Estudo da reação entre o metanol e o acetato de etila em catalisadores Mg/La por espectroscopia no infravermelho acoplada a espectrometria de massas

A transesterificação metílica em meio homogêneo é catalisada por bases, tais como hidróxidos e alcóxidos de sódio ou potássio e se processa em baixa temperatura de reação, mesmo em escala industrial. A utilização de catalisadores formados por sólidos básicos aparece como uma alternativa promissora aos processos homogêneos convencionais, tendo em vista as inúmeras vantagens como a redução da ocorrência das reações indesejáveis de saponificação e redução de custos dos processos pela diminuição do número de operações associadas. Em estudos anteriores realizados pelo grupo, catalisadores a base de Mg/La com diferentes composições químicas (9:1, 1:1 e 1:9) mostraram-se promissores para a obtenção de ésteres metílicos via reação de transesterificação, porém não foi possível fazer uma correlação entre atividade catalítica e as propriedades físico-químicas quando toda a série foi considerada. Assim, a realização de um estudo de caráter fundamental, baseado em reações modelo e uso de moléculas sonda, permite avançar no entendimento das propriedades de superfície destes catalisadores. Portanto, o presente trabalho estuda a reação entre metanol e acetato de etila em catalisadores a base de Mg/La utilizando espectroscopia de reflectância difusa no infravermelho com transformada de Fourier (DRIFTS) acoplada a espectrometria de massas (MS) identificando os intermediários e produtos formados para determinar a rota reacional. As análises de difração de raios X mostram que os precursores são predominantemente compostos por carbonatos hidratados de magnésio (Mg/La 1:1 e 9:1) e de lantânio (Mg/La 1:9). Os perfis de decomposição térmica e difratogramas de raios X obtidos a partir de tratamento térmico in situ indicaram que estes carbonatos se decompõem apenas a partir de 750 C. As análises de Dessorção a Temperatura Programada realizadas com moléculas sonda, metanol e acetato de etila, mostraram a adsorção em maior quantidade do metanol independente da composição química do sólido. A partir dos resultados obtidos por DRIFTS-MS foi proposta uma rota reacional para a reação de transesterificação do acetato de etila e metanol, que ocorre via adsorção do metanol e do acetato de etila na superfície do catalisador, seguida da formação de um intermediário tetraédrico formado pelas moléculas adsorvidas, que sofre um rearranjo formando etanol, acetato de metila, acetona e metano. Simultaneamente, parte do metanol adsorvido como metoxi monodentado é desidrogenado formando formiatos que são dessorvidos na forma de formaldeído e decompostos formando CO2 e H2

Historical knowledge of sharks: ancient science, earliest American encounters, and American science, fisheries, and utilization

In western civilization, the knowledge of the elasmobranch or selachian fishes (sharks and rays) begins with Aristotle (384–322 B.C.). Two of his extant works, the “Historia Animalium” and the “Generation of Animals,” both written about 330 B.C., demonstrate knowledge of elasmobranch fishes acquired by observation. Roman writers of works on natural history, such as Aelian and Pliny, who followed Aristotle, were compilers of available information. Their contribution was that they prevented the Greek knowledge from being lost, but they added few original observations. The fall of Rome, around 476 A.D., brought a period of economic regression and political chaos. These in turn brought intellectual thought to a standstill for nearly one thousand years, the period known as the Dark Ages. It would not be until the middle of the sixteenth century, well into the Renaissance, that knowledge of elasmobranchs would advance again. The works of Belon, Salviani, Rondelet, and Steno mark the beginnings of ichthyology, including the study of sharks and rays. The knowledge of sharks and rays increased slowly during and after the Renaissance, and the introduction of the Linnaean System of Nomenclature in 1735 marks the beginning of modern ichthyology. However, the first major work on sharks would not appear until the early nineteenth century. Knowledge acquired about sea animals usually follows their economic importance and exploitation, and this was also true with sharks. The first to learn about sharks in North America were the native fishermen who learned how, when, and where to catch them for food or for their oils. The early naturalists in America studied the land animals and plants; they had little interest in sharks. When faunistic works on fishes started to appear, naturalists just enumerated the species of sharks that they could discern. Throughout the U.S. colonial period, sharks were seldom utilized for food, although their liver oil or skins were often utilized. Throughout the nineteenth century, the Spiny Dogfish, Squalus acanthias, was the only shark species utilized in a large scale on both coasts. It was fished for its liver oil, which was used as a lubricant, and for lighting and tanning, and for its skin which was used as an abrasive. During the early part of the twentieth century, the Ocean Leather Company was started to process sea animals (primarily sharks) into leather, oil, fertilizer, fins, etc. The Ocean Leather Company enjoyed a monopoly on the shark leather industry for several decades. In 1937, the liver of the Soupfin Shark, Galeorhinus galeus, was found to be a rich source of vitamin A, and because the outbreak of World War II in 1938 interrupted the shipping of vitamin A from European sources, an intensive shark fishery soon developed along the U.S. West Coast. By 1939 the American shark leather fishery had transformed into the shark liver oil fishery of the early 1940’s, encompassing both coasts. By the late 1940’s, these fisheries were depleted because of overfishing and fishing in the nursery areas. Synthetic vitamin A appeared on the market in 1950, causing the fishery to be discontinued. During World War II, shark attacks on the survivors of sunken ships and downed aviators engendered the search for a shark repellent. This led to research aimed at understanding shark behavior and the sensory biology of sharks. From the late 1950’s to the 1980’s, funding from the Office of Naval Research was responsible for most of what was learned about the sensory biology of sharks.

