STRUCTURE AND PROPERTIES OF SEQUENTIALLY POLYMERIZED PROPYLENE-B-[ETHYLENE-CO-PROPYLENE]-B-PROPYLENE COPOLYMERS

The structure and properties of presumed block copolymers of polypropylene (PP) with ethylene-propylene random copolymers (EPR), i.e., PP-EPR and PP-EPR-PP, have been investigated by viscometry, transmission electron microscopy, dynamic mechanical analysis, differential scanning calorimetry, gel permeation chromatography, wide-angle x-ray diffraction, and other techniques testing various mechanical properties. PP-EPR and PP-EPR-PP were synthesized using delta-TiCl3-Et2AlCl as a catalyst system. The results indicate that the intrinsic viscosity of these polymers increases with each block-building step, whereas the intrinsic viscosity of those prepared by chain transfer reaction (strong chain-transfer reagent hydrogen was introduced between block-building steps during polymerization) hardly changes with the reaction time. Compared with PP / EPR blends, PP-EPR-PP block copolymers have lower PP and polyethylene crystallinity, and lower melting and crystallization temperatures of crystalline EPR. Two relaxation peaks of PP and EPR appear in the dynamic spectra of blends. They merge into a very broad relaxation peak with block sequence products of the same composition, indicating good compatibility between PP and EPR in the presence of block copolymers. Varying the PP and EPR content affects the crystallinity, density, and morphological structure of the products, which in turn affects the tensile strength and elongation at break. Because of their superior mechanical properties, sequential polymerization products containing PP-EPR and PP-EPR-PP block copolymers may have potential as compatibilizing agents for isotactic polypropylene and polyethylene blends or as potential heat-resistant thermoplastic elastomers.

CHARACTERIZATION OF BLENDS OF POLYPROPYLENE WITH A SEMIRIGID LIQUID-CRYSTAL COPOLYESTER

Blends with a liquid-crystal polymers (LCP) as one component show, in general, very interesting properties. Reduction of shear visocity and improvement of mechanical properties are very remarkable. High melting temperatures and high costs of the LCP limit the use of these blends. A new class of thermotropic LCPs with flexible spaces, with relatively low melting temperatures, can overcome the first problem. In this work, rheological and mechanical properties of blends of polypropylene with low contents of this LCP are presented. Torque during extrusion and viscosity decrease with LCP content. Elastic modulus is remarkably increased when the LCP phase is oriented.

CHARACTERIZATION OF GAMMA-IRRADIATED CRYSTALLINE POLYMER .3. THERMAL-BEHAVIOR OF GAMMA-IRRADIATED POLYAMIDE-1010

Thermal behaviour of gamma-irradiated plain PA1010 and PA1010 containing different amounts of difunctional cross-linking agent BMI was investigated. In DSC endo- and exotherm, it was found that during irradiation, the presence of BMI markedly changes the melting and crystallisation characteristics of PA1010. A supposition that the network of BMI-containing specimens is rather loose in structure was proposed to explain the discrepancy in thermal behaviour between these two kinds of specimens. The supposition was further ascertained by the less brittleness in mechanical property of specimens containing BMI. Besides, the complexity of the thermal behaviour of gamma-irradiated PA1010 was discussed and attributed mainly to the increase in sigma-e, the fold surface free energy of chain fold crystals.

CHARACTERIZATION, MORPHOLOGY AND THERMAL-PROPERTIES OF ETHYLENE PROPYLENE BLOCK COPOLYMERS

Characterization, morphology and thermal properties of commercial ethylene-propylene block copolymers have been studied by C-13 nuclear magnetic resonance (n.m.r.) spectroscopy, differential scanning calorimetry (d.s.c.), dynamic mechanical analysis (d.m.a.) and scanning electron microscopy (SEM). The results obtained show that there exists some ethylene-propylene random copolymer in the block copolymers extractable by n-heptane. The possibility of forming PP-b-PE diblock copolymer is questionable on the basis of the effects of residual propene and the chain-transfer reaction in the sequential copolymerization. A difference in the thermal properties between commercial ethylene-propylene block copolymers and PP/PE blends was noticed, which cannot be used to identify PP-b-PE diblock copolymer. The multiphase structure has been confirmed by d.m.a. and SEM, with ethylene-propylene random copolymer and polyethylene forming the domains in the matrix of polypropylene.

