Flux Partitioning of Species Approach in Binary Interdiffusion Process

Validation of the flux partitioning of species model has been illustrated. Various combinations of inequality expression for the fluxes of species A and B in two successively grown hypothetical intermetallic phases in the interdiffusion zone have been considered within the constraints of this concept. Furthermore, ratio of intrinsic diffusivities of the species A and B in those two phases has been correlated in four different cases. Moreover, complete and or partial validation or invalidation of this model with respect to both the species, has been proven theoretically and also discussed with the Co-Si system as an example.

Avaliação de catalisadores à base de estanho visando à produção de biodiesel

Atualmente, existe um crescente interesse por fontes de energia renováveis e o desenvolvimento de novas tecnologias para a produção de biocombustíveis. O biodiesel é uma fonte alternativa de combustível bastante atrativa em relação ao diesel em decorrência de seus benefícios ambientais. A obtenção de biodiesel é geralmente realizada através de reações de transesterificação de óleos vegetais com álcool de cadeia curta. Entretanto, também se pode produzi-lo através da esterificação de ácidos graxos livres utilizando-se matérias-primas de baixa qualidade como rejeitos industriais, domésticos ou gorduras animais. O estudo de catalisadores que melhorem os resultados destas reações tem importante papel no desenvolvimento da produção de biodiesel. Normalmente, utilizam-se catalisadores básicos como o NaOH, nas reações de transesterificação. No entanto, o uso destes catalisadores causa impactos ambientais, além de promover a reação de saponificação quando a matéria-prima apresenta teores significativos de acidez, reduzindo o rendimento e dificultando a separação de fases. Este trabalho apresenta o estudo de catalisadores ácidos, à base de estanho, com ênfase especial no sulfato de estanho II, voltados para utilização na reação de esterificação de cargas contendo elevados teores em ácidos graxos. Avaliou-se a influência das variáveis: temperatura, concentração do catalisador, tipo de sistema reacional, quantidade de etanol, tipo de álcool, acidez, natureza dos ácidos graxos e temperatura de calcinação. Uma comparação entre os catalisadores, a questão da reutilização do catalisador e das mudanças proporcionadas pelo tratamento térmico ao qual foram submetidos também foram analisadas. Dentre os catalisadores estudados, os de sulfato de estanho mostraram maior atividade catalítica frente à reação estudada, os mais promissores sendo os calcinados até a temperatura de 500C. O principal motivo para os altos rendimentos encontrados foi associado ao comportamento pseudo-homogêneo do SnSO4, que se solubiliza, acidificando o meio reacional durante as reações de esterificação

Digestão nitro-sulfúrica de fígado de peixe Mugil liza em forno de micro-ondas com radiação focalizada para determinar elementos de interesse ambiental por ICPMS

O presente estudo propõe uma metodologia para dissolução de tecidos biológicos em sistema de micro-ondas com radiação focalizada e posterior análise elementar por espectrometria de massas com plasma acoplado indutivamente (ICPMS). Foram determinados os elementos arsênio (As), cádmio (Cd), cobre (Cu), chumbo (Pb), níquel (Ni), vanádio (V) e zinco (Zn). A matriz nitro-peroxo-sulfúrica foi comparada com outra sem o ácido sulfúrico e apresentou melhor padrão de recuperação (acima de 90%) na quantificação dos elementos certificados no material de referência TORT-2. As interferências causadas pela presença do ácido sulfúrico na matriz digestora foram contornadas com o uso da célula de reação/colisão com gás hélio (He) e adição deste ácido na composição da curva de quantificação. O ganho analítico proporcionado pelo método de digestão em matriz sulfúrica, em sistema não pressurizado, baseia-se no incremento da temperatura reacional e na degradação completa da matéria orgânica. As digestões tradicionalmente realizadas para quantificação por ICPMS, compostas unicamente de ácido nítrico (HNO3) e peróxido de hidrogênio (H2O2), não apresentam a mesma eficiência na degradação da matéria orgânica em sistemas abertos. Por fim, este método foi aplicado satisfatoriamente em amostras de tecido hepático de peixe Mugil liza (tainha), comprovando sua eficiência em monitorar a bioacumulação, utilizando-se da sensibilidade da técnica multielementar de ICPMS

