Strategies to Optimize Biosensors Based on Impedance Spectroscopy to Detect Phytic Acid Using Layer-by-Layer Films

Impedance spectroscopy has been proven a powerful tool for reaching high sensitivity in sensor arrays made with nanostructured films in the so-called electronic tongue systems, whose distinguishing ability may be enhanced with sensing units capable of molecular recognition. In this study we show that for optimized sensors and bio-sensors the dielectric relaxation processes involved in impedance measurements should also be considered, in addition to an adequate choice of sensing materials. We used sensing units made from layer-by-layer (LbL) films with alternating layers of the polyeletrolytes, poly(allylamine) hydrochloride (PAH) and poly(vinyl sulfonate) (PVS), or LbL films of PAH alternated with layers of the enzyme phytase, all adsorbed on gold interdigitate electrodes. Surprisingly, the detection of phytic acid was as effective in the PVS/PAH sensing system as with the PAH/phytase system, in spite of the specific interactions of the latter. This was attributed to the dependence of the relaxation processes on nonspecific interactions such as electrostatic cross-linking and possibly on the distinct film architecture as the phytase layers were found to grow as columns on the LbL film, in contrast to the molecularly thin PAH/PVS films. Using projection techniques, we were able to detect phytic acid at the micromolar level with either of the sensing units in a data analysis procedure that allows for further optimization.

Triple Structural Transition below Room Temperature in the Antifilarial Drug Diethylcarbamazine Citrate

A very unusual triple structural transition pattern below room temperature was observed for the antifilarial drug diethylcarbamazine citrate. Besides the first thermal, crystallographic, and vibrational investigations of this first-line drug used in clinical treatment for lymphatic filariasis, a noteworthy behavior with three structural transformations as a function of temperature was demonstrated by differential scanning calorimetry, Raman spectroscopy, and single-crystal X-ray diffractometry. Our X-ray data on single crystals allow for a complete featuring and understanding of all transitions, since the four structures associated with the three solid-solid phase transformations were accurately determined. Two of three structural transitions show an order-disorder mechanism and temperature hysteresis with exothermic peaks at 224 K (T(1)`) and 213 K (T(2)`) upon cooling and endothermic ones at 248 K (T(1)) and 226 K (T(2)) upon heating. The other transition occurs at 108 K (T(3)) and it is temperature-rate sensitive. Molecular displacements onto the (010) plane and conformational changes of the diethylcarbamazine backbone as a consequence of the C-H center dot center dot center dot N hydrogen bonding formation/cleavage between drug molecules explain the mechanism of the transitions at T(1)`/T(2). However, such changes are observed only on alternate columns of the drug intercalated by citrate chains, which leads to a doubling of the lattice period along the a axis of the 235 K structure with respect to the 150 and 293 K structures. At T(2)`/T(1), these structural alterations occur in all columns of the drug. At T(3), there is a rotation on the axis of the N-C bond between the carbamoyl moiety and an ethyl group of one crystallographically independent diethylcarbamazine molecule besides molecular shifts and other conformational alterations. The impact of this study is based on the fascinating finding in which the versatile capability of structural adaptation dependent on the thermal history was observed for a relatively simple organic salt, diethylcarbamazine citrate.

Columnar joints in the Patino Formation sandstones, Eastern Paraguay: a dynamic interaction between dyke intrusion, quartz dissolution and cooling-induced fractures

The Patino Formation sandstones, which crop out in Aregua neighborhood in Eastern Paraguay and show columnar joints near the contact zone with a nephelinite dyke, have as their main characteristics the high proportion of syntaxial quartz overgrowth and a porosity originated from different processes, initially by dissolution and later by partial filling and fracturing. Features like the presence of floating grains in the syntaxial cement, the transitional interpenetrative contact between the silica-rich cement and grains as well as the intense fracture porosity are strong indications that the cement has been formed by dissolution and reprecipitation of quartz from the framework under the effect of thermal expansion followed by rapid contraction. The increase of the silica-rich cement towards the dyke in association with the orthogonal disposition of the columns relative to dyke walls are indicative that the igneous body may represent the main heat source for the interstitial aqueous solutions previously existing in the sediments. At macroscopic scale, the increasing of internal tensions in the sandstones is responsible for the nucleation of polygons, leading to the individualization of prisms, which are interconnected by a system of joints, formed firstly on isotherm surfaces of low temperature and later on successive adjacent planes towards the dyke heat source.