COMPATIBILIZING EFFECT OF POLY(ETHYLENE OXIDE)-B-POLYSTYRENE-B-POLY(ETHYLENE OXIDE) IN PHENOLPHTHALEIN POLY(ETHER ETHER KETONE) POLY(2,6-DIMETHYL-1,4-PHENYLENE OXIDE) BLENDS

The morphology and mechanical behaviour of phenolphthalein poly(ether ether ketone) (PEK-C)/poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) blends has been investigated. A poly(ethylene oxide)-b-polystyrene-b-poly(ethylene oxide) (PEO-PS-PEO) triblock copolymer was used as compatibilizer. It was found that PEO-PS-PEO has a compatibilizing effect on the PEK-C/PPO blends. The addition of PEO-PS-PEO to the blends greatly improves phase dispersion and interfacial interfacial adhesion and also enhances the ultimate tensile strength and Young's modulus at compositions ranging from 30 to 70% PEK-C. However, all the values of the ultimate tensile strength within the whole composition range are lower than those expected by simple additivity, probably owing to the poor mechanical properties of PEO-PS-PEO copolymer.

Assembly of the protoplasm of Codium fragile (Bryopsidales, Chlorophyta) into new protoplasts

The cell organelles of the coenocytic alga Codium fragile (Sur.) Hariot aggregated rapidly and protoplasts were formed when its protoplasm was extruded out in seawater. Continuous observation showed that there were long and gelatinous threads connecting the cell organelles. The threads contracted, and thus the cell organelles aggregated into protoplasmic masses. The enzyme digestion experiments and Coomassie Brilliant Blue and Anthrone stainings showed that the long and gelatinous threads involved in the formation of the protoplasts might include protein and saccharides as structure components. Nile Red staining indicated that the protoplast primary envelope was non-lipid at first, and then lipid materials integrated into its surface gradually. The fluorescent brightener staining indicated that the cell wall did not regenerate in the newly formed protoplasts and they all disintegrated within 72 h after formation. Transmission electron microscopy of the cell wall of wild C. fragile showed electron-dense material embedded in the whole cell wall at regular intervals. The experiments indicated that C. fragile would be a suitable model alga for studying the formation of protoplasts.

羟基自由基降解琼胶及其产物的活性研究

琼胶是一种从石花菜等红藻中提取的，目前生产工艺和结构等方面研究比较成熟的海藻多糖，广泛应用于医药、仪器等行业。但是，海藻多糖因为具有分子量大，粘度大，溶解度较小的等特点，而使其应用范围受到限制。利用降解的手段对其进行修饰，降低分子量和粘度，改善溶解性，可以拓展其应用范围。并且根据文献报道，琼 胶寡糖具有一些特殊的生物活性，如抗氧化性，抗炎症等。因此，对琼胶降解的研究具有生要意义。本研究中，为了选择一种合适的降解方法，进行了几种水解方法的尝试，其中包括在不同湿度和酸度下盐酸水解，过氧化氢和醋酸催化水解，Fenton体系羟基自由基降解。对于酸水解和Fenton体系氧化还原降解方法，通过粘度法对反应的速度进行了比较，表明氧化还原降解反应中琼胶的粘度降低比较快，并且具有代表性和新意，确定为本实验的降解琼胶的方法并对氧化还原降解所得的产物进行了活性实验。通过模仿自然界普遍存在的氧化还原降解反应，利用Vc诱导的Fenton体系产生的羟基自由基氧化还原降解琼胶得到低分子量的琼胶。降解产物经过高速离心、60％乙醇沉淀，除去分子量比较大的降解产物和磷酸盐，得到可溶于60％乙醇的分子量估计小于3000的降争产物，其产率为85％。利用经Sephadex-G25凝胶色谱分离所香的不同分子量的级分进行分子量和α－葡萄糖苷酶抑制活性关系的实验。降解产物对α－葡萄糖苷酶的抑制率和各级分的浓度呈线性正相关，并且各级分的IC_(50)则随着分子量的降低而降低。另外，对所得的降解产物混合物进行了红外吸收光谱、质子去偶核磁共震碳谱和负离子基质辅助激光诱导－飞行时间质谱结构分析。结果表明，氧化还原降解反应的专一性差，在得到寡糖的同时，在光谱图中出现一些比较复杂的副产物的结构信息。最后，根据MTT法的原理，以有体皮肤成纤维细胞为材料，通过紫外线辐射产生自由基造成氧化损伤，研究降解产物对成纤维细胞的保护作用。当无紫外线辐射时，降解产物对成纤维细胞具有显著的促进生长增殖作用：当经UVa、UBb辐射时则可以显著地表现出对损伤的保护作用，并且这种促进生长和保护作用呈显著的量效关系，表明降解产物具有清除基自由基的作用。但是，因为氧化还原降解以应的机理尚不十分明的以及琼羟胶的特殊结构，使得反应的副产物很难预测，也就使得分离工作难以进行，所以，根据目前所得的信息，尚不能确定是降解产物的什么级分产生的以上两种生物活性。

