Isolation of lignans glycosides from Alibertia sessilis (Vell.) K. Schum. (Rubiaceae) by preparative high-performance liquid chromatography

Enantiomeric aglycone lignans contained in a mixture were separated from a fraction of the extract of the stems of Alibertia sessilis (Vell.) K. Schum. (Rubiaceae) by preparative high-performance liquid chromatography. An efficient and fast separation can be achieved with methanol-water (30:70, v/v). Their structures were identified as (+)-lyoniresinol 3alpha-O-beta-glucopyranoside and (-)-lyoniresinol 3alpha-O-beta-glucopyranoside, being reported for the first time in Rubiaceae.

Biheterocyclic ligands: synthesis, characterization and coordinating properties of bis(4-amino-5-mercapto-1,2,4-triazol-3-yl) alkanes with transition metal ions and their thermokinetic and biological studies

The Co(II), Ni(II) and Cu(II) metal ions complexes of Bis(4-amino-5-mercapto-1,2,4-triazol-3-yl) alkanes (BATs) have been prepared and characterized by elemental analysis, conductivity measurements infrared, magnetic susceptibility, the electronic spectral data and thermal studies. Based on spectral and magnetic results, the ligands are tetradentate coordinating through the N and S-atoms of BATs; six-coordinated octahedral or distorted octahedral and some times four-coordinated square planar were proposed for these complexes. Activation energies computed for the thermal decomposition steps were compared. The ligands and their metal complexes were tested in vitro for their biological effects. Their activities against two gram-positive, two gram-negative bacteria and two fungal species were found to vary from moderate to very strong.

Kinetic modeling of mechanisms of industrially important organic reactions in gas and liquid phase

This dissertation is based on 5 articles which deal with reaction mechanisms of the following selected industrially important organic reactions: 1. dehydrocyclization of n-butylbenzene to produce naphthalene 2. dehydrocyclization of 1-(p-tolyl)-2-methylbutane (MB) to produce 2,6-dimethylnaphthalene 3. esterification of neopentyl glycol (NPG) with different carboxylic acids to produce monoesters 4. skeletal isomerization of 1-pentene to produce 2-methyl-1-butene and 2-methyl-2-butene The results of initial- and integral-rate experiments of n-butylbenzene dehydrocyclization over selfmade chromia/alumina catalyst were applied when investigating reaction 2. Reaction 2 was performed using commercial chromia/alumina of different acidity, platina on silica and vanadium/calcium/alumina as catalysts. On all catalysts used for the dehydrocyclization, major reactions were fragmentation of MB and 1-(p-tolyl)-2-methylbutenes (MBes), dehydrogenation of MB, double bond transfer, hydrogenation and 1,6-cyclization of MBes. Minor reactions were 1,5-cyclization of MBes and methyl group fragmentation of 1,6- cyclization products. Esterification reactions of NPG were performed using three different carboxylic acids: propionic, isobutyric and 2-ethylhexanoic acid. Commercial heterogeneous gellular (Dowex 50WX2), macroreticular (Amberlyst 15) type resins and homogeneous para-toluene sulfonic acid were used as catalysts. At first NPG reacted with carboxylic acids to form corresponding monoester and water. Then monoester esterified with carboxylic acid to form corresponding diester. In disproportionation reaction two monoester molecules formed NPG and corresponding diester. All these three reactions can attain equilibrium. Concerning esterification, water was removed from the reactor in order to prevent backward reaction. Skeletal isomerization experiments of 1-pentene were performed over HZSM-22 catalyst. Isomerization reactions of three different kind were detected: double bond, cis-trans and skeletal isomerization. Minor side reaction were dimerization and fragmentation. Monomolecular and bimolecular reaction mechanisms for skeletal isomerization explained experimental results almost equally well. Pseudohomogeneous kinetic parameters of reactions 1 and 2 were estimated by usual least squares fitting. Concerning reactions 3 and 4 kinetic parameters were estimated by the leastsquares method, but also the possible cross-correlation and identifiability of parameters were determined using Markov chain Monte Carlo (MCMC) method. Finally using MCMC method, the estimation of model parameters and predictions were performed according to the Bayesian paradigm. According to the fitting results suggested reaction mechanisms explained experimental results rather well. When the possible cross-correlation and identifiability of parameters (Reactions 3 and 4) were determined using MCMC method, the parameters identified well, and no pathological cross-correlation could be seen between any parameter pair.