Algorithms for two-dimensional cutting stock and strip packing problems using dynamic programming and column generation

We investigate several two-dimensional guillotine cutting stock problems and their variants in which orthogonal rotations are allowed. We first present two dynamic programming based algorithms for the Rectangular Knapsack (RK) problem and its variants in which the patterns must be staged. The first algorithm solves the recurrence formula proposed by Beasley; the second algorithm - for staged patterns - also uses a recurrence formula. We show that if the items are not so small compared to the dimensions of the bin, then these algorithms require polynomial time. Using these algorithms we solved all instances of the RK problem found at the OR-LIBRARY, including one for which no optimal solution was known. We also consider the Two-dimensional Cutting Stock problem. We present a column generation based algorithm for this problem that uses the first algorithm above mentioned to generate the columns. We propose two strategies to tackle the residual instances. We also investigate a variant of this problem where the bins have different sizes. At last, we study the Two-dimensional Strip Packing problem. We also present a column generation based algorithm for this problem that uses the second algorithm above mentioned where staged patterns are imposed. In this case we solve instances for two-, three- and four-staged patterns. We report on some computational experiments with the various algorithms we propose in this paper. The results indicate that these algorithms seem to be suitable for solving real-world instances. We give a detailed description (a pseudo-code) of all the algorithms presented here, so that the reader may easily implement these algorithms. (c) 2007 Elsevier B.V. All rights reserved.

Fluorimetric determination of intra- and extracellular free amino acids in the microalgae Tetraselmis gracilis (Prasinophyceae) using monolithic column in reversed phase mode

This paper describes the development and application of an RP HPLC method using a C(18) monolithic stationary phase for the separation and quantification of extra- and intracellular amino acids in a batch cultivation of the marine alga Tetraselmis gracilis. Fluorimetric detection was made after separation of the o-phthaldialdehyde 2-mercaptoethanol (OPA-2MCE) derivatives using a binary gradient elution. Separation of 19 amino acids was achieved with resolution >1.5 in about 39 min at a flow rate of 1.5 mL/min. RSD of analyses in seawater medium ranged from 0.36% for Orn (0.50 mu mol/L) to 12% for Ile (0.10 mu mol/L). The main constituents of the intracellular dissolved free amino acids (DFAAs) in the exponential growth phase were arginine (Arg), asparagine (Asn), alanine (Ala), aspartic acid (Asp), glutamic acid (Glu), serine (Ser), glycine (Gly), glutamine (Gln), and leucine (Leu). The major amino acids excreted to the media were valine (Val), Ala, Ser, and Gly. The monolithic phase facilitates the analysis by shortening the separation time and saving solvents and instrumentation costs (indeed conventional HPLC instrumentation can be used, running at lower pressures than those ones used with packed particle columns).

Purification and partial characterization of a midgut membrane-bound alpha-glucosidase from Quesada gigas (Hemiptera: Cicadidae)

Adults of Quesada gigas (Hemiptera: Cicadidae) have a major alpha-glucosidase bound to the perimicrovillar membranes, which are lipoprotein membranes that surround the midgut cell microvilli in Hemiptera and Thysanoptera. Determination of the spatial distribution of alpha-glucosidases in Q. gigas midgut showed that this activity is not equally distributed between soluble and membrane-bound isoforms. The major membrane-bound enzyme was solubilized in the detergent Triton X-100 and purified to homogeneity by means of gel filtration on Sephacryl S-100, and ion-exchange on High Q and Mono Q columns. The purified alpha-glucosidase is a protein with a pH optimum of 6.0 against the synthetic substrate p-nitrophenyl alpha-D-glucoside and M(r) of 61,000 (SDS-PAGE). Taking into account V(Max)/K(M) ratios, the enzyme is more active on maltose than sucrose and prefers oligomaltodextrins up to maltopentaose, with lower efficiency for longer chain maltodextrins. The Q gigas alpha-glucosidase was immunolocalized in perimicrovillar membranes by using a monospecific polyclonal antibody raised against the purified enzyme from Dysdercus peruvianus. The role of this enzyme in xylem fluid digestion and its possible involvement in osmoregulation is discussed. (C) 2009 Elsevier Inc. All rights reserved.