Zooplankton functional groups on the continental shelf of the yellow sea

Zooplankton plays a vital role in marine ecosystems. Variations in the zooplankton species composition, biomass, and secondary production will change the structure and function of the ecosystem. How to describe this process and make it easier to be modeled in the Yellow Sea ecosystem is the main purpose of this paper. The zooplankton functional groups approach, which is considered a good method of linking the structure of food webs and the energy flow in the ecosystems, is used to describe the main contributors of secondary produciton of the Yellow Sea ecosystem. The zooplankton can be classified into six functional groups: giant crustaceans, large copepods, small copepods, chaetognaths, medusae, and salps. The giant crustaceans, large copepods, and small copepods groups, which are the main food resources for fish, are defined depending on the size spectrum. Medusae and chaetognaths are the two gelatinous carnivorous groups, which compete with fish for food. The salps group, acting as passive filter-feeders, competes with other species feeding on phytoplankton, but their energy could not be efficiently transferred to higher trophic levels. From the viewpoint of biomass, which is the basis of the food web, and feeding activities, the contributions of each functional group to the ecosystem were evaluated; the seasonal variations, geographical distribution patterns, and species composition of each functional group were analyzed. The average zooplankton biomass was 2.1 g dry wt m(-2) in spring, to which the giant crustaceans, large copepods, and small copepods contributed 19, 44, and 26%, respectively. High biomasses of the large copepods and small copepods were distributed at the coastal waters, while the giant crustaceans were mainly located at offshore area. In summer, the mean biomass was 3.1 g dry wt m(-2), which was mostly contributed by the giant crustaceans (73%), and high biomasses of the giant crustaceans, large copepods, and small copepods were all distributed in the central part of the Yellow Sea. During autumn, the mean biomass was 1.8 g dry wt m(-2), which was similarly constituted by the giant crustaceans, large copepods, and small copepods (36, 33, and 23%, respectively), and high biomasses of the giant crustaceans and large copepods occurred in the central part of the Yellow Sea, while the small copepods were mainly located at offshore stations. The giant crustaceans and large copepods dominated the zooplankton biomass (2.9 g dry wt m(-2)) in winter, contributing respectively 57 and 27%, and they, as well as the small copepods, were all mainly located in the central part of the Yellow Sea. The chaetognaths group was mainly located in the northern part of the Yellow Sea during all seasons, but contributed less to the biomass compared with the other groups. The medusae and salps groups were distributed unevenly, with sporadic dynamics, mainly along the coastline and at the northern part of the Yellow Sea. No more than 10 species belonging to the respective functional groups dominated the zooplankton biomass and controlled the dynamics of the zooplankton community. The clear picture of the seasonal and spatial variations of each zooplankton functional group makes the complicated Yellow Sea ecosystem easier to be understood and modeled. (C) 2010 Elsevier Ltd. All rights reserved.

