Síntese e caracterização de vidros teluritos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Caracterização térmica de compostos orgânicos usando a técnica de lente térmica

Utilizou-se a técnica de espectroscopia de lente térmica com dois feixes quase paralelos em modo descasado para estudar as propriedades térmicas de cinco óleos vegetais e de um composto específico de oleína de palma e p-caroteno (OP+BC), preparado no laboratório. As medidas de difusividade térmica foram obtidas do ajuste entre a curva experimental do sinal temporal de lente térmica no fotodetector com a equação obtida no modelo aberrante de lente térmica com modos descasados, tendo em conta a difração de Fresnel para o campo distante. São reportadas as medidas da difusividade térmica de diversos óleos vegetais da Amazônia e do composto OP+BC. É verificado um crescimento exponencial da difusividade térmica com a concentração, o que se atribui à estrutura molecular do p-caroteno. Até o momento, os resultados são inéditos e não têm sido reportados na literatura.

Espectroscopia de Lente Térmica aplicada ao sistema Ácido oléico/Beta Caroteno

Neste trabalho apresentamos um estudo na mistura formada pelo betacaroteno diluído em ácido oleico (BC:AO) em diferentes concentrações, usando-se para isso a técnica fototérmica chamada de Lente Térmica. Procuramos variar os diferentes parâmetros de controle como: a espessura da amostra, a sua concentração, a potência do laser de excitação, etc. Aplicamos o modelo aberrante desenvolvido por Shen para encontrar a difusividade térmica, a variação do índice de refração com a temperatura (dn/dT), e a magnitude do sinal de lente térmica, nas amostras. Verificamos, com base no modelo teórico apresentado no capítulo 2, que se o aumento da potência e da concentração é muito grande e atinge um certo valor, parâmetros como difusividade térmica passam a apresentar distorções nos valores medidos. Observamos também que a mistura BC:AO apresenta absorção não linear, mesmo para potências pequenas do laser de excitação usado. As contribuições apresentadas neste trabalho são inéditas e devem contribuir para um melhor entendimento das propriedades térmicas do sistema BC:AO ou de sistemas similares como alguns óleos vegetais que são ricos em ácido oleico e betacaroteno.

Propriedades ópticas e térmicas da oleína de palma

Usamos uma metodologia experimental para investigar propriedades ópticas e térmicas da oleína de palma (OP), a fração líquida do azeite de palma (Elaies guineensis) obtida por fracionamento natural, com propriedades físicas que diferem apreciavelmente do azeite. Em uma primeira abordagem, estudamos os espectros de absorção e emissão monitorando a modificação dos espectros com o aumento da concentração β-caroteno misturado com OP, o que permitiu encontrar o coeficiente de absorção molar do β-caroteno (ε = 920,802 mol ^-1.cm^-1.L). Este valor é muito baixo em relação aos conhecidos para o β-caroteno diluído em um solvente puro, como o benzeno ou o n-hexano. Experimentos feitos com β-caroteno diluído em hexano nos permitiram medir ε = 117.900 L.mol^-1.cm^-1, que representa aproximadamente 18% abaixo dos valores reportados na literatura. Em uma segunda abordagem, os espectros de absorção foram usados para medir o coeficiente de absorção da OP, A = 0,028 cm^-1 em 532 nm, o comprimento de onda de um laser usado como fonte de excitação no estudo das propriedades térmicas da OP usando a técnica de lente térmica. Neste sentido foi medido também o coeficiente térmico do índice de refração da OP, dn/dt = - 3,821 x 10 ^-4 °C ^-1. Estes resultados, associados ao modelo aberrante para estudos de espectroscopia de lente térmica, levaram à medição do coeficiente de difusão, D = 2,19 ± 0,11 x 10^-4 cm²/s, e da condutividade térmica, k = 5,96 ± 0,08 W/m°C. Embora as medidas das propriedades térmicas da OP não sejam ainda conhecidas na literatura, observa-se que elas têm as mesmas ordens de grandeza daquelas já conhecidas para outros óleos vegetais que foram relatadas na literatura.

