Monomer conversion of composite dental resins photoactivated by a halogen lamp and a LED: a FT-Raman spectroscopy study

Eighteen circular blocks of resins cured either by a LED or a halogen lamp (20, 40 and 60 s), had their top (T) and bottom (B) surfaces studied using a FT-Raman spectrometer. Systematic changes in the intensity of the methacrylate C=C stretching mode at 1638 cm-1 as a function of exposure duration were observed. The calculated degree of conversion (DC) ranged from 45.0% (B) to 52.0% (T) and from 49.0% (B) to 55.0% (T) for the LED and halogen lamp, respectively. LED and halogen light produced similar DC values with 40 and 60 s of irradiation.

Gramática aplicada a ELE: la perífrasis “ir a + infinitivo” y el futuro sintético

La presencia en español de dos construcciones —la perífrasis «IR A+Infinitivo» y lasformas verbales sintéticas terminadas en –rá— que pueden alternarse en determinadoscontextos como mecanismos para expresar la futuridad en español ha llevado a unageneralización en el uso de tales construcciones descuidando la vertiente pragmática delas mismas, y, en consecuencia, se ha tendido a ofrecer al estudiante de ELE unaconsideración básicamente gramatical de los usos de la perífrasis y del futuro sintético. Eneste sentido, el objetivo de nuestra propuesta busca establecer las principales divergencias de carácter pragmático que —creemos— deberían incorporarse a la explicación de estos contenidos gramaticales.

Desenvolvimento e validação de metodologia analítica por CLAE-IR para determinação de artemisinina em Artemisia annua L

The aim of this work was to develop and validate an analytical methodology for determination of artemisinin used as antimalaric. The method was based on high performace liquid chromatography, using a CN column with mobile phase composed of methanol : H2O 50:50 (V/V). The results showed that the method presented linearity from 50 to 1500 µg/mL. It was considered selective, accurate, precise according to the specific resolution from ANVISA, the Brazilian regulatory agency.

Selective hydrogenation of furfural on Ir/TiO2 catalysts

Titania-supported Ir catalysts were used in the hydrogenation of furfural. Reactions were carried out in a stirred batch type reactor at 0.62MPa and 363K using a 0.10M solution of furfural in a 1:1 mixture n-heptane -ethanol as solvent. Catalysts containing 2 wt% of Ir were reduced in H2 flow at different temperatures in the range 473-773K. The catalysts were characterized by H2 chemisorption, TEM, TPR, TPD of NH3 and XPS. Conversion of furfural is higher at lower reduction temperatures, but leads to byproducts whereas reduction at higher temperatures shows selectivity to furfuryl alcohol close to 100%.

Avaliação da eficiência das técnicas ESI-MS e ATR/FTIR na determinação de adulteração de BX com querosene e óleo residual

Direct infusion electrospray ionization mass spectrometry in the negative ion mode, ESI(-)-MS and Fourier transform infrared spectroscopy (FTIR) were used together with partial least squares (PLS) as a tool to determine B3 adulteration (B3 - mixture of 3% v/v of biodiesel in diesel) with kerosene and residual oil.

Fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy and chemometric techniques for the determination of adulteration in petrodiesel/biodiesel blends

We propose an analytical method based on fourier transform infrared-attenuated total reflectance (FTIR-ATR) spectroscopy to detect the adulteration of petrodiesel and petrodiesel/palm biodiesel blends with African crude palm oil. The infrared spectral fingerprints from the sample analysis were used to perform principal components analysis (PCA) and to construct a prediction model using partial least squares (PLS) regression. The PCA results separated the samples into three groups, allowing identification of those subjected to adulteration with palm oil. The obtained model shows a good predictive capacity for determining the concentration of palm oil in petrodiesel/biodiesel blends. Advantages of the proposed method include cost-effectiveness and speed; it is also environmentally friendly.

Análise exploratória aplicada a espectros de reflexão total atenuada no infravermelho com transformada de Fourier (ATR-FTIR) de blendas de biodiesel/diesel

In this study, hierarchical cluster analysis (HCA) and principal component analysis (PCA) were used to classify blends produced from diesel S500 and different kinds of biodiesel produced by the TDSP methodology. The different kinds of biodiesel studied in this work were produced from three raw materials: soybean oil, waste cooking oil and hydrogenated vegetable oil. Methylic and ethylic routes were employed for the production of biodiesel. HCA and PCA were performed on the data from attenuated total reflectance Fourier transform infrared spectroscopy, showing the separation of the blends into groups according to biodiesel content present in the blends and to the kind of biodiesel used to form the mixtures.