Deformation measurement of a human chest experiencing global motion

Current state-of-the-art techniques for determination of the change in volume of human chests, used in lung-function measurement, calculate the volume bounded by a reconstructed chest surface and its projection on to an approximately parallel static plane over a series of time instants. This method works well so long as the subject does not move globally relative to the reconstructed surface's co-ordinate system. In practice this means the subject has to be braced, which restricts the technique's use. We present here a method to compensate for global motion of the subject, allowing accurate measurement while free-standing, and also while undergoing intentional motion. © 2012 Springer-Verlag.

Rapid patterning of 1-D collagenous topography as an ECM protein fibril platform for image cytometry.

Cellular behavior is strongly influenced by the architecture and pattern of its interfacing extracellular matrix (ECM). For an artificial culture system which could eventually benefit the translation of scientific findings into therapeutic development, the system should capture the key characteristics of a physiological microenvironment. At the same time, it should also enable standardized, high throughput data acquisition. Since an ECM is composed of different fibrous proteins, studying cellular interaction with individual fibrils will be of physiological relevance. In this study, we employ near-field electrospinning to create ordered patterns of collagenous fibrils of gelatin, based on an acetic acid and ethyl acetate aqueous co-solvent system. Tunable conformations of micro-fibrils were directly deposited onto soft polymeric substrates in a single step. We observe that global topographical features of straight lines, beads-on-strings, and curls are dictated by solution conductivity; whereas the finer details such as the fiber cross-sectional profile are tuned by solution viscosity. Using these fibril constructs as cellular assays, we study EA.hy926 endothelial cells' response to ROCK inhibition, because of ROCK's key role in the regulation of cell shape. The fibril array was shown to modulate the cellular morphology towards a pre-capillary cord-like phenotype, which was otherwise not observed on a flat 2-D substrate. Further facilitated by quantitative analysis of morphological parameters, the fibril platform also provides better dissection in the cells' response to a H1152 ROCK inhibitor. In conclusion, the near-field electrospun fibril constructs provide a more physiologically-relevant platform compared to a featureless 2-D surface, and simultaneously permit statistical single-cell image cytometry using conventional microscopy systems. The patterning approach described here is also expected to form the basics for depositing other protein fibrils, seen among potential applications as culture platforms for drug screening.

