Surface-enhanced Raman study of electrochemical and photocatalytic degradation of the azo dye Janus Green B

The photocatalytic degradation of Janus Green B azo dye over silver modified titanium dioxide films was investigated by surface-enhanced Raman spectroscopy (SERS). An optimized SERS-active substrate was employed to study the photodegradation reaction of Janus Green B. Considering that photocatalytic degradation processes of organic molecules adsorbed on TiO2 might involve either their oxidation or reduction reaction, the vibrational spectroelectrochemical study of the dye was also performed, in order to clarify the transformations involved in initial steps of its photochemical decomposition. In order to understand the changes in Raman spectra of Janus Green B after photodegradation and/or electrochemical processes, a vibrational assignment of the main Raman active modes of the dye was carried out, based on a detailed resonance Raman profile. Products formed by electrochemical and photochemical degradation processes were compared. The obtained results revealed that the first steps of the degradation process of Janus Green B involve a reductive mechanism. (C) 2007 Published by Elsevier B.V.

Hydrogen production by steam reforming of ethanol over Ni-based catalysts promoted with noble metals

The catalytic activity of Ni/La(2)O(3)-Al(2)O(3) Catalysts modified with noble metals(Pt and Pd) was investigated in the steam reforming of ethanol. The catalysts were characterized by ICP, S(BFT), X-ray diffraction, temperature-programmed reduction, UV-vis diffuse reflectance spectroscopy and X-ray absorption fine structure (XANES). The results showed that the formation of inactive nickel aluminate was prevented by the presence of La(2)O(3) dispersed on the alumina. The promoting effect of noble metals included a marked decrease in the reduction temperatures of NiO species interacting with the support. due to the hydrogen spillover effect, facilitating greatly the reduction of the promoted catalysts. it was seen that the addition of noble metal stabilized the Ni sites in the reduced state throughout the reaction, increasing ethanol conversion and decreasing coke formation, irrespective of the nature or loading of the noble metal. (C) 2009 Elsevier B.V. All rights reserved.

The effect of ultra-low proton concentration on the electrocatalytic reduction of nitrate over platinum

The electrocatalytic reduction of NO3- (aq) over platinum has been investigated in sulfuric acid solutions with proton concentrations between 1 mM and 50 mM. Cyclic voltammetry indicates that for [H+] < 10 mM, NO3- (aq) is reduced in two distinct regions of potential: one reduction peak occurs at approximately 0.1 V vs. RHE and one occurs at -0.13 V vs. RHE. This second reduction peak has never before been observed, and is not present for proton concentrations >10 mM, where hydrogen electroreduction prevails below 0.0 V vs. RHE. Chronoamperometry shows that the kinetics of the two reduction peaks are distinct, suggesting that the two reduction peaks may correspond to the evolution of different products. Results are discussed in the context of tuning the product selectivity of the electrocatalytic reduction of NO3- (aq). (C) 2007 Elsevier B.V. All rights reserved.

Carbon dioxide reforming of ethanol over Ni/Y(2)O(3)-ZrO(2) catalysts

Supported nickel catalysts of composition Ni/Y(2)O(3)-ZrO(2) were synthesized in one step by the polymerization method and compared with a nickel catalyst prepared by wet impregnation. Stronger interactions were observed in the formed catalysts between NiO species and the oxygen vacancies of the Y(2)O(3)-ZrO(2) in the catalysts made by polymerization, and these were attributed to less agglomeration of the NiO during the synthesis of the catalysts in one step. The dry reforming of ethanol was catalyzed with a maximum CO(2) conversion of 61% on the 5NiYZ catalyst at 800 degrees C, representing a better response than for the catalyst of the same composition prepared by wet impregnation. (C) 2009 Published by Elsevier B.V.

Determination of fluoxetine in plasma by gas chromatography-mass spectrometry using stir bar sorptive extraction

This article presents a method employing stir bar sorptive extraction (SBSE) with in situ derivatization, in combination with either thermal or liquid desorption on-line coupled to gas chromatography-mass spectrometry for the analysis of fluoxetine in plasma samples. Ethyl chloroformate was employed as derivatizing agent producing symmetrical peaks. Parameters such as solvent polarity, time for analyte desorption, and extraction time, were evaluated. During the validation process, the developed method presented specificity, linearity (R-2 > 0.99), precision (R.S.D. < 15%), and limits of quantification (LOQ) of 30 and 1.37 pg mL(-1), when liquid and thermal desorption were employed, respectively. This simple and highly sensitive method showed to be adequate for the measurement-of fluoxetine in typical and trace concentration levels. (c) 2008 Elsevier B.V. All rights reserved.

