Degradation of 17 alpha-ethinylestradiol in aqueous solution by ozonation

This study investigates the ozonation of 17 alpha-ethinylestradiol (EE2) in aqueous solution. The affecting factors on the degradation of EE2 were studied and described in details, such as initial EE2 concentration, initial pH value and ozone concentration. In addition, some parameters such as pH. electrical conductivity, mineralization efficiency and degradation products were monitored during the process. The mineralization efficiency of EE2 could reach 53.9%. During the ozonation process the rapid decrease of pH and the sharp increase of electrical conductivity indicated the fort-nation of acidic by-products, small fragments and ions which were confirmed by high performance liquid chromatography (HPLC) and gas chromatography-mass spectrometry (GUMS) analysis. Results showed that there were intermediate products of smaller molecule with higher polarity produced during the course of EE2 degradation. Then a possible reaction pathway for EE2 degradation involving all intermediates detected is proposed. During the ozonation process EE2 was first oxidized into hydroxyl-semiquinone isomers which were subsequently degraded into low molecular weight compounds such as oxalic acid, malonate, glutarate, and so on. Furthermore. these organic acids are easily oxidized by ozone into carbon dioxide (CO2). This work shows that ozonation process is promising for the removal of EE2. The results can provide some useful information for the potential treatment of EE2 by ozonation in aqueous solution. (c) 2005 Elsevier B.V. All rights reserved.

Molecular basis of transferrin polymorphism in goldfish (Carassius auratus)

Transferrin (TF) polymorphism was investigated in a color variety of goldfish (Carassius auratus), and its molecular basis analyzed. Three TF variants (A(1), A(2) and B-1) were identified from an inbred strain of the goldfish, of which A(1) and B-1 displayed a large electrophoretic difference on both native and SDS-PAGE gels. The TF cDNAs corresponding to variants A(1) and B-1 were cloned and sequenced from A(1)A(1), A(1)B(1) and B1B1 individuals, and their deduced amino acid sequences were analyzed. Substantial amino acid variation occurred between variants A(1) and B-1, with significant differences in peptide length, theoretical molecular weight (Mw) and isoelectric point (pI). No potential glycosylation sites were observed in the two amino acid sequences, which excluded the possibility that carbohydrate difference might cause electrophoretic variation among the TF variants. Further analysis suggested that the distinct electrophoretic mobility of the two variants A(1) and B-1 by SDS-PAGE resulted from their Mw difference, while the difference by the native PAGE could be explained by their pI variation. Furthermore, genomic DNA fragments containing the transferrin alleles were amplified and subjected to RFLP analysis in A(1)A(1), A(1)B(1) and B1B1 individuals. The data revealed characteristic banding patterns for each TF genotype, and demonstrated that the TF alleles A(1) and B-1 could be used as a co-dominant marker system. The initial work relating to the goldfish TF variants will benefit the understanding of the evolutionary and functional significance of TF polymorphism in fish.

Quantitative structure-property relationship study on reductive dehalogenation of selected halogenated aliphatic hydrocarbons in sediment slurries

In this study, by the use of partial least squares (PLS) method and 26 quantum chemical descriptors computed by PM3 Hamiltonian, a quantitative structure-property relationship (QSPR) model was developed for reductive dehalogenation rate constants of 13 halogenated aliphatic compounds in sediment slurry under anaerobic conditions. The model can be used to explain the dehalogenation mechanism. Halogenated aliphatic compounds with great energy of the lowest unoccupied molecular orbital (E-lumo), total energy (TE), electronic energy (EE), the smallest bond order of the carbon-halogen bonds (BO) and the most positive net atomic charges on an atom of the molecule (q(+)) values tend to be reductively dehalogenated slow, whereas halogenated aliphatic compounds with high values of molecular weight (Mw), average molecular polarizability (a) and core-core repulsion energy (CCR) values tend to be reductively dehalogenated fastest. (C) 2001 Published by Elsevier Science Ltd.