Estimation of standard enthalpy of formation of alkanes in gaseous state by calculating size, structural and electronic parameters in the molecules

A quantitative analysis is made on the correlation ship of thermodynamic property, i.e., standard enthalpy of formation (ΔH fº) with Kier's molecular connectivity index(¹Xv),vander waal's volume (Vw) electrotopological state index (E) and refractotopological state index (R) in gaseous state of alkanes. The regression analysis reveals a significant linear correlation of standard enthalpy of formation (ΔH fº) with ¹Xv, Vw, E and R. The equations obtained by regression analysis may be used to estimate standard enthalpy of formation (ΔH fº) of alkanes in gaseous state.

Biochemical Modification of Thermomechanical Pulp Fibers

The first objective of this study was to find out reliable laboratory methods to predict the effect of enzymes on specific energy consumption and fiber properties of TMP pulp. The second one was to find with interactive software called “Knowledge discovery in databases” enzymes or other additives that can be used in finding a solution to reduce energy consumption of TMP pulp. The chemical composition of wood and enzymes, which have activity on main wood components were presented in the literature part of the work. The results of previous research in energy reduction of TMP process with enzymes were also highlighted. The main principles of knowledge discovery have been included in literature part too. The experimental part of the work contains the methods description in which the standard size chip, crushed chip and fiberized spruce chip (fiberized pulp) were used. Different types of enzymatic treatment with different dosages and time were tested during the experiments and showed. Pectinase, endoglucanase and mixture of enzymes were used for evaluation of method reliability. The fines content and fiber length of pulp was measured and used as evidence of enzymes' effect. The refining method with “Bauer” laboratory disc refiner was evaluated as not highly reliable. It was not able to provide high repeatability of results, because of uncontrolled feeding capacity and refining consistency. The refining method with Valley refiner did not have a lot of variables and showed stable and repeatable results in energy saving. The results of experiments showed that efficient enzymes impregnation is probably the main target with enzymes application for energy saving. During the work the fiberized pulp showed high accessibility to enzymatic treatment and liquid penetration without special impregnating equipment. The reason was that fiberized pulp has larger wood surface area and thereby the contact area between the enzymatic solution and wood is also larger. Standard size chip and crushed chip treatment without special impregnator of enzymatic solution was evaluated as not efficient and did not show visible, repeatable results in energy consumption decrease. Thereby it was concluded that using of fiberized pulp and Valley refiner for measurements of enzymes' effectiveness in SEC decrease is more suitable than normal size chip and crushed chip with “Bauer” refiner. Endoglucanase with 5 kg/t dosage showed about 20% energy consumption decrease. Mixture of enzymes with 1.5 kg/t dosage showed about 15% decrease of energy consumption during the refining. Pectinase at different dosages and treatment times did not show significant effect on energy consumption. Results of knowledge discovery in databases showed the xylanase, cellulase and pectinase blend as most promising for energy reduction in TMP process. Surfactants were determined as effective additives for energy saving with enzymes.

Variação de vazão de gotejadores de fluxo normal enterrados na irrigação de café

Este trabalho teve como objetivo obter informações sobre o desempenho de gotejadores enterrados (irrigação subsuperficial), quanto ao aspecto de variação de vazão em função da intrusão radicular da cultura do café. As mudas de café foram irrigadas por sete modelos diferentes de gotejadores de fluxo normal, instalados a duas profundidades (15 e 30 cm da superfície do solo) e em dois níveis de depleção de água no solo (tratamentos úmido e seco). O trabalho foi conduzido em vasos e sob ambiente controlado, utilizando mudas de cafeeiro em estágio inicial de desenvolvimento. Concluiu-se que, até os 120 dias do início do experimento, não houve modelo de emissor que se destacasse quanto à penetração de raízes e, a partir daí, diferenças na suscetibilidade dos modelos foram observadas, podendo-se agrupar os modelos avaliados em função do grau de redução de vazão. Os níveis de irrigação não apresentaram resultados conclusivos até 120 dias do início do experimento, porém, considerando todo o período do experimento, observaram-se evidências de que o sistema radicular é mais agressivo na camada mais profunda de solo (30 cm) e para o tratamento úmido.

Modelo dinâmico de simulação e otimização da força normal de reação do solo para um mecanismo de corte basal

O modelo físico foi baseado no método de Newton-Euler, sendo o mesmo desenvolvido utilizando o programa computacional científico Mathematica®. Realizaram-se várias simulações, nas quais se procurou obter a força normal de reação do solo variando velocidades de avanço (0,69; 1,12; 1,48; 1,82 e 2,12 m s-1); perfis de solo (senoidal, rampa ascendente e descendente) e altura do camalhão (0,025 e 0,05 m). Após as simulações iniciais, o mecanismo foi otimizado utilizando o programa computacional científico Matlab®, tendo como critério (função-objetivo) a minimização da força normal de reação do perfil (F N) e como variáveis de projeto os comprimentos das barras (L1y, L2, l3 e L4), altura da operação (L7), o comprimento inicial da mola (Lmo) e a constante elástica da mola (k t). A falta de robustez do mecanismo em relação à variável altura de operação foi contornada por meio do uso de mola com baixa rigidez e grande comprimento. Os resultados demonstraram que o mecanismo otimizado obteve desempenho de flutuação muito bom, em relação ao mecanismo inicial.