Polydimethylsiloxane/polypyrrole stir bar sorptive extraction and liquid chromatography (SBSE/LC-UV) analysis of antidepressants in plasma samples

A new polymeric coating consisting of a dual-phase, polydimethylsiloxane (PDMS) and polypyrrole (PPY) was developed for the stir bar sorptive extraction (SBSE) of antidepressants (mirtazapine, citalopram, paroxetine, duloxetine, fluoxetine and sertraline) from plasma samples, followed by liquid chromatography analysis (SBSE/LC-UV). The extractions were based on both adsorption (PPY) and sorption (PDMS) mechanisms. SBSE variables, such as extraction time, temperature, pH of the matrix, and desorption time were optimized, in order to achieve suitable analytical sensitivity in a short time period. The PDMS/PPY coated stir bar showed high extraction efficiency (sensitivity and selectivity) toward the target analytes. The quantification limits (LOQ) of the SBSE/LC-UV method ranged from 20 ng mL(-1) to 50 ng mL(-1), and the linear range was from LOQ to 500 ng mL(-1), with a determination coefficient higher than 0.99. The inter-day precision of the SBSE/LC-UV method presented a variation coefficient lower than 15%. The efficiency of the SBSE/LC-UV method was proved by analysis of plasma samples from elderly depressed patients. (C) 2008 Elsevier B.V. All rights reserved.

The hand of God is over their hands (Q. 48:10) : on the notion of covenant in al-Ṭabarī’s account of Karbalāʾ

This article is an analysis of the story of the killing of Ḥusayn b. ʿAlī at Karbalāʾ in 61/680, as it is presented by Abū Jaʿfar Muḥammad b. Jarīr al-Ṭabarī (d. 310/923). The main argument is that the notion of the divine covenant, which permeates the Qur’an, constitutes a framework through which al-Ṭabarī views this event. The Qur’anic idea of the covenant is read in structural/thematic continuity with the Hebrew Bible account of the covenant between Yahweh and the Hebrew people, which has, in turn, been traced back in its basic form to Late Bronze Era treaties between rulers and their vassals.   The present study focusses on four speeches ascribed to Ḥusayn during the encounter he and his group had with the vanguard of the Kūfan army led by al-Ḥurr. These are analysed in accordance with their use of Qur’anic covenant vocabulary. They are also categorised within the broader framework of the eight standard characteristics of Ancient West Asian and Biblical covenants, as presented by George Mendenhall and Gary Herion, which have recently been developed in a Qur’anic context by Rosalind Ward Gwynne. This article argues that al-Ṭabarī’s Karbalāʾ narrative presents the pact of loyalty to Ḥusayn as a clear extension of the divine covenant.

Type 5 Design B Port Side

Print No:24; Discontinued stamp JUN 15 1918; handwritten "DISCONTINUED. 6-19-18." handwritten note written over stamp.

Type 8 Design B Port Side

print no 121, "1B.g. no 9." printed over "Blue Grey"; Discontinued stamp JUL 23 1918

Potentialities of two solventless extraction approaches—Stir bar sorptive extraction and headspace solid-phase microextraction for determination of higher alcohol acetates, isoamyl esters and ethyl esters in wines