来自易变山羊草抗禾谷孢囊线虫基因的克隆与序列分析

禾谷孢囊线虫（Heterodera avenae）是严重危害禾谷类作物的病原线虫之一,它广泛分布于澳大利亚、欧洲、北美、印度和中国等世界主要小麦产区,使作物严重减产,造成巨大的经济损失。目前最有效的防治措施之一是将外源抗性基因导入栽培小麦(Triticum aestivum L.)，培育抗禾谷孢囊线虫的新品种。但迄今为止抗禾谷孢囊线虫基因克隆研究的相关报道却很少。 本实验根据此前从抗禾谷孢囊线虫材料E-10扩增得到的与来自节节麦（Aegilops tauschii）的抗禾谷孢囊线虫基因Cre3高度同源的序列Rccn4,设计出三条嵌套引物,采用SON-PCR(single oligonucleotide nested PCR)方法,从E-10基因组DNA中得到一个长为1264 bp的扩增产物(命名为Rccn-L),测序比对结果显示,这一序列将Rccn4的3’端延伸了1209 bp,与抗禾谷孢囊线虫Cre3基因核苷酸同源性为86﹪，核苷酸编码区长1026 bp，含一个不完整的开放阅读框,一个终止密码子，没有起始密码子和内含子结构,编码一个342个氨基酸残基的蛋白质。该蛋白质等电点为5.19，分子量为38112.6Da。从序列的第113位开始到第332位是NBS-LRR类抗病性基因LRR区,呈现XXLXXLXXL重复。LRR编码区内亮氨酸残基的含量达17﹪，与抗禾谷孢囊线虫Cre3基因LRR编码区的核苷酸和氨基酸同源性分别为89﹪和78﹪。本实验首次将SON-PCR成功地运用于植物基因克隆，为植物基因克隆提供了又一有效方法。 此外,还根据Cre3基因及其他的NBS-LRR类植物抗性基因的NBS和LRR区保守序列设计了两对特异性引物，从禾谷孢囊线虫抗性材料易变山羊草基因组DNA中扩增到两个相应的目标条带。测序分析结果表明，它们的长度分别为532bp和1175bp，构成了一个有32bp的共同序列的NBS-LRR编码区。其序列总长为1675bp（命名为RCCN），含有一个不完整的开放阅读框，没有起始密码子、终止密码子和内含子结构。其中编码序列为1673bp，可编码一个557个氨基酸的蛋白质，等电点（pI）为5.39，分子量为63537.5Da。与Cre3的核苷酸和氨基酸同源性分别为87.8﹪和77﹪。RCCN氨基酸序列中含有已知抗病基因NBS区域的几个保守模体：kinase2区的ILDD、kinase3的（ⅰ）ESKILVTTRSK，（ⅱ）KGSPLAARTVGG，（ⅲ）RRCFAYCS及EGF。RCCN NBS区与Cre3 NBS区的核苷酸和氨基酸的同源性分别为96.4﹪和94﹪。从氨基酸序列的274位到548位为LRR保守区，呈现不规则的aXXLXXLXXL（其中a代表I，V，L，F或M）重复，其中亮氨酸的含量为15.6﹪。该区域与Cre3的LRR区的核苷酸和氨基酸同源性分别为80.8﹪和74﹪。推测该序列可能为一个抗禾谷孢囊线虫的新基因。 本文对抗禾谷孢囊线虫基因的克隆研究，为进一步克隆基因全序列，探索其结构与功能，和研究该基因表达与调控提供了关键信息。同时也为通过基因工程途径将抗性基因向优良小麦品种高效、定向转移，最终培育出小麦抗禾谷孢囊线虫新品种奠定了基础。 Cereal cyst nematode (CCN) is a damaging pathogen of broad acre cereal crops in Australia, Europe, North America, India and China. It affects wheat, barley, oat and triticale and causes yield loss of up to 80%. At present, Transferring resistance genes against CCN into wheat cultivars and breeding varieties are considered one of the most effective methods for controlling the CCN. However, there are very limited reports concerning the cloning studies of resistance genes against the cereal cyst nematode. According to the sequence of Rccn4 which had high similarity to the nucleotide binding site (NBS) coding region of cereal cyst nematode resistance gene, Cre3， We designed three 3’ nested primers. Using single oligonucleotide nested PCR (SON-PCR) we successfully amplified one band, Rccn-L, of 1264bp from E-10 which is the wheat-Ae.variabilis translocation line containing the cereal cyst nematode resistance gene of Ae.variabilis. We found that this band of interesting is the 3’ flanking sequence of 1209bp in size of Rccn4. The coding region was 1026bp, which contained an incomplete open reading frame and a terminator codon, without initiation codon and intron, encoding a peptide of 342 amino acid residues, and shared 86﹪nucleotide sequence identity with Cre3. This peptide had a conserved LRR domain, containing the imperfect repeats,XXLXXLXXL, which contains 17﹪ leucine residues and shares, respectively, 89﹪ nucleotide sequence and 78﹪ amino acid sequence identity with the LRR sequence of Cre3 locus. This research firstly used SON-PCR in the research of plant genome successfully, which indicated that SON-PCR is another method of cloning plant gene. At the same time, According to the conversed motif of NBS and LRR region of cereal cyst nematode resistance gene Cre3 from wild wheat (Triticum tauschlii L.) and the known NBS-LRR group resistance genes, we designed two pairs of specific primers for NBS and LRR region respectively. One band of approximately 530bp was amplified using the specific primers for conversed NBS region and one band of approximately 1200bp was amplified with the specific primers for conversed LRR region. After sequencing, we found that these two sequences included 32bp common nucleotide sequence and have 1675 bp in total, which was registered as RCCN in the Genbank. RCCN contained a NBS-LRR domain and an incomplete open reading frame without initiation codon, terminator codon and inxon. Its exon encodes a peptide of 557 amino acid residues. The molecular weight of the protein from the amino acid was 63.537 KDa. The amino acid sequence of RCCN contained conserved motif: ILDD, ESKILVTTRSK, KGSPLAARTVGG, RRCFAYCS, EGF，LRR. RCCN shares 87.8﹪ nucleotide sequence and 77﹪ amino acid sequence identity with cereal cyst nematode gene Cre3. It might be a novel cereal cyst nematode resistance gene. These research results of cloning the resistance genes against cereal cyst nematode bring a great promise for transferring resistance genes into wheat cultivars and breeding new wheat varieties against cereal cyst nematode by gene engineering. And these results also lay the hard foundation for the expressing researches of these genes.

