Procesado, estructura y propiedades de materiales compuestos de matriz termoplástica y nanorefuerzos de carbono

208 p.

Relation between TMAOase activity and content of formaldehyde in fillet minces and bellyflap minces from gadoid fishes

Minced fish is a significant component of a number of frozen fishery products like fish fingers, cakes and patties. Predominately minced fish is produced from gadoid species (Alaska pollack, cod, saithe, hake and others) possessing the enzyme trimethylamine oxide demethylase (TMAOase, E.C. 4.1.2.32) (Rehbein and Schreiber 1984). TMAOase catalyses the degradation of trimethylamine oxide (TMAO) to formaldehyde (FA) and dimethylamine (DMA), preferentially during frozen storage of products (Hultin 1992). In most gadoid species light muscle contains only low activity of TMAOase, the activity of red muscle and bellyflaps being somewhat higher. In contrast, the TMAOase activity in blood, kidney and other tissues, residues of which may contaminate minced fish flesh, may be higher for several orders of magnitude (Rehbein and Schreiber 1984).

Anwendungsmöglichkeiten instrumenteller Texturanalyse zur Charakterisierung industriell hergestellter Farcen

Commercially processed and for industrial purpose destined minces of several fish species were characterised with regard to their texture using texture profile analysis (TPA) of boiled specimen and by measuring the penetration force on raw minces as well as with regard to their colour by instrumental measurements of CIELab values. Concerning the parameters investigated the minces were in most cases significantly different. It was evident that the fish species is responsible for the functional properties of these intermediate products. For the TPA the influence of the measurement conditions was demonstrated and an appropriate method derived. IEF of proteins was used to verify the declared fish species. Unfortunately, this was not possible in all cases due to the lack of comparable pattern. Both the DMA and FA content were found to be in the normal range except those for saithe.

Variation der Gehalte an flüchtigen stickstoffhaltigen Basen und "TVB-N" in Rotbarsch

Die Gehalte an den flüchtigen stickstoffhaltigen Aminen, Amoniak, Dimethylamin (DMA), Trimethylamin (TMA) sowie Trimethylaminoxid (TMAO) und der durch Direktdestillation nach milder Alkalisierung mit Magnesiumoxid erhaltende Wert an sogenanntem flüchtigen Basenstickstoff (TVB-N) wurden an fangfrischen Exemplaren von Rotbarsch untersucht.

Copolímeros à base de estireno e anidrido maleico: caracterização e estudo viscosimétrico

Copolímeros à base de estireno e anidrido maleico (SMA) são materiais sintéticos comercialmente disponíveis, obtidos pela reação dos dois monômeros citados em diferentes proporções, resultando em materiais versáteis, e disponíveis em diferentes graus de massas e porcentagens molares de anidrido maleico. São considerados polímeros funcionais devido à reatividade do grupamento anidrido maleico presente na cadeia polimérica. Por este motivo, esses materiais possuem vasta gama de aplicações, e elevada importância em diversas áreas, principalmente por terem baixa toxicidade, boa resistência térmica e boa estabilidade dimensional. Dessa forma, para melhor aplicação desses copolímeros, é muito importante o conhecimento dos parâmetros relativos ao seu comportamento em solução. A viscosimetria, em especial, é um método simples, útil e apropriado para fornecer essas informações. Os parâmetros viscosimétricos podem ser matematicamente calculados por extrapolação gráfica, entretanto a geração dos dados experimentais é mais demorada. Em contrapartida, é possível que a determinação experimental seja feita de forma mais rápida, por um único ponto, procedimento esse que desperta tanto o interesse acadêmico quanto o industrial. Neste trabalho, foram empregados os dois métodos de cálculo, utilizando solventes puros, misturas de solventes e três amostras de copolímeros à base de SMA. As determinações foram conduzidas a 40C. Os copolímeros utilizados possuiam teores de anidrido maleico de 50%, 45% e 40%, sendo os dois últimos esterificados com butil-metil-éster e sec-butil-metil-éster, respectivamente. Os solventes utilizados foram: N-metil-pirrolidona (NMP), tetrahidrofurano (THF) e suas respectivas misturas 1:1 com metil-etil-cetona (MEK), ou seja, (NMP:MEK) e THF:MEK, sendo a MEK um não solvente para o copolímero não esterificado. As equações utilizadas para extrapolação gráfica foram as de Huggins, Kraemer e Schulz-Blaschke. As equações empregadas em um único ponto foram as de Solomon-Ciuta, Deb-Chanterjee e novamente Schulz-Blaschke. Os resultados obtidos foram comparados e avaliou-se a possibilidade da utilização do método mais rápido, por um único ponto, para os sistemas estudados através dos desvios percentuais tendo como padrão os resultados da equação de Huggins. A equação de Deb-Chanterjee foi a mais adequada aos sistemas em NMP, que foi também o melhor solvente para as amostras. Os resultados obtidos na mistura NMP:MEK sugeriram que a viscosimetria pode ter sido um método sensível às pequenas diferenças estruturais entre os grupos pendentes nas amostras esterificadas. Paralelamente, realizou-se análises de espectroscopia na região do infravermelho (FTIR), análise termogravimétrica (TGA) e ensaios dinâmico-mecânicos (DMA) para a caracterização estrutural e térmica das amostras. Somente os resultados obtidos a partir de DMA indicaram diferenças entre as amostras esterificadas