External polyacrylate-coating as alternative material for preparation of photopolymerized sol-gel monolithic column

Photopolymerized sol-gel monolithic columns for use in capillary electrochromatography were prepared in 125 mu m i.d. polyacrylate-coated fused-silica capillaries. The polyacrylate-coating, unlike the polyimide one, is transparent to the radiation used (approximate to 370 nm), and thus, no coating removal is necessary. This is a very important particularity since intrinsic capillary column characteristics, such as flexibility and mechanical resistance, are unchanged. A mixture containing metacryloxypropyltrimethoxysilane (MPTMS) as the polymeric precursor, hydrochloric acid as the catalyst, toluene as the porogen and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819) as the photoinitiator was irradiated at 370 nm for 20 min inside the capillaries to prepare the columns through sol-gel approach. The versatility and viability of the use of polyacrilate as a new capillary external coating were shown through preparation of two columns under different conditions, which were tested in electrochromatography for separation of standard mixture containing thiourea (marker compound), propylbenzene, phenanthrene and pyrene. (C) 2008 Elsevier B.V. All rights reserved.

Molecular mass distribution of dextran in Brazilian sugar and insoluble deposits of cachaca

The dextran molecular mass distribution profile in 77 sugar samples from Brazil and twelve insoluble deposits (alcoholic flocks) samples from sugared cachacas (Brazilian sugar cane spirit) is described in terms of number-average molecular mass M,,, weight-average molecular mass M(w), Z-average molecular mass M,, and polydispersity. The analyses were performed by size-exclusion chromatography, using a refractive index detector. In most of the sugar samples, it was possible to identify two major groups of dextrans with Mw averages of 5 x 10(6) and 5 x 10(4) Da. Based on the evaluated parameters, the dextran distribution profile is about the same in samples analyzed over five seasons, and, therefore, it is likely that the Brazilian product pattern will not change very much over the years. In insoluble deposits from sugared cachacas, dextrans with Mw values in the order of the 10(5) Da were the most frequent ones, being present in 58% of the samples. (c) 2008 Elsevier Ltd. All rights reserved.

Removal of Zn(2+) from Electroplating Wastewater Using Modified Wood Sawdust and Sugarcane Bagasse

This paper describes the preparation of new adsorbents derived from sugarcane bagasse and wood sawdust (Manilkara sp.) to remove zinc (II) ions from electroplating wastewater. The first part deals with the chemical modification of sugarcane bagasse and wood sawdust, using succinic anhydride to introduce carboxylic acid functions into the material. The obtained materials (modified sugarcane bagasse MB2 and modified wood sawdust MS2) were then characterized by infrared spectroscopy (IR) and used in adsorption experiments. The adsorption experiments evaluates Zn(2+) removal from aqueous single metal solution and real electroplating wastewater on both batch and continuous experiments using fixed-bed columns prepared in laboratorial scale with the obtained adsorbents. Adsorption isotherms were then developed using Langmuir model and the Thomas kinetic model. The calculated Zn(2+) adsorption capacities were found to be 145 mg/g for MS2 and 125 mg/g for MB2 in single metal aqueous solution, whereas for the industrial wastewater these values were 61 mg/g for MS2 and 55 mg/g for MB2.

Layout och typografi i vetenskapliga artiklar : En kartläggning av konventioner gällande grafisk formgivning inom matematik, medicin och utbildningsvetenskap

En deskriptiv visuell innehållsanalys genomfördes med en korpus bestående av vetenskapliga artiklar från 30 topprankade tidskrifter jämnt fördelade på de tre disciplinerna matematik, medicin och utbildningsvetenskap, med syfte att undersöka om det fanns ett samband mellan tidskrifternas disciplintillhörighet och den grafiska formgivningen. Kartläggningen omfattade layout (bl.a. sidformat, spalter, marginalstorlek, användning av grafiska element, placering av tabeller, figurer och pagina) och typografiskt utseende hos titel, rubriker, brödtext och abstrakt (t.ex. teckenstorlek, textjustering, teckengrovlek, typsnitt, färg och radavstånd). Resultaten visar att disciplinerna använde olika men även gemensamma konventioner i sitt grafiska utseende. Matematik uppvisade enkelspaltig layout med liten typografisk variation, genomgående användning av typsnitt från familjen Transitional eller Transitional/Didone för hela dokumentet, avsaknad av kulört färg och sällan användning av grafiska element. Medicin uppvisade större variation med användning av kulört färg, icke-centrerad typografi med både sansseriff- och seriff-typsnitt, grafiska element och ramar som förstärker det ofta använda dubbelspaltiga gridsystemet. Utbildningsvetenskap uppvisade en grafisk design som återfanns i båda disciplinerna, men påminde mest om matematik till utseendet. Kodbok ingår i sin helhet som bilaga. Uppsatsen i sig är delvis formgiven med utgångspunkt i de erhållna resultaten.