青藏高原青稞淀粉资源的评价

青稞（Hordeum vulgare L.var．nudum Hook．f.），即裸大麦，是兼食用、饲用和酿造于一体的作物，有着重要的利用价值。淀粉是青稞籽粒中含量最多、最重要的碳水化合物，淀粉含量、直支淀粉比将会直接影响淀粉的功能特性，进而影响淀粉的应用领域。我国青藏高原青稞的栽培和食用历史悠久，特色青稞资源极其丰富。目前关于青藏高原青稞淀粉特性的报道还不多见，筛选和培育特色淀粉青稞利于拓展青稞的应用领域, 从而提高其经济价值。 本研究以114份青藏高原青稞品种(系)为实验材料，通过SDS-PAGE对材料的胚乳淀粉颗粒结合蛋白（SGAPs）进行分离，确定各蛋白的分子量大小、组合类型和多态性等。然后按照国标法测试材料的籽粒总淀粉含量和直链淀粉含量，通过微型糊化粘度仪分析相应的淀粉糊化特性，最后使用显微镜观察比较了青稞的淀粉颗粒形态特征。主要结果如下： 1、114种青稞中共分离出20种不同的SGAP条带，条带分子量为35.00～112.39 KDa，分布频率为12.28～97.37%。材料含有的SGAPs条带数从10到14不等，超过一半的材料含11种SGAP条带。20种条带形成16种组合类型，其中西藏地区青稞包含所有16个组合类型，四川地区青稞包含其中12个组合类型。青藏高原青稞籽粒淀粉颗粒结合蛋白的差异很大，遗传多样性丰富。 2、114份青稞的总淀粉含量、直链淀粉含量、直支淀粉比、峰值粘度、糊化温度和峰值温度的变幅分别为51.26～66.70%、14.64～29.74%、0.17～0.42、194～1135BU、58.8～65.2℃和81.4～92.4℃，相应的平均值分别为59.82%、23.60%、0.31、722.30BU、62.1℃和88.8℃。群体在总淀粉含量、直链淀粉含量、直支淀粉比、峰值粘度、糊化温度和峰值温度上的分布具有明显的正态性；所有胚乳淀粉体的淀粉粒都呈复粒结构。对西藏和四川的材料进行了分组比较， 两地区的青稞在直链淀粉含量和直支淀粉比上的差异达到显著水平。 3、筛选出18份具有特殊淀粉特性的青稞品种，其中5份材料的总淀粉含量超过65%，包括NB63-1、NB67、甘孜白六棱、98221-1和NB63；3份材料的直链淀粉含量大于29%，包括藏青85、藏青3号和喜马拉6号；8份材料的直支淀粉比小于0.25，包括99033-6、春青稞、阿坝330、Jan-03、米麦114、396、NB63-1和92013；7份材料的糊化温度低于60℃，同时材料的峰值粘度大于1000BU,并且峰值温度低于90℃，包括足捉春、Jan-03、阿坝330、米麦114、春青稞、20003和阿青5号。 4、各淀粉特性间存在高度相关性。直链淀粉含量和直支淀粉比与糊化温度成极显著正相关，与峰值粘度成极显著负相关，与A型淀粉粒数量和大小呈负相关。不同SGAPs组合的品种之间，淀粉含量和淀粉糊化特性间差异均达显著水平。SGAP2、SGAP5、SGAP6和SGAP7可能对籽粒直链淀粉含量、直支淀粉比和糊化温度有正向效应；SGAP3、SGAP9∼SGAP20可能对峰值粘度有正向效应。 本研究对青藏高原青稞淀粉资源进行了较为全面的评价，对该区青稞淀粉特性有了系统的认识。研究筛选出的特殊青稞品种可作为青稞育种和青稞淀粉工业应用的潜在资源，淀粉特性差异巨大的众多青稞品种也为拓宽青稞应用领域提供了丰富的资源保障。本研究对部分SGAPs在性质上的鉴定和功能上的初步推断为青稞材料的筛选提供了指导，也为品质育种提供了理论参考。 Hulless barley (naked barley, Hordeum vulgare L.) is a short- season, early maturing crop with a wide range of adaptation. It has been attracting more and more attention due to its superior nutrition and extensive industrial applications. Starch is the main ingredient in hulless barley seeds which makes up 65 percent of hulless barley’s dry weight. The ratio of the amylose/amylopectin and the size, shape, distribution of starch granules can affect the physico-chemical and functional properties of starch, which may turn affect its utilizations. The Qinghai-Tibet Plateau, which is located in southwestern China, is a typical area of vertical agricultural ecosystem and one of the barley origin centers with abundant hulless barley resources. There are little reports about hulless barley in Qinghai-Tibet Plateau at present. To screen and cultivate some characteristic hulless barley can improve its value. An improved SDS-PAGE was used to identify SGAPs combination of 114 hulless barley varieties. Starch content (total starch and amylose starch) was determined according to the standard methods GB5006-85 and GB/T 15683 using PerkinElmer M341 Precision Automatic Polarimeter and UV spectrophotometer 755B respectively. The pasting properties were measured by BRABENDER Micrio Visco-Amylo- Graph 803201. The morphology of starch granules were observed and compared with Axioplan 2 Imaging light