Processos de formação de ligações cruzadas de polietileno de alto peso molecular

No projeto desenvolvido, ligações cruzadas foram formadas no polietileno de alta densidade e alto peso molecular, grade HS5103, através dos processos reticulação por peróxidos e silanos, com o objetivo de se avaliar o efeito da introdução de ligações cruzadas nas propriedades térmicas e mecânicas deste PEAD. Misturas entre o HS5103 e os peróxidos orgânicos, 2,5-Dimetil-2,5-di(terc-butilperoxi)hexano (DHBP) e peróxido de dicumila (DCP), foram produzidas e analisadas para a avaliação do efeito dos tipos de peróxido na reticulação e propriedades do PEAD e para determinação da concentração e do tipo de peróxido a ser utilizado como agente iniciador de reticulação por silano. Ensaios de índice de fluidez (MFI), reometria capilar, extração de polímero por xileno (teor de gel), análise termogravimétrica (TGA), calorimetria diferencial de varredura (DSC) e tração foram realizados para caracterização das misturas com peróxidos. Os resultados indicaram aumento da viscosidade com o aumento da concentração de peróxido, sendo o DHBP o que apresentou maior índice de aumento; não houve mudanças relevantes nas propriedades mecânicas e, ocorreu aumento do grau de cristalinidade, sendo mais significativo nas amostras com DCP. Após avaliação dos resultados citados, para as amostras a serem reticuladas via silano, foi promovida a graftização de diferentes concentrações de viniltrimetóxisilano (VTMS) na presença de 0,01%p/p de DCP com a adição de 0,05%p/p de catalisador, posteriormente a reticulação foi promovida em água. As amostras produzidas foram caracterizadas por ensaios de teor de gel, análise dinâmico-mecânica (DMA), espectroscopia de absorção no infravermelho (FTIR), TGA, ensaios de desgaste por deslizamento e tração. Nas amostras com silano a formação de ligações cruzadas foi gradativa, apresentando de 8% de gel para amostra com 0,5%p/p de VTMS a 57 % para amostra com1,5% p/p de silano, maior concentração utilizada. A análise dinâmico-mecânica (DMA) realizada evidenciou que houve um aumento densidade de ligações cruzadas e do módulo de armazenamento após temperatura de fusão com o teor de silano, concordando com os resultados de teor de gel. As análises de FTIR mostraram que houve a graftização e a formação de ligações cruzadas no PEAD HS5103. Não se observou um aumento significativo para o limite de resistência para o PEAD modificado. E os testes de desgaste por deslizamento indicaram um aumento da resistência ao desgaste das amostras reagidas com VTMS.

