）、石墨烯和3种官能团接枝石墨烯掺杂聚乙烯的复合模型。研究表明,相比石墨烯直接掺杂聚乙烯,羧基（-COOH）、氨基(-NH2)和羟基(-OH)接枝石墨烯能够更加有效地提高聚乙烯的玻璃化温度（分别提高了16k、7k、5k）、减弱聚乙烯分子链的移动和降低聚乙烯的热膨胀系数、均方位移(MSD),从而使得聚乙烯复合体系的热学性能得到了有效增强;此外发现石墨烯的掺杂能够提高复合模型的力学模量,其中官能团接枝石墨烯改进效果更明显,室温下弹性模量和剪切模量的提升幅度由不接枝的33.98%、36.18%,提升到了44%和42.89%（羧基功能化体系）。研究结果可为聚乙烯绝缘材料的热老化抑制和力学性能的改善提供有益的参考。     

Impact of γ-rays on constructional,optical and thermal behavior of alkaline and non alkaline low density polyethylene

ABSTRACT

In this study, we investigated the graft copolymerization of methyl methacrylate (MMA) onto low-density polyethylene (LDPE) in the presence of aniline as an inhibitor by gamma radiation. An alkaline treatment was carried out for the prepared graft copolymer. The structural properties of the prepared samples were examined via X-ray diffraction (XRD) and scanning electron microscopy (SEM). The XRD peaks were slightly shifted, indicating an interaction between MMA and the polyethylene matrix. The morphology of the samples confirmed the homogenous grafted phase scattered onto the LDPE surface. Analysis of the absorption spectra indicated an allowed indirect transition mechanism. The Urbach energy (E_U) results showed that the value of the E_U for grafted LDPE was found to be higher than that of pure LDPE—up to 15?kGy irradiation dose, although this value decreases upon grafting. However, the value of the E_U for alkaline-treated grafted films decreases systematically by increasing the degree of grafting. The thermogravimetric analysis (TGA) of the sample indicated that the thermal stability of LDPE samples is significantly changed by grafting MMA onto it. Horowitz and Metzger's models were utilized to measure the activation energy of the thermal decomposition of all samples.     

A 1H NMR Study of Palladium(II) Coordination Compounds with 2-Aminooxypropanoic Acid and Its Methyl Ester

The ¹H NMR spectra of 2-aminooxypropanoic acid, its methyl ester and their hydrochlorides have been inspected. The interaction of these ligands with palladium(II) has been investigated in deuterium oxide and in dimethyl sulfoxide. The metal has been found to form a chelate with the acid, whereas its esters coordinated to the metal through the nitrogen atom of the aminooxy group only. In dimethyl sulfoxide, also the methyl esters and hydrochlorides of 2-aminooxybutanoic, 2-aminooxy-3-methylpentanoic,as well as the ester of 2-aminooxyhexanoic and the hydrochoride of the ester of 2-aminooxy-3-phenylpropanoic acid have been studied.     

Determination of the aggregation number of hydrophobic domains in a microphase-separated gel of hydrophobically modified polyacrylic acid

Hydrophobic association in a microphase-separated hydrogel of hydrophobically modified polyacrylic acid is studied by methods of small-angle neutron scattering and fluorescent spectroscopy with the use of pyrene as a probe substance. A fluorescence quenching technique is developed for determining the aggregation numbers of hydrophobic domains in weakly swollen polymeric gels. It is shown that the introduction of charged units into the gel leads to a decrease in the domains’ aggregation number because of the electrostatic repulsion of similarly charged units on their surface.     

Preparation and Properties of Chlorinated Polyethylene-Chlorinating/Grafting-Poly (Acrylic acid) and its Sodium-Salt Ionomer

Acrylic acid (AA) was grafted onto high-density polyethylene (HDPE) by in-situ chlorination graft copolymerization (ISCGC), yielding a graft copolymer composed of chlorinated polyethylene (CPE) as backbone and poly (acrylic acid) (PAA) as branch chains. The reaction process and the preparation of its carboxylated ionomers were studied. The structure of the graft copolymer and the ionomer were characterized by FTIR, gel permeation chromatography (GPC), and degree of grafting (GD). The influence of factors related to the main and side reactions, including the monomer concentration, chlorine contents of the product, and reaction temperature were investigated. Additionally, the effects of these factors on the reaction are described. The aim of the research was to investigate how chlorinated polyethylene grafted with poly (acrylic acid) (CPE-cg-PAA) and its sodium-salt ionomer could be prepared and their relative effect on thermal and mechanical properties.     

Organosilane grafted acid-activated beidellite clay for the removal of non-ionic alachlor and anionic imazaquin

Clay adsorbents were prepared via two-step method to remove nonionic alachlor and anionic imazaquin herbicides from water. Firstly, layered beidellite clay, a member of smectite family, was treated with acid in hydrothermal process; secondly, common silane coupling agents, 3-chloro-propyl trimethoxysilane or triethoxy silane, were grafted on the acid treated samples to prepare adsorbent materials. The organically modified clay samples were characterized by powder X-ray diffraction, N₂ gas adsorption, and FTIR spectroscopy. It was found that the selective modification of clay samples displayed higher adsorption capacity for herbicides compared with acid activated clay. And the amount of adsorption is increased with increasing the grafting amount of silane groups. Clay grafted with 3-chloro-propyl trimethoxysilane is an excellent adsorbent for both alachlor and imazaquin but triethoxy (octyl) silane grafted clay is more efficient only for alachlor removal.     

XPS studies of metal/polymer interfaces — Thin films of Al on polyacrylic acid and polyethylene

A reactivity experimental study of Al with CH₂ and COOH functionalities in polymers is performed using polyacrylic acid (PAA) and low density polyethylene (LDPE). The Al metal is deposited on the polymer surfaces using in-situ sputter deposition. Using X-ray photoelectron spectroscopy (XPS), an Al oxide-carbide complex is identified at the PAA/Al interface while an Al carbide-like species is observed at the LDPE/Al interface. These conclusions are based on carefully referenced binding energy measurements of the C(1s), O(1s), and Al(2p) core electron levels. Near surface XPS studies involving solvent cast PAA films indicate that they are CH₂ rich, suggesting that a larger than statistical number of carboxylic acid groups are pointing away from the surface towards the bulk. PAA powder, however, is found to have near stoichiometric composition at the surface. The conclusions regarding Al/polymer reactivity agree well with recent literature for other metal/polymer interfaces.