Estudo granulométrico de grãos de soja normal e transgênico

Este trabalho foi desenvolvido com o propósito de estudar o comportamento granulométrico de grãos de soja em função da variação do teor de água. A pesquisa foi realizada com seis variedades, sendo duas transgênicas e quatro comuns, com os teores de água de 10%, 12%, 15%, 20% b.s. A granulometria foi determinada utilizando-se de seis subamostras de 120 grãos para cada teor de água, e as suas dimensões (comprimento, largura e espessura) obtidas por meio de paquímetro digital. Os resultados indicaram que cada variedade de soja comportou-se de maneira diferenciada e que as comuns tiveram comportamento granulométrico diferenciado das transgênicas.

Alternative liquid biofuels for lime kilns

Causticizing plant is an important part of kraft pulp mill. It uses green liquor from recovery boiler as a raw material and consumes lime to produce white liquor, which is an important chemical used in pulping. Lime kiln is a part of the causticizing process. It is used to convert lime mud, a by-product obtained from the causticizing back to lime in high temperatures. This conversion requires a lot of energy. The most common fuels used as energy source for lime kiln are heavy fuel oil and natural gas. In a modern pulp mill lime kiln is the only user of significant amount of fossil fuels. Replacing fossil fuels with biofuels can have prominent economical and environmental benefits. Interest in using biofuels as energy source of lime kiln has become a worldwide issue in the recent years. However fuels used for lime kiln have a lot of certain requirements. The purpose of this work is to study the required characteristics from liquid fuels used in pulp mill lime kiln and to map suitable liquid biofuels already available in the markets. Also taxation of liquid biofuels compared to heavy fuel oil in Finland, Sweden and Germany is shortly introduced.

Derivação biliopancreática com preservação gástrica videolaparoscópica: sistematização técnica

BACKGROUND: The authors describe a videolaparoscopic technical variation of biliopancreatic diversion, and its rationale, as well as its preliminary results.They operated on 12 female patients, age between 26 and 49 years, BMI range 47,4 and 59,5kg/m². There were no intraoperative complications; operative time ranged from 2 to 4,5 hours; discharge in the 3rd. postoperative day. Liquid dietetic recommendations in the early period, and normal diet after the first week. One patient was readmmitted after 1 week with abdominal pain because of excessive ingestion of food; there was deep venous trombosis in one patient. Follow-up showed loss of excess weight of 27,4% after four months. Initial results of the described operation sugests it may be a good alternative to morbid obesity surgical treatment; it is strongly required a multidisciplinar pre and postoperative treatment program.

Structural modelling of liquid ZrO2 and glassy B2O3 by using AB INITIO Molecular Dynamics method

Atomic structure of ZrO2 and B2O3 was investigated in this work. New data under extreme conditions (T = 3100 K) was obtained for the liquid ZrO2 structure. A fractional number of boron was investigated for glassy structure of B2O3. It was shown that it is possible to obtain an agreement for the fractional number between NMR and DFT techniques using a suitable initial configuration.