Of Facebook, Twitter and Social Networking Sites

For those who have read even one of my musings, it will come as no surprise that I find Facebook, Twitter, social networking sites (SNS), and the rest of Webology less than inspiring. If you had read nothing other than the screed I blathered about Google a few columns back, you’d know that I find all this talk about the Web replacing libraries more than a little silly; I find it downright idiotic. Still, one must keep an open mind.

Dimensionamento de pilares esbeltos de concreto armado

O objetivo deste trabalho é o dimensionamento de pilares esbeltos de concreto armado, sob cargas de curta e longa duração, baseado numa análise realística das deformações do mesmo. Apresenta-se três algoritmos numéricos para a obtencão das relações momento fletor-esforço normal-curvatura de uma seção arbitrária de concreto armado, sob flexo-compressão normal. Inclue-se as deformações específicas de fluência e retração do concreto na análise, através de uma alteração nas referidas relações. Apresenta-se alguns critérios de normas, relativos ao dimensionamento de pilares esbeltos de concreto armado e uma comparação dos mesmos, entre si e com o algoritmo numérico desenvolvido. Considerações da NB-1/78 relativas ao projeto de pilares são analisadas, verificando o nivel da precisão obtida. Um procedimento simplificado para a inclusão da fluência do concreto no dimensionamento, proposto pelo CEB, é testado e uma solução para pilares de concreto armado com engastamento elástico simétrico é apresentada, para verificar o nível: do erro cometido ao se estender o conceito de comprimento de flambagem a pilares de concreto armado. Uma série de exemplos experimentais são apresentados, onde a solução numérica para o dimensionamento tem sua precisão verificada. Diversas tabelas foram desenvolvidas para o dimensionamento de pilares esbeltos com secão transversal retangular e armadura simétrica. Todo o estudo é restrito ao caso de flexo-compressão normal.

Analise de estruturas de edificios altos submetidos a carregamentos horizontais e verticais

O presente trabalho tem como objetivo analisar os esforços em estruturas tridimensionais de edificios altos, quando submetidos a carregamentos horizontais e verticais. A estrutura é idealizada como um conjunto de pilares, paredes e vigas podendo ser dispostos de uma maneira assimétrica no plano da laje e variarem suas propriedades geométricas ao longo da altura. A análise é feita pelo método dos deslocamentos. Admite-se que as lajes em cada nível dos pavimentos tenham o funcionamento de diafragma rígido. São utilizados elementos de barra para representação das vigas e pilares. Para a determinação dos esforços em paredes resistentes são apresentados vários elementos obtidos pela analogia de pórticos. Tais elementos são incorporados ao programa possuindo uma formulação bem simples.

Avaliação de processo do Programa de Regionalização do Turismo em 65 municípios turísticos brasileiros