DERIVATIZACIÓN Y CARACTERIZACIÓN ESPECTROSCÓPICA DE UN BIOPOLÍMERO A BASE DE L -LISINA CON ANÁLOGOS DE LA D-BIOTINA: CO -POLI(L-LISINA)-GRAFT -(ε-N-[X-D -BIOTINIL]-L-LISINA)

We report the single-step derivatization reaction of a biopolymer based onL -lysine with D -biotin analogs:Co -poly(L -lysine)-graft-(ε-N -[X-D-biotinyl]-L -lysine) (PLL-X-Biotin). The valeric acid carboxylate of D -biotin is activated to an NHS ester for direct modification of amine groups in proteins and other macromolecules. NHS esters react by nucleophilic attack of an amine in the carbonyl group, releasing the NHS group, and forming a stable amide linkage. NHS-X-Biotin is the simplest biotinylation reagent commercially available. In contrast withD -biotin, it has a longer spacer arm off the valeric acid side chain allowing better binding potential for avidin or streptavidin probes. Derivatization of poly(L -lysine) (PLL) with NHS-X-Biotin led to a copolymer PLL-X-Biotin. UV-Visible, IR-FT and 1H NMR characteristics derived from synthesis are briefly discussed.

2-(4-IODO-2,5-DIMETOXIFENIL)-N-[(2-METOXIFENIL)METIL]ETAMINA OU 25I-NBOME: CARACTERIZAÇÃO QUÍMICA DE UMA DESIGNER DRUG

Drug trafficking and the introduction of new drugs onto the illicit market are one of the main challenges of the forensic community. In this study, the chemical profile of a new designer drug, 2-(4-iodine-2,5-dimethoxyphenyl)-n-[(2-methoxyphenyl)methyl]etamine or 25I-NBOMe was explored using thin layer chromatography (TLC), ultraviolet-visible spectrophotometry (UV-Vis), attenuated total reflection with Fourier transform infrared spectroscopy(ATR-FTIR), gas chromatography mass spectrometry (GC-MS) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS). First, the TLC technique was effective for identifying spots related to 25C-, 25B- and 25I-NBOMe compounds, all with the same retention factor, Rf ≈ 0.50. No spot was detected for 2,5-dimethoxy-4-bromoamphetamine, 2,5-Dimethoxy-4-chloroamphetamine or lysergic acid diethylamide compounds. ATR-FTIR preserved the physical-chemical properties of the material, whereas GC-MS and ESI-MS showed better analytical selectivity. ESI(+)FT-ICR MS was used to identify the exact mass (m/z428.1706 for the [M + H]+ ion), molecular formula (M = C18H22INO3), degree of unsaturation (DBE = 8) and the chemical structure (from collision induced dissociation, CID, experiments) of the 25I-NBOMe compound. Furthermore, the ATR-FTIR and CID results suggested the presence of isomers, where a second structure is proposed as an isomer of the 25I-NBOMe molecule.

Experimental and theoretical investigation of the IR spectra and thermochemistry of four isomers of 2-N,N-dimethylaminecyclohexyl 1-N',N'-dimethylcarbamate

A combined experimental and Density functional theory (DFT) B3LYP/6-311+G* study on the IR spectra of four stable isomers of 2-N,N-dimethylaminecyclohexyl 1-N',N'-dimethylcarbamate was performed. Our theoretical calculations reveal that two new isomers of this compound exist and may be more stable than the known isomers. In addition the entropy, heat capacity, and the enthalpy content of the stable isomers are computed by fitting the calculated data to a standard Shomate equation and IR spectra for the two new isomers are presented.

Determinação de chumbo em álcool combustível por voltametria de redissolução anódica utilizando um eletrodo de pasta de carbono modificado com resina de troca iônica Amberlite IR 120

Um método envolvendo a pré-concentração e redissolução anódica em condições de voltametria de pulso diferencial empregando um eletrodo de pasta de carbono modificado (EPCM) com uma resina de troca iônica Amberlite IR120 foi proposto para a determinação de íons chumbo em álcool combustível. O procedimento é baseado em um pico de oxidação do analito observado em -0,53 V(vs. Ag/AgCl) em solução de HCl. As melhores condições experimentais encontradas foram: 5% (m/m) da Amberlite IR120 para a construção do eletrodo, solução de HCl 0,1 mol L-1, velocidade de varredura de 10 mVs-1, tempo de pré-concentração de 15 min e amplitude de pulso de 100 mV. Utilizando essas condições, o EPCM apresentou uma resposta linear entre a corrente de pico anódica e a concentração de íons chumbo para o intervalo entre 9,9 x 10-9 e 1,2 x 10-6 mol L-1 e um limite de detecção de 7,2 x 10-9 mol L-1. Valores de recuperação entre 96 % e 102 % foram encontrados para amostras de álcool combustível enriquecidas com Pb2+ em níveis de 10-7 mol L-1. O efeito da presença de outros íons concomitantes sobre a resposta voltamétrica do eletrodo também foi avaliado.