Cryopreservation of sperm of common carp, Cyprinus carpio and silver barb, Barbonymus gonionotus for genetically improved seed production

Experiments were conducted to develop and standardize the protocols for cryopreservation of sperm of common carp, Cyprinus carpio and also for using the cryopreserved sperm for fertilization of eggs. Nine extender solutions as Alsever's solution, kurokura-1, kurokura-2, urea egg-yolk, egg-yolk citrate, 0.6% glucose, 0.9% NaCl, Ma and Mb, and five cryoprotectants namely ethanol, methanol, dimethylsulfoxide (DMSO), dimethylamine (DMA) and glycerol were tested. The cryoprotectants were mixed at 10% concentration of the extenders (v/v) to make the cryodiluents. Milt and cryodiluents were mixed at a ratio of 1:9 for Alsever's solution, kurokura-1, kurokura-2, 0.6% glucose and 0.9% NaCl, 1:4 for urea egg-yolk, egg-yolk citrate, Ma and Mb. Among the cryodiluents Alsever's solution mixed with either ethanol or methanol was found to be suitable and it produced more than 90% and 80% spermatozoan motility at equilibrium and post-thaw periods, respectively. Kurokura-1 and kurokura-2 when mixed with the same cryoprotectants showed good spermatozoan motility at equilibrium period (80-90%) but the motility was reduced (30-55%) at post-thaw state. Other extenders did not produce acceptable sperm-motility and in some cases the frozen milt became clotted. Different dilution ratios (1:1, 1:2, 1:4, 1:5, 1:7, 1:9, 1:12, 1:15, 1:20) were formulated for obtaining a suitable milt dilution, the dilution ratio of 1: 9 (milt : cryodiluent) demonstrated the highest post-thaw spermatozoan motility (80%) in Alserver's solution. The optimum concentration of cryoprotectants in the cryodiluents was determined, 10% concentration level was found to be effective to produce the highest number of spermatozoan motility in comparison to the other concentrations (5%, 15%, 20% 30%). Sperm preserved with the cryodiluent Alsever's solution along with either methanol or ethanol was found to be effective to fertilize eggs and produce hatchlings. The hatching rates ranged between 1.48% and 14.76%, compare to control. The fish produced through use of cryopreserved sperm and normal sperm were found to grow well and no significant (P<0.05) growth difference was observed between them. In case of silver barb, Barbonymus gonionotus, sperm tested against six extenders such as egg-yolk citrate, urea-egg-yolk, kurokura-1, kurokura-2, 0.9% NaCl and modified fish ringer (MFR) solution. Cryoprotectants used were the same as those of C. carpio. Milt was diluted with the cryodiluent at a ratio of 1:4 for egg-yolk citrate and urea-egg-yolk, 1:5 for kurokura-1 and 1:9 for 0.9% NaCl, MFR and kurokura-2. The cryoprotectant concentration was maintained at 10% of the extender (v/v) in all the cases. Among the extenders, egg-yolk citrate and urea-egg-yolk mixed with 10% DMSO, methanol and ethanol produced 50% post-thaw spermatozoan motility, whereas DMA and glycerol provided only 10% motility. Trials on milt dilution ratio and cryoprotectant concentration are being conducted. Fertilization trials are also underway.

Bayesian correlated clustering to integrate multiple datasets.

MOTIVATION: The integration of multiple datasets remains a key challenge in systems biology and genomic medicine. Modern high-throughput technologies generate a broad array of different data types, providing distinct-but often complementary-information. We present a Bayesian method for the unsupervised integrative modelling of multiple datasets, which we refer to as MDI (Multiple Dataset Integration). MDI can integrate information from a wide range of different datasets and data types simultaneously (including the ability to model time series data explicitly using Gaussian processes). Each dataset is modelled using a Dirichlet-multinomial allocation (DMA) mixture model, with dependencies between these models captured through parameters that describe the agreement among the datasets. RESULTS: Using a set of six artificially constructed time series datasets, we show that MDI is able to integrate a significant number of datasets simultaneously, and that it successfully captures the underlying structural similarity between the datasets. We also analyse a variety of real Saccharomyces cerevisiae datasets. In the two-dataset case, we show that MDI's performance is comparable with the present state-of-the-art. We then move beyond the capabilities of current approaches and integrate gene expression, chromatin immunoprecipitation-chip and protein-protein interaction data, to identify a set of protein complexes for which genes are co-regulated during the cell cycle. Comparisons to other unsupervised data integration techniques-as well as to non-integrative approaches-demonstrate that MDI is competitive, while also providing information that would be difficult or impossible to extract using other methods.