Este estudo apresenta uma pesquisa realizada em 65 municípios turísticos brasileiros, no período de dezembro de 2007 a fevereiro de 2008, cujo objetivo é avaliar a implementação do Programa de Regionalização do Turismo nesses municípios. Este programa é o eixo principal das políticas públicas do turismo brasileiro, lançado pelo Ministério do Turismo em 2004. Para compreensão dessa política pública do turismo, realizou-se uma pesquisa documental nos arquivos do Ministério do Turismo, neste descrevem-se o Plano Nacional de Turismo (2003-2007) e o Programa de Regionalização do Turismo; também se realizou uma revisão de literatura sobre os princípios e conceitos em que se alicerça o programa: descentralização participativa, integração, sustentabilidade e a elaboração de uma matriz para avaliação de processo utilizada neste trabalho. Faziam parte da pesquisa as 27 capitais estaduais, o Distrito Federal e mais 37 municípios localizados em consolidados destinos turísticos (Floresta Amazônica, Pantanal Mato-grossense, Serras Gaúchas, Cidades Históricas de Minas, Litoral do Nordeste e outros). Por meio da pesquisa de campo e observação sistemática in loco, 23 pesquisadores coletaram informações dos gestores de turismo locais, utilizando-se de formulários fechados. Estes formulários forma elaborados tendo em vista os objetivos dos nove módulos operacionais previstos no Programa de Regionalização do Turismo e seus indicadores de resultados previamente determinados. As respostas, depois da tabuladas e calculadas suas frequências, foram transformadas em gráficos de colunas para fornecer uma visão clara da atual situação do programa em relação à sua implementação nos municípios. Analisando os resultados, obteve-se que, dos nove módulos do programa, quatro foram implementados com eficácia restrita nos municípios, necessitando de ajustes em suas ações operacionais, por parte dos municípios; outros quatro módulos alcançaram resultados mais modestos quanto à sua implementação, demandando melhor acompanhamento e correções por conta dos gestores de turismo; e um módulo teve resultado ineficaz, pois foi implementado em apenas sete municípios, este sim, merecendo maior atenção na sua estruturação, nos seus objetivos, competências delegadas e estratégias. Confrontando esses resultados com a revisão teórica aqui levantada, verificou-se que o processo descentralizador aflorou a fragilidade dos municípios que não cumprem com suas atribuições previstas no programa; evidenciou-se uma fraca integração entre municípios e entre setores público/privado, no sentido de formarem ¿redes¿ de relacionamento e mostrou que o principal programa público de turismo do Brasil está carente de monitoramento e avaliação.

O efeito da carga compressiva repetitiva sobre a placa de crescimento : estudo experimental em ratos

Os impactos repetitivos decorrentes do esporte podem interferir no crescimento ósseo. Com o objetivo de tentar elucidar o efeito mecânico dos impactos repetitivos sobre a placa de crescimento ósseo, da tíbia proximal, um estudo experimental em ratos foi realizado. Inicialmente, foi desenvolvida uma máquina para a produção de impactos repetitivos na tíbia dos ratos. Os impactos repetitivos foram produzidos na tíbia direita em uma amostra de 60 ratos wistar, divididos em 6 grupos de 10 cada, sendo a esquerda o controle. A magnitude de impacto foi de aproximadamente 3,5 vezes a massa corporal dos ratos. Após os dias de impacto, os ratos foram sacrificados e as tíbias foram medidas. Em seguida um estudo histológico da placa de crescimento foi realizado. Foram medidas, a espessura total da placa de crescimento, a espessura da zona de repouso, de proliferação e hipertrófica e de calcificação juntas. Os resultados mostraram diferença significativa no comprimento da tíbia nos testes intra-grupos para os grupos 3, 4,e 5 (p≤0,05), e intergrupos para a tíbia direita e esquerda (p≤0,05). A placa de crescimento mostrou uma menor espessura significativa na tíbia direita (p≤0,05). Na esquerda não houve alteração significativa da espessura da placa (p=0,109). As zonas de repouso e proliferativa da placa da tíbia direita, e o número médio de células nas colunas da zona proliferativa apresentaram diferenças significativas intergrupos (p= 0,013, p=0,042 e p=0,017, respectivamente). As zonas hipertrófica e de calcificação apresentaram diferença significativas nas tíbias direita e esquerda (p 0,048 e 0=0,020, respectivamente). As análises múltiplas confirmaram que não existiram evidências de calcificação precoce da placa, com a magnitude de impacto produzida. Não houve mudança significativa nas zonas hipertrófica e de calcificação. A conclusão é de que os impactos repetitivos diminuem a espessura da placa de crescimento proximal da tíbia durante a puberdade, principalmente quando o tempo de impacto ultrapassa a metade do período de puberdade. Com a interrupção de 10 dias na produção dos impactos, permaneceu a diminuição da espessura da placa proximal da tíbia. A cargas de impactos de aproximadamente 3,5 vezes a massa corporal não são suficientes para exibir evidências de calcificação precoce da placa de crescimento.