塑料压力管道热板焊接接头瞬时应力有限元分析

基于热粘弹性积分型本构关系,考虑材料性能依赖于温度变化及相变潜热的影响,利用有限元软件ANSYS热-力耦合及载荷步功能模拟结晶型高密度聚乙烯塑料压力管道热板焊接过程。并对焊接接头的应力分布进行有限元分析,得到了环向、轴向及径向瞬态应力分布规律。采用盲孔法和锯切法测量焊后残余应力,实测结果与数值分析基本吻合。

高密度聚乙烯塑料压力管道热板焊接头应力分布有限元分析

基于热粘弹性积分型本构关系,考虑材料性能依赖于温度变化及相变潜热的影响,利用AN SYS热-力耦合及载荷步功能模拟结晶型高密度聚乙烯(HDPE)塑料压力管道热板焊接过程,并对焊接接头的应力分布进行有限元分析,得到了环向、轴向以及径向瞬态应力分布的基本规律。采用盲孔法和锯切法测量焊后残余应力,实测结果与数值分析基本符合

广西合山固体废弃物制备地质聚合物胶凝材料

Geopolymer gelatinous material was prepared by ferroalloy slag (signed with NKT in laboratory) and circulating fluidization bed slag (CFB slag, signed with NM in laboratory) produced from Heshan city, Guangxi zhuang autonomous region, China. The mechanical properties of the geopolymer made of high content ferroalloy slag can reach the standard of 42.5# portland blastfurnace-slag cement, and it’s processing technology is more simple and not need of mill and burn and will not produce harmful gas. By means of chemical and XRD analyses, it is concluded that NKT is a kind of acidity water-granulated slag with better activation and fit to be activated by alkali activators. Low-cost industrial gypsum (signed with NG in laboratory), analytic reagent oxide(signed with NH in laboratory) and sulfate(signed with NS in laboratory) were selected as alkali activation in the experiment. The results showed NH is a good alkali activator for NKT. Both NH and NG can activate ferroally slag’s activities, but NS can’t alone. The activation effect of superimposing activation of NH and NG excel by separateness. Based on those experiments, optimization compounds were carried out: (1) NKT: NH: NG = 80: 10: 10 and (2) NM: NKT: NS: NG: NH = 10: 70: 2: 8: 10。. The soundness of the test blocks is good by boiling examination. Through XRD, SEM, IR, NMR analyses of geopolymer, the reaction mechanism of geopolymer prepared by alkalescent activating in solid wastes was discussed in the thesis first. It is point out, there is difference in reaction mechanism between traditional geopolymer preparation and the preparation of alkalescent activating solid wastes because NG is a industry product. There is the similar process of depolymerization and reunion of Si-O bond. The latter preparation process generate new subtance but the former doesn’t. In the experiment, we found a performance of NKT that the water requirement of normal consistency of geopolymer reduces with increasing content of NKT. The result shows NKT has some ability to reduce water requirement. The performance is worthy of further research and utilization. Making use of solid wastes to prepare geopolymer, not only can settle environment problem caused by a great deal of dump of NKT, but also settle the shortage of natural resources. Moreover it could take economic, environmental and social benefits and settle thoroughly contradiction in the environment protection and regional economy development and promote circulation economy development.

Formulações nanobiotecnológicas para vetorização da Curcumina e seus derivados

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Ciências Farmacêuticas

SCANNING ACOUSTIC MICROSCOPE FOR CHARACTERIZATION OF ARTERIAL PLAQUE

Unstable arterial plaque is likely the key component of atherosclerosis, a disease which is responsible for two-thirds of heart attacks and strokes, leading to approximately 1 million deaths in the United States. Ultrasound imaging is able to detect plaque but as of yet is not able to distinguish unstable plaque from stable plaque. In this work a scanning acoustic microscope (SAM) was implemented and validated as tool to measure the acoustic properties of a sample. The goal for the SAM is to be able to provide quantitative measurements of the acoustic properties of different plaque types, to understand the physical basis by which plaque may be identified acoustically. The SAM consists of a spherically focused transducer which operates in pulse-echo mode and is scanned in a 2D raster pattern over a sample. A plane wave analysis is presented which allows the impedance, attenuation and phase velocity of a sample to be de- termined from measurements of the echoes from the front and back of the sample. After the measurements, the attenuation and phase velocity were analysed to ensure that they were consistent with causality. The backscatter coefficient of the samples was obtained using the technique outlined by Chen et al [8]. The transducer used here was able to determine acoustic properties from 10-40 MHz. The results for the impedance, attenuation and phase velocity were validated for high and low-density polyethylene against published results. The plane wave approximation was validated by measuring the properties throughout the focal region and throughout a range of incidence angles from the transducer. The SAM was used to characterize a set of recipes for tissue-mimicking phantoms which demonstrate indepen- dent control over the impedance, attenuation, phase velocity and backscatter coefficient. An initial feasibility study on a human artery was performed.