microscopy. The following were the results obtained: 1. There were 20 major SGAPs presented in 114 varieties, with the molecular weight ranged from 35.00 to 112.39 KDa, and the frequencies ranged from 12.28% to 97.37%. The number of SGAP bands in each accession varied from 10 to 14, more than half of the population had 11 bands. There were 16 distinct SGAP patterns in the 114 varieties, the Tibet hulless barley had all of the 16 types and the Sichuan hulless barley had 12 types. The results indicated the Qinghai-Tibet Plateau hulless barley had a polymorphism of the SGAPs. 2. The ranges of the total starch content, amylose content, Am/Ap, peak viscosity, pasting temperature and peak temperature of the 114 hulless barley were 51.26～66.70%,14.64～29.74%,0.17～0.42,194～1135BU,58.8～65.2 and 81.4℃～92.4, with an average of ℃59.82%, 23.60%, 0.31, 722.30BU, 62.1 and 88.8,℃℃ respectively. The distributions of the total starch content, amylose content, Am/Ap, peak viscosity, pasting temperature and peak temperature were visibly normal school. All of the amyloplasts in endosperm of varieties showed bimodal size distributions.The main starch properties of hulless barley from Tibet and Sichuan were separated and compared, the differences on amylose content and Am/Ap were obvious. 3. Eighteen accessions which had special starch properties were screened out. Five accessions with total starch content beyond 65%, including NB63-1, NB67, Ganzibailiuleng, 98221-1 and NB63; three accessions, Zangqing85, Zangqing3 and Ximala6, with the highest amylose content (>29%); five accessions with Am/Ap less than 0.25, including 99033-6, Chun Qingke, A Ba 330, Jan-03, Mi Mai114, 396, NB63-1 and 92013; seven accessions had a pasting temperature under 60, ℃meanwhile their peak viscosity beyond 1000BU and their peak temperature under 90℃，including Zu Cuochun, Jan-03, A Ba 330, Mi Mai 114, Chun Qingke, 20003 and A Qing 5. 4. There were high correlations between starch properties. Amylose content and Am/Ap were positively correlated to pasting temperature, negatively correlated to peak viscosity, negatively correlated to the number and granule size of A-type granule. Different SGAP combinations caused significant diversities in starch content and pasting properties. SGAP2, SGAP5, SGAP6 and SGAP7 may have positive effect on amylose content, Am/Ap and pasting temperature; SGAP3, SGAP9∼SGAP20 may have positive effect on peak viscosity. Our research made a comprehensive evaluation on the hulless barley starch from the Qinghai-Tibet Plateau, we can get a systemic understanding. Some special accessions were screened out can be used on the hulless barley breeding lines and industries utilization.The combination of the SGAPs may become a criterion to evaluate the hulless barley endosperm starch quality. Consequently, the results will be good information for further studies on the hulless barley.