Survey of transportation of liquid bulk chemicals in the Baltic Sea

This study is made as a part of the Chembaltic (Risks of Maritime Transportation of Chemicals in Baltic Sea) project which gathers information on the chemicals transported in the Baltic Sea. The purpose of this study is to provide an overview of handling volumes of liquid bulk chemicals (including liquefied gases) in the Baltic Sea ports and to find out what the most transported liquid bulk chemicals in the Baltic Sea are. Oil and oil products are also viewed in this study but only in a general level. Oils and oil products may also include chemical-related substances (e.g. certain bio-fuels which belong to MARPOL annex II category) in some cargo statistics. Chemicals in packaged form are excluded from the study. Most of the facts about the transport volumes of chemicals presented in this study are based on secondary written sources of Scandinavian, Russian, Baltic and international origin. Furthermore, statistical sources, academic journals, periodicals, newspapers and in later years also different homepages on the Internet have been used as sources of information. Chemical handling volumes in Finnish ports were examined in more detail by using a nationwide vessel traffic system called PortNet. Many previous studies have shown that the Baltic Sea ports are annually handling more than 11 million tonnes of liquid chemicals transported in bulk. Based on this study, it appears that the number may be even higher. The liquid bulk chemicals account for approximately 4 % of the total amount of liquid bulk cargoes handled in the Baltic Sea ports. Most of the liquid bulk chemicals are handled in Finnish and Swedish ports and their proportion of all liquid chemicals handled in the Baltic Sea is altogether over 50 %. The most handled chemicals in the Baltic Sea ports are methanol, sodium hydroxide solution, ammonia, sulphuric and phosphoric acid, pentanes, aromatic free solvents, xylenes, methyl tert-butyl ether (MTBE) and ethanol and ethanol solutions. All of these chemicals are handled at least hundred thousand tonnes or some of them even over 1 million tonnes per year, but since chemical-specific data from all the Baltic Sea countries is not available, the exact tonnages could not be calculated in this study. In addition to these above-mentioned chemicals, there are also other high volume chemicals handled in the Baltic Sea ports (e.g. ethylene, propane and butane) but exact tonnes are missing. Furthermore, high amounts of liquid fertilisers, such as solution of urea and ammonium nitrate in water, are transported in the Baltic Sea. The results of the study can be considered indicative. Updated information about transported chemicals in the Baltic Sea is the first step in the risk assessment of the chemicals. The chemical-specific transportation data help to target hazard or e.g. grounding/collision risk evaluations to chemicals that are handled most or have significant environmental hazard potential. Data gathered in this study will be used as background information in later stages of the Chembaltic project when the risks of the chemicals transported in the Baltic Sea are assessed to highlight the chemicals that require special attention from an environmental point of view in potential marine accident situations in the Baltic Sea area.

Avaliação da expressão do gene MGMT nos tecidos normal e neoplásico de doentes com câncer colorretal

OBJETIVO: Avaliar a expressão tecidual do gene de reparo MGMT comparando a mucosa cólica normal e neoplásica em doentes com câncer colorretal. MÉTODOS: Foram estudados 44 portadores de adenocarcinoma colorretal confirmado por estudo histopatológico. Foram excluídos doentes suspeitos de pertencerem a famílias com câncer colorretal hereditário (HNPCC e PAF) e os portadores de câncer do reto médio e inferior submetidos a tratamento quimioradioterápico neoadjuvante. A expressão do gene MGMT foi avaliada pela técnica da reação de polimerase em cadeia em tempo real (RT-PCR). A comparação dos resultados encontrados para expressão do gene MGMT entre tecidos normais e neoplásicos foi feita pelo teste t de Student pareado, adotando-se nível de significância de 5% (p <0,05). RESULTADOS: A expressão tecidual do gene MGMT em todos os doentes foi menor no tecido neoplásico quando comparada a do tecido normal (p=0,002). CONCLUSÃO: O gene de reparo MGMT encontra-se menos expresso no tecido neoplásico quando comparados aos tecidos normais em portadores de CCR esporádico.

Validação da curva normal de peso fetal estimado pela ultra-sonografia para o diagnóstico do peso neonatal

OBJETIVO: avaliar a concordância entre o peso fetal estimado (PFE) por ultra-sonografia e o neonatal, o desempenho da curva normal de PFE por idade gestacional no diagnóstico de desvios do peso fetal/neonatal e fatores associados. MÉTODOS: participaram do estudo 186 grávidas atendidas de novembro de 1998 a janeiro de 2000, com avaliação ultra-sonográfica até 3 dias antes do parto, determinação do PFE e do índice de líquido amniótico e parto na instituição. O PFE foi calculado e classificado de acordo com a curva de valores normais de PFE em: pequeno para a idade gestacional (PIG), adequado para a idade gestacional (AIG) e grande para a idade gestacional (GIG). A mesma classificação foi feita para o peso neonatal. A variabilidade das medidas e o grau de correlação linear entre o PFE e o peso neonatal foram calculados, bem como a sensibilidade, especificidade e valores preditivos para o uso da curva de valores normais de PFE para o diagnóstico dos desvios do peso neonatal. RESULTADOS: diferença entre o PFE e o peso neonatal variou entre -540 e +594 g, com média de +47,1 g, e as duas medidas apresentaram um coeficiente de correlação linear de 0,94. A curva normal de PFE teve sensibilidade de 100% e especificidade de 90,5% em detectar PIG ao nascimento, e de 94,4 e 92,8%, respectivamente, em detectar GIG, porém os valores preditivos positivos foram baixos para ambos. CONCLUSÕES: a estimativa ultra-sonográfica do peso fetal foi concordante com o peso neonatal, superestimando-o em apenas cerca de 47 g e a curva do PFE teve bom desempenho no rastreamento diagnóstico de recém-nascidos PIG e GIG.