Use of oxygen sensors for the non destructive measurement of oxygen in packaged food and beverage products and its impact on product quality and shelf life

The principal objective of this thesis was to investigate the ability of reversible optical O2 sensors to be incorporated into food/beverage packaging systems to continuously monitor O2 levels in a non-destructive manner immediately postpackaging and over time. Residual levels of O2 present in packs can negatively affect product quality and subsequently, product shelf-life, especially for O2-sensitive foods/beverages. Therefore, the ability of O2 sensors to continuously monitor O2 levels present within food/beverage packages was considered commercially relevant in terms of identifying the consequences of residual O2 on product safety and quality over time. Research commenced with the development of a novel range of O2 sensors based on phosphorescent platinum and palladium octaethylporphyrin-ketones (OEPk) in nano-porous high density polyethylene (HDPE), polypropylene (PP) polytetrafluoroethylene (PTFE) polymer supports. Sensors were calibrated over a temperature range of -10°C to +40°C and deemed suitable for food and beverage packaging applications. This sensor technology was used and demonstrated itself effective in determining failures in packaging containment. This was clearly demonstrated in the packaging of cheese string products. The sensor technology was also assessed across a wide range of packaged products; beer, ready-to-eat salad products, bread and convenience-style, muscle-based processed food products. The O2 sensor technology performed extremely well within all packaging systems. The sensor technology adequately detected O2 levels in; beer bottles prior to and following pasteurisation, modified atmosphere (MA) packs of ready-to-eat salad packs as respiration progressed during product storage and MA packs of bread and convenience-style muscle-based products as mycological growth occurred in food packs over time in the presence and absence of ethanol emitters. The use of the technology, in conjunction with standard food quality assessment techniques, showed remarkable usefulness in determining the impact of actual levels of O2 on specific quality attributes. The O2 sensing probe was modified, miniaturised and automated to screen for the determination of total aerobic viable counts (TVC) in several fish species samples. The test showed good correlation with conventional TVC test (ISO:4833:2003), analytical performance and ruggedness with respect to variation of key assay parameters (probe concentration and pipetting volume). Overall, the respirometric fish TVC test was simple to use, possessed a dynamic microbial range (104-107 cfu/g sample), had an accuracy of +/- one log(cfu/g sample) and was rapid. Its ability to assess highly perishable products such as fish for total microbial growth in <12 hr demonstrates commercial potential.

Large-area nanopatterning of self-assembled monolayers of alkanethiolates by interferometric lithography.

We demonstrate that interferometric lithography provides a fast, simple approach to the production of patterns in self-assembled monolayers (SAMs) with high resolution over square centimeter areas. As a proof of principle, two-beam interference patterns, formed using light from a frequency-doubled argon ion laser (244 nm), were used to pattern methyl-terminated SAMs on gold, facilitating the introduction of hydroxyl-terminated adsorbates and yielding patterns of surface free energy with a pitch of ca. 200 nm. The photopatterning of SAMs on Pd has been demonstrated for the first time, with interferometric exposure yielding patterns of surface free energy with similar features sizes to those obtained on gold. Gold nanostructures were formed by exposing SAMs to UV interference patterns and then immersing the samples in an ethanolic solution of mercaptoethylamine, which etched the metal substrate in exposed areas while unoxidized thiols acted as a resist and protected the metal from dissolution. Macroscopically extended gold nanowires were fabricated using single exposures and arrays of 66 nm gold dots at 180 nm centers were formed using orthogonal exposures in a fast, simple process. Exposure of oligo(ethylene glycol)-terminated SAMs to UV light caused photodegradation of the protein-resistant tail groups in a substrate-independent process. In contrast to many protein patterning methods, which utilize multiple steps to control surface binding, this single step process introduced aldehyde functional groups to the SAM surface at exposures as low as 0.3 J cm(-2), significantly less than the exposure required for oxidation of the thiol headgroup. Although interferometric methods rely upon a continuous gradient of exposure, it was possible to fabricate well-defined protein nanostructures by the introduction of aldehyde groups and removal of protein resistance in nanoscopic regions. Macroscopically extended, nanostructured assemblies of streptavidin were formed. Retention of functionality in the patterned materials was demonstrated by binding of biotinylated proteins.