Swelling behaviour of alginate-chitosan microcapsules prepared by external gelation or internal gelation technology

Swelling behaviour is one of the important properties for microcapsules made by hydrogels, which always affects the diffusion and release of drugs when the microcapsules are applied in drug delivery systems. In this paper, alginate-chitosan microcapsules were prepared by different technologies called external or internal gelation process respectively. With the volume swelling degree (S-w) as an index, the effect of properties of chitosan on the swelling behaviour of both microcapsules was investigated. It was demonstrated that the microcapsules with low molecular weight and high concentration of chitosan gave rise to low S-w. Considering the need of maintaining drug activity and drug loading, neutral pH and short gelation time were favorable. It was also noticed that S-w of internal gelation microcapsules was lower than that of external gelation microcapsules, which was interpreted by the structure analysis of internal or external gelation Ca-alginate beads with the aid of confocal laser scanning microscope. (C) 2004 Elsevier Ltd. All rights reserved.

Enzymatic reaction of the immobilized enzyme on porous silicon studied by matrix-assisted laser desorption/ionization-time of flight-mass spectrometry

Desorption/ionization on silicon mass spectrometry (DIOS-MS) is a matrix-free technique that allows for the direct desorption/ionization of low-molecular-weight compounds with little or no fragmentation of analytes. This technique has a relatively high tolerance for contaminants commonly found in biological samples. DIOS-MS has been applied to determine the activity of immobilized enzymes on the porous silicon surface. Enzyme activities were also monitored with the addition of a competitive inhibitor in the substrate solution. It is demonstrated that this method can be applied to the screening of enzyme inhibitors. Furthermore, a method for peptide mapping analysis by in situ digestion of proteins on the porous silicon surface modified by trypsin, combined with matrix-assisted laser desorption/ionization-time of flight-MS has been developed.