固氮菌突变种DJ35钼铁蛋白和UW3细菌铁蛋白的纯化、特性、晶体生长及鉴定

一、棕色固氮菌突变种DJ35固氮酶钼铁蛋白的纯化、体外重组及结晶研究 　　棕色固氮菌(Azotobacter vinelandii Lipmann)突变种DJ35的菌体破碎后，所得的未经加热的粗提物经DEAE Cellulose 52柱层析后得到部分纯的钼铁蛋白（ΔnifE Av1）和铁蛋白(Av2)。部分纯的ΔnifE Av1再经Sephacryl S-300和Q-Sepharose Fast Flow柱层析进一步纯化，便首次得到SDS凝胶电泳检测为基本纯的ΔnifE Av1。SDS-PAGE及Western blotting的结果表明，ΔnifE Av1具有与野生型棕色固氮菌钼铁蛋白(OP Av1)相同的亚基种类和组成（α2β2）。质子还原活性测定表明，在与Av2进行活性互补时ΔnifE Av1不具有明显的质子还原活性，而与从OP Av1抽提出的FeMoco抽提液保温后便可与Av2实现活性互补。这表明，ΔnifE Av1是一种缺失FeMoco的钼铁蛋白。 　　将ΔnifE Av1用过量的邻菲啰啉(o-phenanthroline)厌氧处理并经Sephadex G-25柱层析分离后，便得到部分丢失Fe的ΔnifE Av1©。在同时存在Av2和MgATP发生系统的条件下，ΔnifE Av1©, 而不是处理前的ΔnifE Av1，可为由KMnO4或Na2CrO4、高柠檬酸铁、Na2S、Na2S2O4 和二硫苏糖醇组成的含Mn或含Cr重组液(RS-Mn或RS-Cr)显著激活，但在缺少MgATP或Av2的条件下，RS-Mn和RS-Cr则不能激活ΔnifE Av1©。这就表明，RS-Mn和RS-Cr对ΔnifE Av1©的激活都需要邻菲啰啉的预处理及Av2和MgATP的同时存在。从分别缺失nifZ和nifB点突变的固氮菌突变种DJ194和UW45中纯化得到的钼铁蛋白，ΔnifZ Av1和NifB- Av1，经邻菲啰啉厌氧处理并经Sephadex G-25柱层析分离后，也分别得到部分丢失Fe的ΔnifZ Av1©和NifB- Av1©。与ΔnifE Av1©一样，这两种蛋白在Av2和MgATP同时存在时也可被RS-Cr和含Mo重组液（RS-Mo）明显激活。 　　为获得可供X-射线衍射的ΔnifE Av1的大单晶，对组成蛋白质沉淀剂的各种化合物的种类和浓度、缓冲液的pH值、结晶方法及蛋白样品的批次、浓度等结晶条件进行了大量优化研究。首次获得了ΔnifE Av1的深棕色短斜四棱柱晶体，并对其蛋白组成进行了鉴定。 二、铬铁蛋白中残存的棕色固氮菌细菌铁蛋白的晶体生长及鉴定 　　从无钼、无氨而含铬的固氮培养基中生长的棕色固氮菌突变种UW3中纯化得到了部分纯的CrFe蛋白。在试图培养CrFe蛋白大晶体时发现，棕色晶体和砖红色晶体可同时或单独出现。SDS-和厌氧天然-PAGE皆表明，棕色晶体主要由与Av1类似大小的亚基（~60 kD）组成，而砖红色晶体则主要由~20 kD亚基组成。Western-blotting表明只有~60 kD亚基可与OP Av1的抗体发生反应，而~20 kD亚基则无这种反应。在部分纯的CrFe蛋白中，~20 kD的蛋白含量远低于~60 kD蛋白的含量，表明由这种小亚基组成的蛋白只是CrFe蛋白中的一种污染蛋白。用3,5-二氨基苯甲酸染色的天然电泳表明，形成砖红色和棕色晶体的蛋白是迁移率不同的两种含铁蛋白。质谱分析表明，该晶体蛋白为棕色固氮菌的细菌铁蛋白（AvBF）。分辨率为2.34 Å的X-射线衍射结果也表明，砖红色晶体属于H3空间群，晶胞参数为a = 124.965 Å, b= 124.965 Å 和 c = 287.406 Å。首次完成的结构解析也表明，这种砖红色晶体确为24聚体的AvBF。 关键词：棕色固氮菌突变种DJ35和UW3; ΔnifE Av1; 铬铁蛋白; 细菌铁蛋白; 纯化和特性; 体外激活组装; 晶体生长及组成鉴定