A stir bar sorptive extraction with liquid desorption followed by large volume injection coupled to gas chromatography–quadrupole mass spectrometry (SBSE-LD/LVI-GC–qMS) was evaluated for the simultaneous determination of higher alcohol acetates (HAA), isoamyl esters (IsoE) and ethyl esters (EE) of fatty acids. The method performance was assessed and compared with other solventless technique, the solid-phase microextraction (SPME) in headspace mode (HS). For both techniques, influential experimental parameters were optimised to provide sensitive and robust methods. The SBSE-LD/LVI methodology was previously optimised in terms of extraction time, influence of ethanol in the matrix, liquid desorption (LD) conditions and instrumental settings. Higher extraction efficiency was obtained using 60 min of extraction time, 10% ethanol content, n-pentane as desorption solvent, 15 min for the back-extraction period, 10 mL min−1 for the solvent vent flow rate and 10 °C for the inlet temperature. For HS-SPME, the fibre coated with 50/30 μm divinylbenzene/carboxen/polydimethylsiloxane (DVB/CAR/PDMS) afforded highest extraction efficiency, providing the best sensitivity for the target volatiles, particularly when the samples were extracted at 25 °C for 60 min under continuous stirring in the presence of sodium chloride (10% (w/v)). Both methodologies showed good linearity over the concentration range tested, with correlation coefficients higher than 0.984 for HS-SPME and 0.982 for SBES-LD approach, for all analytes. A good reproducibility was attained and low detection limits were achieved using both SBSE-LD (0.03–28.96 μg L−1) and HS-SPME (0.02–20.29 μg L−1) methodologies. The quantification limits for SBSE-LD approach ranging from 0.11 to 96.56 μg L−and from 0.06 to 67.63 μg L−1 for HS-SPME. Using the HS-SPME approach an average recovery of about 70% was obtained whilst by using SBSE-LD obtained average recovery were close to 80%. The analytical and procedural advantages and disadvantages of these two methods have been compared. Both analytical methods were used to determine the HAA, IsoE and EE fatty acids content in “Terras Madeirenses” table wines. A total of 16 esters were identified and quantified from the wine extracts by HS-SPME whereas by SBSE-LD technique were found 25 esters which include 2 higher alcohol acetates, 4 isoamyl esters and 19 ethyl esters of fatty acids. Generally SBSE-LD provided higher sensitivity with decreased analysis time.

Optimisation of stir bar sorptive extraction and liquid desorption combined with large volume injection-gas chromatography–quadrupole mass spectrometry for the determination of volatile compounds in wines

Stir bar sorptive extraction and liquid desorption followed by large volume injection coupled to gas chromatography–quadrupole mass spectrometry (SBSE–LD/LVI-GC–qMS) had been applied for the determination of volatiles in wines. The methodology was optimised in terms of extraction time and influence of ethanol in the matrix; LD conditions, and instrumental settings. The optimisation was carried out by using 10 standards representative of the main chemical families of wine, i.e. guaiazulene, E,E-farnesol, β-ionone, geranylacetone, ethyl decanoate, β-citronellol, 2-phenylethanol, linalool, hexyl acetate and hexanol. The methodology shows good linearity over the concentration range tested, with correlation coefficients higher than 0.9821, a good reproducibility was attained (8.9–17.8%), and low detection limits were achieved for nine volatile compounds (0.05–9.09 μg L−1), with the exception of 2-phenylethanol due to low recovery by SBSE. The analytical ability of the SBSE–LD/LVI-GC–qMS methodology was tested in real matrices, such as sparkling and table wines using analytical curves prepared by using the 10 standards where each one was applied to quantify the structurally related compounds. This methodology allowed, in a single run, the quantification of 67 wine volatiles at levels lower than their respective olfactory thresholds. The proposed methodology demonstrated to be easy to work-up, reliable, sensitive and with low sample requirement to monitor the volatile fraction of wine.

Real time B-mode ultrasound in pacas pregnancy (Agouti paca, Linnaeus, 1766)

O objetivo deste estudo foi estabelecer o tempo de prenhez da paca por meio de ultra-sonografia. Nove pacas prenhes foram periodicamente acompanhadas com um transdutor eletrônico setorial bi-frequencial de 5,0 e 7,5 MHz, em modo B, desde a detecção ultra-sonográfica da vesícula embrionária ou do feto até o nascimento dos filhotes. Os animais foram colocados em uma gaiola de ferro de prensagem lateral e permaneceram em posição quadrupedal durante as sessões. Um pano escuro foi usado para cobrir a gaiola e frutas foram oferecidas durante o exame ultra-sonográfico para evitar reações agressivas. Quanto mais precocemente ocorreu a detecção de prenhez, maior foi o período de acompanhamento ultra-sonográfico até o nascimento dos filhotes. Apenas um filhote nasceu por parto, com 796,5 ± 74,36 gramas (valor médio ± desvio padrão da amostra) e 33,46 ± 0,60 centímetros (valor médio ± desvio padrão da amostra) de comprimento (entre a borda rostral do focinho e a extremidade distal da cauda). O período de prenhez da paca abrange 135 a 139 dias.