Highly efficient separation of dsDNA fragments on glass chips by using an ultralow viscosity sieving matrix

A novel protocol has been established to separate dsDNA fragments with high efficiency on glass chips by using an ultralow viscosity sieving matrix with added glucose. Low-molecular-weight hydroxypropylmethylcellulose (HPMC), with a viscosity nearly equivalent to that of water, was used to electrophoretically separate fluorescent inter-calator-labeled double-stranded DNA (dsDNA) fragments on microfluidic glass chips. In comparison with conventional sieving protocols, low-molecular-weight HPMC as sieving matrix could result in reduced running cost and analysis time, in addition to a comparable separation efficiency of dsDNA fragments. In this paper, the addition of glucose was investigated to enhance the separation of DNA in the lowest viscosity polymer evaluated. The effect of staining dye and field strength were also evaluated. At an applied electric field strength of 200 V/cm, satisfactory resolution of the PBR322/HaeIII DNA marker could be achieved within 4 min by using 2% HPMC-5 with 6% glucose added. Coelectrophoresing PCR product along with phiX174/HaeIII DNA sizing marker was also demonstrated by using the ultralow viscosity HPMC-5 solution on a glass chip.

The investigation of exfoliation process of organic modified montmorillonite in thermoplastic polyurethane with different molecular weights

Cloisite 30B (30B) was melt-mixed with two kinds of thermoplastic polyurethane (TPU) with different molecular weights to discern the roles of molecular diffusion and shear in the exfoliation process. The higher level of exfoliation was achieved in TPU matrix with higher molecular weight due to the appropriate viscosity. In order to have an insight into the mechanism of exfoliation, the degree of dispersion and exfoliation of 30B was characterized by wide angle X-ray diffraction and transmission electron microscopy. The layers of 30B were exfoliated via a slippage process, which was also observed in polyamide 12 nanocomposites recently.

Styrene polymerization catalyzed by metal porphyrin complex/MAO for in situ synthesizing polystyrene containing air stable pi cation radicals

A novel catalyst system based on nickel(II) tetraphenylporphyrin (Ni(II)TPP) and methylaluminoxane for styrene polymerization was developed. This catalyst system has a high thermal stability and show fairly good activity. The obtained polystyrene (PS) was isotactic-rich atactic polymer by C-13 NMR analysis, and its molecular weight distribution was rather narrow (M-w/M-n approximate to 1.6, by GPC analysis). ESR revealed that Ni(II)TPP pi cation radicals were formed in the polymerization and could remain in the resulting PS stably. The mechanism of the polymerization was discussed and a special coordination mechanism was proposed. The PS product containing Ni(II)TPP pi cation radicals can be used as a potential functional material.

Morphology and crystalline transition of poly (3-butylthiophene) associated with its polymorphic modifications

Poly (3-butylthiophene) (P3BT) is a much less studied conjugated polymer despite its high crystallizability and thus excellent electrical property. In this work, morphology of P3BT at different crystalline polymorphs and solvent/thermal induced phase transition between form I and U modifications have been intensively investigated by using optical microscopy, electron microscopy, differential scanning calorimetry, and X-ray diffraction. It is shown that a direct deposition from carbon disulfide (CS2) at fast evaporation results in P3BT crystals in form I modification, giving typical whiskerlike morphology. In contrast, low evaporation rate from CS, leads to formation of form II crystals with spherulitic morphology, which is so far scarcely observed in polythiophene.