氮杂环化合物的绿色合成研究

氮杂环化合物大多数都是具有生理活性的物质，例如喹喔啉化合物与苯二氮卓类化合物，因此研究氮杂环化合物骨架的构建方法具有一定意义。绿色化学的迅速发展迫切要求化学家发展清洁、经济和环境较友好条件下的有机合成方法。其中，水相反应与绿色固体酸催化剂的使用都是实现绿色有机合成的重要途径，它们非常具有潜力，近些年受到了广泛关注。本论文的主要工作是围绕水相及固体酸催化条件下两类具有生物活性的含氮杂环小分子的合成方法而开展的，具体包括以下内容： 1. 研究和探索出了两类绿色固体酸催化剂蒙脱土（Mont. K-10）和杂多酸(H4SiW12O40), 在水相条件下成功合成出喹喔啉化合物的有效方法。两个催化体系都以无毒无公害的水作反应溶剂，实验条件温和，操作安全简便，反应速度快，底物普适性强，产率高，且产物易分离收集。两类固体酸催化剂，对设备腐蚀性小，可回收循环使用，对环境无公害; 蒙脱土催化大部分底物能得到当量产率的产物，硅钨酸催化催化剂负载量小。 2. 实现了无溶剂条件下，以杂多酸（H3PW12O40）作催化剂，高效合成1,5-苯二氮卓衍生物的合成方法。该催化体系具有以下一些优势：实验条件温和，反应速度较快，底物普适性良好，产物易分离收集，反应过程中没有加入其它有机溶剂，绿色环保。 ‘Green Chemistry’ is currently a major issue of modern chemistry. It is widely acknowledged that there is a growing need for more environmentally acceptable processes in the chemical industry. New green catalysts and green reaction media are the important and efficient strategies in green chemistry. New green catalysts include solid acid catalysts, solid base catalysts, metal catalysts not only possess higher activity and selectivity, but also are easily separated from reaction system. Green reaction media include water, supercritical fluids and ionic liquids can not only substitute traditional toxic and harmed organic solvents, but also improve reaction activity and selectivity. Meanwhile water is a promising green reaction medium for use in modern chemistry because it has a number of advantages such as the cheapest solvent available on earth, being non-hazardous and non-toxic to the environment. Solid acids had also attracted much attention for realizing green chemistry due to their unique acidity, high activity and efficiency as organic catalysts. Nitrogen-containing heterocyclic compounds of different ring sizes such as quinoxaline and benzodiazepine are the important pharmacologically active compounds. Due to the wide biological significance of these compounds, the synthesis of these types of compounds have received a great deal of attention. Despite the large availability of methods to construct nitrogen-containing heterocyclic compounds, there is still a strong need to further explore green methods to efficiently and safely synthesize these compounds. Thus, we aim at developing efficient and green methodology for the synthesis of quinoxaline and benzodiazepine carried out under water condition with solid acid catalysts. The contents of this dissertation are listed as the following: 1. We have developed two catalytic systems for the synthesis quinoxaline via the condensation of an aryl 1,2-diamine with a 1,2-diketone compound in the presence of Mont. K-10 or H4SiW12O40 as a catalyst in water solvent. Both of these two methods can be applied to wide range of substrates, tolerating aryl 1,2-diamine/1,2-diketone with the electron donating/drawing substituent. Operational simplicity, the ambient conditions, use of an economically convenient catalyst, use of water as a desirable solvent, high yields and short reaction times are the key features of these two protocols. 2. We developed a convenient and efficient protocol for the synthesis of a variety of 1,5-benzodiazepines in high yields via condensation of aryl o-phenylenediamine derivatives with a variety of ketones using H3PW12O40 as a green recyclable and heterogeneous catalyst under solvent-free condition. The simple experiment procedure combined with ease of recovery and reuse of this catalyst make this procedure quite simple, more convenient and environmentally benign.