Random regressions models to describe the genetic variation of milk yield over multiple parities in Buffaloes

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Avaliação da deposição da calda de pulverização em função da densidade populacional de Brachiaria plantaginea, do volume e do ângulo de aplicação

O presente trabalho teve por objetivo avaliar a quantidade de calda de pulverização depositada nas folhas de Brachiaria plantaginea, em aplicações de pós-emergência precoce, em que se variou o volume de calda de pulverização, a densidade de plantas m-2 e o ângulo de posicionamento da ponta de pulverização na barra de aplicação. Para isso, foram conduzidos três experimentos em condições de laboratório. Nestes estudos, o volume de calda de pulverização foi obtido por meio da variação da velocidade de deslocamento de um veículo composto por plataforma e quatro rolamentos tracionados por um motor elétrico. Foi utilizada a ponta de pulverização XR Teejet 8001 EVS, na pressão de 241,4 kPa. O delineamento experimental utilizado foi o inteiramente casualizado, com cinco repetições. No primeiro experimento, os volumes utilizados foram de 1147,57; 860,68; 573,78; 459,02; 344,27; 229,51; 114,75; e 57,37 L ha-1 de calda de pulverização, com densidade de 600 plantas m-2. No segundo experimento foram estudadas as densidades de 300, 600, 900 e 1.200 plantas m-2; neste caso, utilizou-se o volume de 229,51 L ha-1 de calda de pulverização. No terceiro experimento avaliou-se o posicionamento do ângulo da ponta de pulverização na barra de aplicação e utilizou-se a densidade de 600 plantas m-2. Estudaram-se os ângulos de -30º, -15º, 90º, +15º e +30º e os volumes de calda de pulverização de 198,76; 221,69; 229,51; 221,69; e 198,76 L ha-1, respectivamente. Foram adotados sinais negativos para o sentido de deslocamento do veículo e sinais positivos para o sentido contrário ao deslocamento. As avaliações do depósito de calda de pulverização, na planta e no solo, foram feitas utilizando-se condutividade elétrica. A porcentagem de depósito de calda de pulverização nas plantas de B. plantaginea foi incrementada com a redução do volume de calda pulverizada por hectare. O depósito de calda por planta foi maior nas densidades maiores de plantas. O ângulo de posicionamento da ponta de pulverização na barra de aplicação incrementou o depósito de calda nas plantas de B. plantaginea, quando comparado com o ângulo de 90º.

Freqüência de hemolisinas anti-A e anti-B em doadores de sangue do Hemocentro de Botucatu

O Sistema ABO foi descoberto em 1900 e permanece até hoje como sendo o sistema mais importante dentro da prática transfusional. A transfusão ABO incorreta pode resultar na morte do paciente, com uma reação hemolítica intravascular, seguida de alterações imunológicas e bioquímicas. Os anticorpos ABO estão presentes nos soros dos indivíduos, dirigidos contra os antígenos A e/ou B ausentes nas hemácias. Embora as transfusões com pequenas quantias de plasmas incompatíveis sejam geralmente consideradas uma prática segura, alguns casos de reações hemolíticas por plasma incompatível são encontrados na literatura. Tendo em vista a pequena quantidade de estudos sobre as hemolisinas anti-A e anti-B e a importância desses anticorpos na prática transfusional, objetivamos neste trabalho verificar a freqüência dessas hemolisinas em doadores de sangue do Hemocentro da Unesp de Botucatu. Foram analisadas 600 amostras de soros de doadores do grupo O para presença ou ausência das hemolisinas anti-A e anti-B. Desses doadores, 77 (12,8%) foram classificados como perigosos por apresentarem em seu soro altos títulos de hemolisinas e 523 (87,2%) como não perigosos por apresentarem baixos títulos. No grupo dos doadores perigosos, 45 (58,4%) foram reativos para hemolisina anti-A, 11 (14,2%) reativos para hemolisina anti-B e 21 (27,2%) reativos para ambas. O título de aglutininas superior a 1/100 já considera o doador O como perigoso. Assim, o teste realizado em nossa rotina é suficiente para detecção de altos títulos fazendo com que os pacientes dos outros grupos sangüíneos não corram o risco de reação transfusional se necessitarem de transfusão sangüínea não-isogrupo.