Metal dependent control of cis-/trans-1,4 regioselectivity in 1,3-butadiene polymerization catalyzed by transition metal complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine

Fe(III), Cr(III), Fe(II), Co(II) and Ni(II) chloride complexes supported by 2,6-bis[1-(iminophenyl)ethyl]pyridine have been synthesized and characterized along with single crystal X-ray diffraction. These complexes, in combination with MAO, have been examined in butadiene polymerization. The catalytic activity and regioselectivity are strongly controlled by metal center and cocatalyst (MAO/Co ratio dependent in the case of Co(II) complex). The activity decreases in the order of Fe(III) > Co(II) > Cr(III) approximate to Ni (II) complexes, in consistent with the space around the metal center. Polybutadiene with different microstructure content, from high trans-1,4 units (88-95% for iron(III) and Cr(III)), medium trans-1,4 and cis-1,4 units (55% and 35%, respectively, for iron(II)) to high cis-1,4 units 79% for Co(II) and 97% for Ni(II) call be easily achieved by varying of the metal center.

Preparation of Polyacrylamide Aqueous Dispersions Using Poly(sodium acrylic acid) as Stabilizer

High-solids, low-viscosity, stable polyacrylamide (PAM) aqueous dispersions were prepared by dispersion polymerization of acrylamide in aqueous solution of ammonium sulfate (AS) using Poly (sodium acrylic acid) (PAANa) as the stabilizer, ammonium persulfate (APS) or 2,2'-Azobis (N,N'-dimethyleneisobutyramidine) dihydrochloride (VA-044) as the initiator. The molecular weight of the formed PAM, ranged from 710, 000 g/mol to 4,330,000 g/mol, was controlled by the addition of sodium formate as a conventional chain-transfer agent. The progress of a typical AM dispersion polymerization was monitored with aqueous size exclusion chromatography. The influences, of the AS concentration, the poly(sodium acrylic acid) concentration, the initiator type and concentration, the chain-transfer agent concentration and temperature Oil the monomer conversion, the dispersion viscosity, the PAM molecular weight and distribution, the particle size and morphology were systematically investigated.

Ethylene Polymerization by the New Chromium Catalysts Based on Amino-Pyrrolide Ligands

A series of amino-pyrrolide ligands (1-4a) and their derivatives aminothiophene ligand (5a), amino-indole ligand (6a) were prepared. Chromium catalysts, which were generated in situ by mixing the ligands with CrCl3(thf)(3) in toluene, were tested for ethylene polymerization. The preliminary screening results revealed that the tridentate amino-pyrrolide ligands containing soft pendant donor, 3a, 4a/CrCl3(thf)(3) systems displayed high catalytic activities towards ethylene polymerization in the presence of modified methyaluminoxane. The electronic and steric factors attached to the ligand backbone significantly affected both the catalyst activity and the polymer molecular weight. Complex 4b was obtained by the reaction of CrCl3(thf)(3) with one equivalent of the lithium salts of 4a, which was the most efficient ligand among the tested ones. The effect of polymerization parameters such as cocatalyst concentration, ethylene pressure, reaction temperature, and time on polymerization behavior were investigated in detail. The resulting polymer obtained by 4b display wax-like and possess linear structure, low molecular weight, and unimodal distribution.

SYNTHESIS AND CHARACTERIZATION OF HYPERBRANCHED VINYL POLYMERS FROM RAFT POLYMERIZATION OF AN ASYMMETRIC DIVINYL MONOMER

Hyperbranched vinyl polymers were prepared by reversible addition-fragmentation chain transfer ( RAFT) polymerization of a styrenic asymmetric divinyl monomer. This was achieved by using cumyl dithiobenzoate or S-dodecyl-S'-(alpha,alpha'-dimethyl-alpha ''-acetic acid) trithiocarbonate as the chain transfer agent, 1,1'-azobis(cyclohexanecarbonitrile) or thermal initiation as a source of radicals. Cross-linking was inhibited by a rapid RAFT-based equilibrium between active propagation chains and dormant species, and thus a hyperbranched polymer with a monomer conversion as high as 80% was obtained. The hyperbranched structure and properties of the resultant polymers were characterized by a combination of H-1-NMR spectroscopy and a triple detection size exclusion chromatography (TRI-SEC). The hyperbranched vinyl polymer has a broad molecular weight distributions and a low Mark-Houwink exponent alpha value compared with the linear counterpart.