影响沼气甲基产孢弧菌生长及其甲烷单加氧酶活性的若干因素研究

本文叙述了影响甲烷氧化细菌沼气甲基产孢弧菌81Z菌株生长和甲烷单加氧酶(MMO)活性的若干因素。沼气甲基产孢弧菌81Z菌株细胞生长被高浓度PO43-(>8mM),NH4+([NH4cl]>500mg/l)抑制；[CuSO4·5H2O]在0～4mg/l范围内。生长随[Cu2+]升高而加强，低[Cu2+](0.1mg/l CuSO4·5H2O)培养基中，添加Cocl2·6H2O(0.238mg/l)；促进菌体细胞生长。发酵罐分批培养过程中，生长延迟期过后，沼气甲基产孢弧菌81Z菌株细胞MMO比活很快达到最高，并稳定至对数生长中后期，随即急剧下降至初始水平。发现沼气甲基产孢弧菌81Z细胞中存在一种MMO活性，它不同于已报道过的两种MMO,MMOL最适PH6.2～6.4，4℃相对稳定，其产生不受培养基中[Cu2+]调控能与甲醇-甲醇脱氢酶系统相偶联，在无细胞抽提液中其活性被400μM[Cu2+]抑制。在低[Cu2+]发酵罐培养条件下，沼气甲基产孢弧菌81Z菌株产生可溶性MMC，其最适PH7.0，4℃不稳定，可被DE-52分离为三组分：A、B、C。为了获得沼气甲基产孢弧菌81Z细胞MMO的最佳催化活性，①采用高[Cu2+]培养基进行发酵罐培养，收集对数生长中期的细胞；②选择反应缓冲液PH6.3；③反应体系中添加5mM甲醇或甲酸是有效的方法。在本研究所采取过的最佳条件下，测得MMO活性为15.9nmol/min·mg干细胞，是以前报道的该菌株活性0.97nmol/min·mg干细胞的十六倍。Some factors which influence growth and MMO activity of Methylosporovibrio methanica 81Z were described. The growth of Methylosporovibrio methanica 81Z is inhibited by high concentration of PO43-(8mM)or NH4+(500mg/lNH4cl). The growth of Methylosporovibrio methanica 81Z increased with rising of copper concentration up to 4mg/l CuSO4·5H2O. At low copper concentration(0.1mg/lCuSO4·5H2O),adding Cocl2·6H2O(0.238mg/l)could enhance the growth of Methylosporovibrio methanica 81Z.With batch culture of Methylosporovibrio methanica 81Z in a fermentor, after lag phase, the activity of MMO reached the highest level rapidly and steady until later log phase, then falled to initial level.MMOL activity differenct from that of two types of MMO reported before was found from Methylosporovibrio methanica 81Z with optimum PH value from 6.2 to 6.4 and relative stabilty at 4℃. Synthsis of the MMOL was not regulated by copper concentaration in medium. Its activity could couple with methane-l-methanoldehydrogenase system, and in cell-free extract, were inhibited by 400μm copper ion. At low copper concentration(0.1mg/lCuSO4·5H2O) and in a fermentor, Methylosporovibrio methanica 81Z could syntheis soluble MMO similar to solble MMO reported before by Palton and Patel. Its optimum PH value was 7.0. It was unstable at 4℃. It could be resoluted into three components: A, B, and C. It was effentive for obtaining the maxtmum MMO with Methylosporovibrio methanica 81Z that (1) to keep high copper concentration(4mg/lCuSO4·5H2O) in a fermentor and harvest cell at middlel lag phase;(2) to choose 6.3 as the PH value of reaction buffer;(3)and to add 5mM methanol or formate into reaction system. In this dy, the MMO activity of cells of Methylosporovibrio methanica 81Z was reached 15.9 nmol/min.mg, dry weight, sixteen times as high as the value(0.97nmol/min.mg, dry weight) reported with the same strain.

Effect of entrance-channel asymmetry on the isospin dependence of nucleon emission in heavy ion collisions

Using the isospin- and momentum-dependent hadronic transport model 1BUU04, we have investigated the influence of the entrance-channel isospin asymmetry on the sensitivity of the pre-equilibrium neutron/proton ratio to symmetry energy in central heavy-ion collisions induced by high-energy radioactive beams. Our analysis and discussion are based on the dynamical simulations of the three isotopic reaction Systems Sn-132+Sn-124, Sn-124+Sn-112 and Sn-112+(112)Su which are of the same total proton number but, different isospin asymmetry. We find that, the kinetic-energy distributions of the pre-equilibrium neutron/proton ratio are quite sensitive to the density-dependence of symmetry energy at incident beam energy E/A = 400 MeV, and the sensitivity increases as the isospin asymmetry of the reaction system increases.

Probing the high density behavior of the symmetry energy by using the free neutron-proton ratio

Based on the isospin- and momentum-dependent transport model IBUU04, the transverse momentum distributions of the free neutron-proton ratio in the Sn-132+(124) Sn reaction system at mid-central collisions with beam energies of 400/A MeV, 600/A MeV and 800/A MeV are studied by using two different symmetry energies. It is found that the free neutron-proton ratio as a function of the transverse momentum at the mid-rapidity is very sensitive to the density dependency of the symmetry energy especially at incident energies around 400/AMeV.