Studies on the biochemical composition of some freshwater fishes. Pt. 2. Liver

Although considerable work has been done on the composition of fish liver oils, most of which includes the study of various vitamins and fatty acids, little attention has been paid towards the composition of fish liver as a whole.

Analysis of the piston ring/liner oil film development during warm-up for an SI-engine

A one-dimensional ring-pack lubrication model developed at MIT is applied to simulate the oil film behavior during the warm-up period of a Kohler spark ignition engine [1]. This is done by making assumptions for the evolution of the oil temperatures during warm-up and that the oil control ring during downstrokes is fully flooded. The ring-pack lubrication model includes features such as three different lubrication regimes, i.e. pure hydrodynamic lubrication, boundary lubrication and pure asperity contact, non-steady wetting of both inlet and outlet of the piston ring, capability to use all ring face profiles that can be approximated by piece-wise polynomials and, finally, the ability to model the rheology of multi-grade oils. Not surprisingly, the simulations show that by far the most important parameter is the temperature dependence of the oil viscosity. This dependence is subsequently examined further by choosing different oils. The baseline oil is SAE 10W30 and results are compared to those using the SAE 30 and the SAE 10W50 oils.

Comparison of stabilised/solidified mixes of model drill cuttings based on the North Sea and Red Sea Areas

Following the global stringent legislations regulating the wastes generated from the drilling process of oil exploration and production activities, the management of hazardous drill cuttings has become one of the pressing needs confronting the petroleum industry. Most of the prevalent treatment techniques adopted by oil companies are extremely expensive and/or the treated product has to be landfilled without any potential end-use; thereby rendering these solutions unsustainable. The technique of stabilisation/solidification is being investigated in this research to treat drill cuttings prior to landfilling or for potential re-use in construction products. Two case studies were explored namely North Sea and Red Sea. Given the known difficulties with stabilising/solidifying oils and chlorides, this research made use of model drill cutting mixes based on typical drill cutting from the two case studies, which contained 4.2% and 10.95% average concentrations of hydrocarbons; and 2.03% and 2.13% of chlorides, by weight respectively. A number of different binders, including a range of conventional viz. Portland cement (PC) as well as less-conventional viz. zeolite, or waste binders viz. cement kiln dust (CKD), fly ash and compost were tested to assess their ability to treat the North Sea and Red Sea model drill cuttings. The dry binder content by weight was 10%, 20% and 30%. In addition, raw drill cuttings from one of the North Sea offshore rigs were stabilised/solidified using 30% PC. The characteristics of the final stabilised/solidified product were finally compared to those of thermally treated cuttings. The effectiveness of the treatment using the different binder systems was compared in the light of the aforementioned two contaminants only. A set of physical tests (unconfined compressive strength (UCS)), chemical tests (NRA leachability) and micro-structural examinations (using scanning electron microscopy (SEM), and X-ray diffraction (XRD)) were used to evaluate the relative performance of the different binder mixes in treating the drill cuttings. The results showed that the observed UCS covered a wide range of values indicating various feasible end-use scenarios for the treated cuttings within the construction industry. The teachability results showed the reduction of the model drill cuttings to a stable non-reactive hazardous waste, compliant with the UK acceptance criteria for non-hazardous landfills: (a) by most of the 30% and 20% binders for chloride concentrations, and (b) by the 20% and 30% of compost-PC and CKD-PC binders for the Red Sea cuttings. The 20% and 30% compost-PC and CKD-PC binders successfully reduced the leached oil concentration of the North Sea cuttings to inert levels. Copyright 2007, Society of Petroleum Engineers.