Determination of sulfur in diesel using ATR/FTIR and multivariate calibration

The aim of this present work was to provide a more fast, simple and less expensive to analyze sulfur content in diesel samples than by the standard methods currently used. Thus, samples of diesel fuel with sulfur concentrations varying from 400 and 2500 mgkg-1 were analyzed by two methodologies: X-ray fluorescence, according to ASTM D4294 and by Fourier transform infrared spectrometry (FTIR). The spectral data obtained from FTIR were used to build multivariate calibration models by partial least squares (PLS). Four models were built in three different ways: 1) a model using the full spectra (665 to 4000 cm-1), 2) two models using some specific spectrum regions and 3) a model with variable selected by classic method of variable selection stepwise. The model obtained by variable selection stepwise and the model built with region spectra between 665 and 856 cm-1 and 1145 and 2717 cm-1 showed better results in the determination of sulfur content.

Hopeinen Kairamo-mitali FT Ilkka Koivistolle

Kairamo-mitalit 2008.

Mentoring: ir ou não ir, eis a questão: um estudo qualitativo

Para melhor compreender a adesão dos alunos a um Programa de Mentoring, o Programa Tutores FMUSP, este estudo qualitativo explorou as razões apresentadas pelos estudantes em relação ao seu envolvimento com a atividade, no período 2004-2005, antes e depois de mudanças estruturais no programa (inserção da atividade na grade horária). Os estudantes avaliam anualmente o programa por meio de um questionário estruturado - "O Tutorando". Nele, uma questão específica sobre adesão é apresentada e foi analisada neste estudo. A análise dos resultados mostra que a troca de experiência entre alunos de diferentes anos, mediada por um tutor habilidoso, promove uma visão ampliada do curso e da profissão e motiva os alunos a participarem mais do programa. Tutores que se desligam do programa, agendamento irregular dos encontros, comunicação não efetiva, discussão de temas desinteressantes contribuem para uma baixa adesão. A inserção do programa na grade horária oficial resolveu importantes problemas, mas muitos alunos ainda preferem usar o tempo do Mentoring para outras atividades acadêmicas ou necessidades pessoais. O mentoring informal e grupos com uma dinâmica ruim também justificam, para os alunos, uma menor adesão. O sucesso de um Programa de Mentoring, no que diz respeito à adesão dos alunos, mostra estar vinculado não apenas a uma estrutura adequada, mas também às características pessoais e valores dos participantes.

Grafeenioksidin pelkistys grafeenin kaltaiseksi materiaaliksi

Grafeeni on tällä hetkellä yksi tutkituimmista materiaaleista ja sillä on paljon mahdollisia käyttötarkoituksia esimerkiksi nanoelektroniikassa, sensoreissa, nanokomposiiteissa ja vetyvarastona. Tällä hetkellä tehokkaan valmistusmenetelmän puuttuminen kuitenkin on esteenä grafeenin hyödyntämiselle laajassa mittakaavassa. Yksi lupaavimmista grafeenin valmistusmenetelmistä tällä hetkellä on grafeenioksidin pelkistäminen. Tässä tutkielmassa oli tarkoitus tutustua grafeenioksidin pelkistysmenetelmiin ja vertailla niitä toisiinsa. Työn kokeellisessa osassa oli tarkoituksena tutkia grafeenioksidin sähkökemiallista pelkistystä lähinnä in situ pintaherkistetyllä Raman-spektroskopialla (SERS) ja pintaherkistetyllä vaimentuneeseen kokonaisheijastukseen perustuvalla IR-spektroskopialla (ATR-SEIRAS). Työhön kuului myös SEIRAS-kennon ja -mittaussysteemin kehittäminen, koska Turun yliopistossa ei aikaisemmin ollut tehty SEIRAS-mittauksia. Työssä onnistuttiin pelkistämään grafeenioksidikalvo sähkökemiallisesti ainakin osittain. Pelkistymisen havaittiin tapahtuvan välillä -0,3 V – (-0,9) V (vs. Ag/AgCl) ja muutosten havaittiin olevan irreversiibeleitä. Työssä saatiin myös kehitettyä menetelmä SEIRASaktiivisen kultakalvon valmistamiseen Turun yliopistossa käytettävään kennoon ja selvitettyä toimiva mittaustapa. Työssä myös todettiin, että menetelmä sopii hyvin grafeenioksidin pelkistyksen seuraamiseen.