Effects of ammonia and cetyltrimethylammonium bromide (CTAB) on morphologies of ZnO nano- and micromaterials under solvothermal process

Submicrometer zinc oxide (ZnO) with different morphologies including spindle-like, pencil-like, branch rod-like and frizzy flower-like shapes, have been hydrothermally synthesized in mixed solvents of ethanol and water at 140 degrees C. It was found that the volumes of added ammonia, surfactant (cetyltrimethylammonium bromide, CTAB), and mixed solvent play crucial roles in morphological control of ZnO nanostructures. Increasing the volume of ammonia added to the reaction system, the shape of ZnO evolves from spindle into branch rod-like. Synergetic influence between CTAB and ammonia can only be observed at high concentration of ammonia.

Micelle-assisted synthesis of polyaniline/magnetite nanorods by in situ self-assembly process

Polyaniline/magnetite nanocomposites consisting of polyaniline (PANI) nanorods surrounded by magnetite nanoparticles were prepared via an in situ self-assembly process in the presence of PANI nanorods. The synthesis is based on the well-known chemical oxidative polymerization of aniline in an acidic environment, with ammonium persulfate (APS) as the oxidant. An organic acid (dodecylbenzenesulfonic acid, DBSA) was used to replace the conventional strong acidic (1 M HCl) environment. Here, dodecylbenzenesulfonic acid is used not only as dopant, but also as surfactant in our reaction system.

Effect of hydroxyl and amino groups on electrochemiluminescence activity of tertiary amines at low tris(2,2 '-bipyridyl)ruthenium(II) concentrations

ECL of several amines containing different numbers of hydroxyl and amino groups was investigated. N-butyldiethanolamine is found to be more effective than 2-(dibutylamino)ethanol at gold and platinum electrodes, and is the most effective coreactant reported until now. Surprisingly, ECL intensities of monoamines, such as 2-(dibutylamino)ethanol and N-butyldiethanolamine, are much stronger than that of diamines including N,N,N',N'-tetrakis-(2-hydroxyethyl)-ethylenediamine and N,N,N',N'-tetrakis-(2-hydroxypropyl)ethlenediamine. The striking contrast between ECL signals of the investigated monoamines and diamines may result from more significant side reactions of diamines, such as the intramolecular side reactions between oxidative amine cation radicals and reductive amine free radicals.

Controlled synthesis of monodisperse nanocrystals by a two-phase approach without the separation of nucleation and growth processes

The synthesis of monodisperse nanocrystals is an important topic in the field of nanomaterials not only for practical applications, but also for scientific interest in fundamental research. In this feature article, we mainly focus on synthesis of monodisperse nanocrystals by a two-phase approach without the separation of nucleation and growth processes, and report some progress made recently in the observation and understanding of nucleation and growth of semiconductor nanocrystals. Firstly, a novel two-phase approach to monodisperse nanocrystals, which is different from the well-established synthesis models, is discussed. We demonstrate that the two-phase approach has a quite lengthy nucleation process, and can be applied to the synthesis of many kinds of binary monodisperse nanocrystals.

Synthesis and characterization of functional poly(gamma-benzyl-L-glutamate) (PBLG) as a hydrophobic precursor

Four kinds of functional poly(gamma-benzyl-L-glutamate) (PBLG) copolymers containing chloro, azido, allyl or propargyl groups on the side chains were synthesized through ester exchange reactions of PBLG with functional alcohols without any protection and de-protection process. Hydrolysis of PBLG, which was found during the ester exchange reaction under low ratios of alcohol to the repeat units of PBLG, was thoroughly investigated, and could be successfully depressed by addition of certain amount of benzyl alcohol to the reaction system. Click chemistry reactions of the azidized or propargylated copolymers, thiol-ene reaction of the allyllated copolymer were taken successfully, indicating that the functional groups on the copolymers were still reactive.