Weighted least squares with expectation-maximization algorithm for burst detection in U.K. water distribution systems

Flow measurement data at the district meter area (DMA) level has the potential for burst detection in the water distribution systems. This work investigates using a polynomial function fitted to the historic flow measurements based on a weighted least-squares method for automatic burst detection in the U.K. water distribution networks. This approach, when used in conjunction with an expectationmaximization (EM) algorithm, can automatically select useful data from the historic flow measurements, which may contain normal and abnormal operating conditions in the distribution network, e.g., water burst. Thus, the model can estimate the normal water flow (nonburst condition), and hence the burst size on the water distribution system can be calculated from the difference between the measured flow and the estimated flow. The distinguishing feature of this method is that the burst detection is fully unsupervised, and the burst events that have occurred in the historic data do not affect the procedure and bias the burst detection algorithm. Experimental validation of the method has been carried out using a series of flushing events that simulate burst conditions to confirm that the simulated burst sizes are capable of being estimated correctly. This method was also applied to eight DMAs with known real burst events, and the results of burst detections are shown to relate to the water company's records of pipeline reparation work. © 2014 American Society of Civil Engineers.

基于虚拟机架构的系统攻击与防范技术研究

随着虚拟机架构的日渐流行，虚拟机平台的安全性越来越重要。研究虚拟机平台下的系统攻击和防范技术，对于化解系统面临的安全威胁，保障系统的安全运行具有十分重要的意义。 本文以开源的虚拟机系统 Xen 为研究对象，分别研究了针对虚拟机监控器（VMM）和客户机的攻击与防范技术。 对于虚拟机监控器， 本文分析了一个利用DMA技术攻击VMM的恶意程序，并讨论了使用 IOMMU防范该类型攻击的方法。 对于客户机，本文分析了内核 Rootkit 的常见攻击技术，并给出了一个虚拟机架构下防范 Rootkit的方法。 该方法通过写保护来保证内核关键资源的完整性，并通过 Xen对页表的保护来确保写保护的有效性。在 2.6 版本的Linux上进行的实验表明，该方法能够有效防止多种Rootkit的攻击。

铬污染土壤修复过程中土壤细菌群落多样性的RFLP分析

对污染土壤修复过程中土壤细菌群落多样性的变化进行研究。【方法】以淹水培养后的模拟铬污染土壤为供试材料,通过直接提取土壤中总细菌DNA,利用细菌专一引物克隆细菌16S rDNA片段,分别建立克隆文库。利用PCR-RFLP技术,分析比较了土壤淹水10 d(对照,S1)、添加Cr(Ⅵ)淹水10 d(S2)、添加Cr(Ⅵ)和Fe(OH)3淹水10 d(S3)及20 d(S4)4个处理中土壤细菌群落的变化。【结果】用专一引物克隆细菌16S rDNA片段,分别建立了克隆文库;用限制性内切酶RsaⅠ进行细菌16S rDNA PCR-RFLP分析,分别得到123,120,97和69个酶切类型,库容值分别为54.92%,55.43%,65.33%和76.60%;Shannon-Wiener指数、Gini指数、物种丰富度指数(dMa)和物种均匀度指数(Jgi)均表现为S1>S2>S3>S4,以上4个指数的变异系数分别为11.51%,1.84%,23.64%和1.55%;基于细菌多样性参数的聚类分析结果,将对照S1和添加Cr(Ⅵ)处理的S2归于一类,而2个添加Fe处理的土壤S3和S4聚为一类。【结论】经过10 d淹水处理,...