Purification and properties of Aspartate aminotransferase (E.C. 2.6.1.1) from skeletal muscle of Cirrhina mrigala

Aspartate aminotransferase (E.C. 2.6.1.1.) from the skeletal muscle of fresh water fish Cirrhina mrigala has been purified 40 fold by ammonium sulphate fractionation, adsorption on alumina Csub(8) gel and chromatography using DEAE-cellulose column and the properties of the purified enzyme studied. The pH optimum of the enzyme is 7.8. The Km value of aspartic acid and 2-oxoglutaric acid are found to be 2.8 x 10sub(-3) M and 1.0 x 10sub(-4) M respectively. The activity of enzyme is inhibited by p-chloromercurybenzoate, hydroxylamine hydrochloride and sodium cyanide. The inhibition by pchloromercurybenzoate is reversed by reduced glutathione, B-mercaptoethanol and cysteine. Dicarboxylic acids such as maleic acid, malic acid and succinic acid inhibit the enzyme activity. The enzyme is not activated by any of the metal ions tested and heavy metal ions such as mercury and silver strongly inhibit the enzyme activity.

Physics in fish processing technology

To design, develop and put into operation an equipment either to increase the productivity or to improve the existing technique to obtain a better quality of the product, the fishery engineer/scientist should have a comprehensive knowledge of fundamental principles involved in the process. Many a technique in fish processing technology, whether it applies to freezing, dehydration or canning, involves always a type of heat transfer, which is dependent to a certain extent on the external physical parameters like temperature. humidity, pressure, air flow etc. and also on the thermodynamic properties of fish muscle in the temperature ranges encountered. Similarly informations on other physical values like dielectric constant and dielectric loss in the design of quick trawlers and in quality assessment of frozen/iced fish, refractive index and viscosity in the measurement of the saturation and polymerisation of fish oils and shear strength in the judgement of textural qualities of cooked fish are also equally important.

A review on oil sardine 3. Oil and meal industry

The author reviews the advances in the oil and meal industries related to the oil sardine fishery (Sardinella longiceps) since the 1920s. Data on the production of by-produced produced in Kerala over the period 1964- 69 are tabulated. Details of the properties of the commercial oil are given, and the values compared to those for other similar oils. The use of oil sardine for industrial purposes - the oil has been used to cure leather, temper metals and as fungicides or insecticides - and the production of fish meal and fish protein concentrate is considered.

Structural and functional properties of the hemoglobin components from the Caspian Sea Acipenser persicus and Acipenser stellatus

Hemoglobin (Hb) variability is a commonly used index of phylogenetic differentiation and molecular adaptation in fish. In the current study, the structural and functional characteristics of Hbs from two Sturgeon species of the Southern Caspian Sea Basin were investigated. After extraction and separation of hemoglobin from whole blood , the polyacrylamide gel electrophoresis (SDSPAGE), native-PAGE and isoelectric focusing (IEF) were used to confirm Hb variability in these fishes. Ion-exchange on CM-cellulose chromatography was used for purification of the dominant Hbs from these fishes. The accuracy of the methods was confirmed by IEF and SDS-PAGE. Spectral studies using fluorescence spectrophotometery, circular dichroism spectropolarimetry (CD) analysis and UV–vis spectrophotometery. Oxygen affinities of these Hbs were compared using Hb-oxygen dissociation curves. Also, the dominant Hbs from these blood fishes were utilized for further experiments. The behavior of Hbs during the denaturation process by n-dodecyl trimethylammonium bromide (DTAB) is investigated by UV–vis spectrophotometer and circular dichroism spectropolarimetry. The thermal denaturation properties of the Hbs wereinvestigated by differential scanning calorimetry (DSC) and Hbs aggregation performed chemically in the presence of dithiotreitol (DTT) by UV–vis spectrophotometer and chemometric study. The results demonstrate a significant relationship between stability of fish hemoglobins and the ability of fish for entering to deeper depths. The UV–Vis absorption spectra identified species of hemoglobin and showed the concentration of oxyHb and metHb decreases and deoxyHb increases upon interaction with DTAB. Besides the UV–vis spectrophotometry, the interaction of DTAB with hemoglobins has been studied using circular dichroism spectropolarimetry analysis. This experiment was utilized to measure the unfolding mechanism and compared alpha-helix secondary structure under different conditions for Hbs. The results reveal that the Acipenser stellatus Hb in comparison with Acipenser persicus Hb has more stability and more structural compactness. Besides, the results confirm the hypothesis that there is a meaningful relation between average habitat depth, partial oxygen pressure, oxygen affinity, structural compactness of Hb, and its stability.