氮肥缺失对旱地土壤细菌群落多样性的影响

本文旨在研究氮肥缺失对旱地土壤细菌群落多样性的影响。采用直接提取土壤微生物总DNA的方法,对不施肥(CK)、适量施肥(F1)、和缺氮施肥(F2)3种不同施肥水平土样DNA进行提取,扩增细菌16S rDNA基因片段,建立克隆文库。用限制性内切酶HhaI和RsaI进行PCR-RFLP分析,分别得到146、187、11个酶切类型。采用α多样性的测度对试验结果进行分析统计结果表明,不同处理间土壤细菌的多样性(H′、Ds和Dg)和物种丰富度(dMa、R2和E)均为F1>CK>F2;λ、dMa、E和H′指数在不同施肥处理间的变异系数达到56.96%~163.1%,尤其Simpson指数λ是非常敏感的指标,处理间的差异最大,表明氮肥缺失严重影响土壤细菌群落多样性,合理施肥有利于土壤细菌的多样性。

Lewis酸引发的LLDPE/PS共混体系的原位反应增容及其结构与性能研究

本文以单组分和双组分Lewis酸为催化剂，采用反应加工的方法，制备了原位反应增容的线性低密度聚乙烯/聚苯乙烯共混物（LLDPE/PS），并对原位反应增容的机理、增容体系的结构性能以及Lewis酸对共混组分的降解作用进行了系统研究。 以FTIR和NMR为手段、二甲苯为模拟化合物，确认LLDPE/PS共混体系在Lewis酸为催化剂作用下发生了LLDPE与PS的接枝反应，LLDPE接枝在PS苯环的对位上。形成的原位接枝共聚物对体系起增容作用。 使用溶剂抽提、SEM、DMA、流变和DSC等手段对以单组分Lewis酸AlCl3 为催化剂的LLDPE/PS共混物的结构性能进行了研究。从溶剂抽提前后的重量比计算了接枝物的含量。催化剂用量较低时体系中的接枝物含量随AlCl3的增加而提高，随着AlCl3进一步增加，接枝物含量不会增加反而下降，发现AlCl3导致均聚物的降解。研究结果表明，共混体系中加入适量的AlCl3催化剂后，分散相尺寸减小，分布均匀，储能模量增加，低频区的复数黏度升高。但AlCl3用量过高时使共混物的分散相尺寸增加，分布均匀度下降，储能模量和复数黏度降低。以GPC为手段研究了单组分 Lewis酸AlCl3对共混组分的降解作用，发现对PS的降解作用显著。 由于单组分Lewis酸催化剂会导致共混组分降解，使共混体系的物理机械性能变劣，为此，我们在LLDPE/PS共混物中引入了双组分Lewis酸催化剂（Me3SiCl、InCl3•4H2O）。结果表明双组分Lewis酸催化剂不但能够催化LLDPE和PS的原位接枝反应，获得高性能的LLDPE/PS合金材料，而且不会引发共混组分PS的降解。在催化剂用量固定时，采用双组分催化剂时共混物的拉伸强度随着LLDPE含量的增加几乎保持不变，但冲击强度有十分明显的提高。对比了加入催化剂前后共混物形貌的变化，增容后的共混物中分散相粒子尺寸显著降低，证明了双Lewis酸良好的催化性能。 对以双Lewis酸为催化剂的共混物的流变行为和结晶行为进行了研究。随着催化剂的加入，两相之间的相互作用增强，因此共混物的复数黏度，储能模量和损耗模量都有不同程度的提高。增容后的LLDPE相区变小，因而在冷却过程中出现不同程度的分步结晶现象。 对单组分和双组分Lewis酸催化剂原位反应增容LLDPE/PS共混体系的机理进行了探讨。机理为Friedel-Crafts烷基化反应。在采用单组分Lewis酸催化剂时， AlCl3与体系中含有的微量水等杂质发生反应，形成一个复合物，然后进一步与聚乙烯中的不饱和的双键发生反应形成碳正离子，并攻击LLDPE分子链从而形成大分子的碳正离子LLDPE+，而这些LLDPE+则通过电子的重排而发生剪切断裂。在催化剂的存在下，这些断裂的LLDPE片断取代PS中的苯环上的质子而发生接枝反应，从而形成LLDPE-g-PS共聚物。采用双组分Lewis酸催化剂时，首先发生双Lewis酸的耦合；耦合后的Lewis酸与水等杂质反应生成复合物，然后与非饱和的LLDPE分子反应生成初级碳正离子；初级碳正离子进攻LLDPE主链，生成较大的碳正离子；LLDPE+碳正离子取代PS苯环对位的质子而生成接枝共聚物。

SEBS、POE与异氰酸酯的接枝反应及其对PA6、PBT的增韧研究

本工作采用熔融反应接枝的方法将(3-异氰酸酯基-4-甲基)苯氨基甲酸-2-丙烯酯(TAI)引入到聚苯乙烯-b-聚(乙烯-co-丁烯)-b-聚苯乙烯三嵌段共聚物(SEBS)上，以实现SEBS的功能化。红外光谱表明TAI已经成功接枝到SEBS上。GPC测试表明接枝后SEBS具有高的分子量与宽的分子量分布。DMA分析证明，接枝后聚(乙烯-co-丁烯) (PEB)段的玻璃化转变提高。对未参与接枝的单体的分析表明，单体TAI是个不容易自聚的单体，并对接枝过程的机理进行了研究。 为了提高TAI的存储稳定性和解决反应过程中的毒性大的问题，采用己内酰胺为封端剂对TAI中的异氰酸酯进行了封端。红外光谱和核磁共振结果表明，己内酰胺封端的TAI（BTAI）中含有双键和封闭型异氰酸酯结构，不存在着活泼的异氰酸酯。红外光谱结果表明，在高温下BTAI可以重新产生活泼的异氰酸酯基团。DSC与TG/DTA研究证明，BTAI的初始解离温度大约为135 C。采用熔融反应接枝的方法将BTAI接枝到SEBS和乙烯-辛烯共聚物（POE）分子上。研究表明，接枝率随着单体含量或引发剂含量的增加而增加。接枝以后的SEBS与POE的剪切变稀行为都比未接枝的SEBS与POE要明显。 利用BTAI功能化的SEBS和POE两种弹性体，通过熔融反应共混方法制备了PA6合金。两种弹性体与PA6共混物的红外光谱和流变行为的研究表明，在反应共混中形成了新的接枝共聚物。共混物的脆断面的场发射扫描电镜照片表明，共混物形成一种海-岛结构，而反应共混物的具有更均匀的粒子分散性，更小的粒子尺寸。PA6/SEBS-g-BTAI共混的透射电镜照片说明，共混物中形成了一种以PS为核-PEB为壳的核壳结构。与相应的物理共混物相比，通过反应共混制备的PA6合金（PA6/SEBS-g-BTAI合金和PA6/POE-g-BTAI合金）的拉伸强度、杨氏模量得到了提高。两种反应共混物的缺口冲击强度得到了非常明显的提高，合金材料的缺口冲击强度可以达到1000 J/m 以上。共混物中弹性体对PA6的结晶起到了成核的作用，结晶温度提高。形成的共聚物阻碍了PA6的分子链的运动，使得PA6的结晶温度下降。 本工作还利用上述制备的POE-g-BTAI和SEBS-g-BTAI两种功能化的弹性体与聚对苯二甲酸丁二醇酯（PBT）进行共混。研究表明，在反应共混过程中PBT中的反应基团与释放出的异氰酸酯发生反应，生成了新的共聚物。通过共混物的脆断面的FESEM图片可以看到，POE与PBT的共混物中，POE以球状粒子分散在PBT中，并且反应共混物的粒子分散均匀，粒子尺寸变小。与POE/PBT共混不同的是，在PBT与SEBS共混过程中，二者形成了交错结构，而反应共混在较低含量就形成了交错结构。POE与PBT反应共混物的缺口冲击强度得到了很大的提高，冲击强度可以达到1100 J/m以上，而PBT与SEBS的反应共混物的冲击强度改变不大。相对于物理共混物，两种弹性体与PBT的反应共混物的拉伸强度与拉伸模量都得到了提高。弹性体的加入提高了PBT的结晶温度，反应共混物的结晶温度低于物理共混物的结晶温度，说明弹性体的加入起到了PBT的成核剂的作用，生成的共聚物亦阻碍了PBT的分子链的移动。 关键词：聚苯乙烯-b-聚(乙烯-co-丁烯)-b-聚苯乙烯三嵌段共聚物；乙烯-辛烯共聚物；封闭型异氰酸酯；反应加工；聚酰胺6；聚对苯二甲酸丁二醇酯