Propriedades ópticas de materiais híbridos de sílica dopados com nanocristais de CdSe/ZnS

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

High fluorescence quantum efficiency of CdSe/ZnS quantum dots embedded in GPTS/TEOS-derived organic/silica hybrid colloids

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Effect of Ag nanoparticles on the radiative properties of tellurite glasses doped with Er3+, Yb3+ and Tm3+ ions

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Spectroscopic investigation and heat generation of Yb3+/Ho3+ codoped aluminosilicate glasses looking for the emission at 2 μm

Energy transfer (ET) and heat generation processes in Yb3+/Ho3+-codoped low-silica calcium aluminosilicate glasses were investigated using thermal lens (TL) and photoluminescence measurements looking for the emission around 2.0 μm. Stepwise ET processes from Yb3+ to Ho3+, upon excitation at 0.976 μm, produced highly efficient emission in the mid-infrared range at around 2.0 μm, with high fluorescence quantum efficiency (η1 ∼ 0.85 and independent of Ho3+ concentration) and relatively very low thermal loading (<0.4) for concentration up to 1.5% of Ho2O3. An equation was deduced for the description of the TL results that provided the absolute value of η1 and the number of emitted photons at 2.0 μm per absorbed pump photon by the Yb3+ ions, the latter reaching 60% for the highest Ho3+ concentration. These results suggest that the studied codoped system would be a promising candidate for the construction of photonic devices, especially for medical applications.

Fundamentals of optical detection of small particles

This paper reviews a number of used and/or proposed ideas for optical detection of small particles including single molecules. Different techniques (direct absorption and scattering, interferometry, use of sub Poissonian statistics, cavity enhancement, and thermal lens detection) are compared in terms of signal-to-noise ratio. It is shown that scattering (resonance and non resonance) fundamentally remains the method of choice for most applications.

Identification of abundant alkyl ether glycerophospholipids in the human lens by tandem mass spectrometry techniques

Previous studies have shown that the human lens contains glycerophospholipids with ether linkages. These lipids differ from conventional glycerophospholipids in that the sn-1 substituent is attached to the glycerol backbone via an 1-O-alkyl or an 1-O-alk-1'-enyl ether rather than an ester bond. The present investigation employed a combination of collision-induced dissociation (CID) and ozone-induced dissociation (OzID) to unambiguously distinguish such 1-O-alkyl and 1-O-alk-1'-enyl ethers. Using these methodologies the human lens was found to contain several abundant 1-O-alkyl glycerophos-phoethanolamines, including GPEtn(16:0e/9Z-18:1), GPEtn(11Z-18:1e/9Z-18:1), and GPEtn(18:0e/9Z-18:1), as well as a related series of unusual 1-O-alkyl glycerophosphoserines, including GPSer(16:0e/9Z-18:1), GPSer(11Z-18:1e/9Z-18:1), GPSer(18:0e/9Z-18:1) that to our knowledge have not previously been observed in human tissue. Isomeric 1-O-alk-1'-enyl ethers were absent or in low abundance. Examination of the double bond position within the phospholipids using OzID revealed that several positional isomers were present, including sites of unsaturation at the n-9, n-7, and even n-5 positions. Tandem CID/OzID experiments revealed a preference for double bonds in the n-7 position of 1-O-ether linked chains, while n-9 double bonds predominated in the ester-linked fatty acids [e.g., GPEtn(11Z-18:1e/9Z-18:1) and GPSer(11Z-18:1e/9Z-18:1)]. Different combinations of these double bond positional isomers within chains at the sn-1 and sn-2 positions point to a remarkable molecular diversity of ether-lipids within the human lens.

Imaging of human lens lipids by desorption electrospray ionization mass spectrometry

The lipid composition of the human lens is distinct from most other tissues in that it is high in dihydrosphingomyelin and the most abundant glycerophospholipids in the lens are unusual 1-O-alkyl-ether linked phosphatidylethanolamines and phosphatidylserines. In this study, desorption electrospray ionization (DESI) mass spectrometry-imaging was used to determine the distribution of these lipids in the human lens along with other lipids including, ceramides, ceramide-1-phosphates, and lyso 1-O-alkyl ethers. To achieve this, 25 μm lens slices were mounted onto glass slides and analyzed using a linear ion-trap mass spectrometer equipped with a custom-built, 2-D automated DESI source. In contrast to other tissues that have been previously analyzed by DESI, the presence of a strong acid in the spray solvent was required to desorb lipids directly from lens tissue. Distinctive distributions were observed for [M + H]+ ions arising from each lipid class. Of particular interest were ionized 1-O-alkyl phosphatidylethanolamines and phosphatidylserines, PE (18:1e/18:1), and PS (18:1e/18:1), which were found in a thin ring in the outermost region of the lens. This distribution was confirmed by quantitative analysis of lenses that were sectioned into four distinct regions (outer, barrier, inner, and core), extracted and analyzed by electrospray ionization tandem mass spectrometry. DESI-imaging also revealed a complementary distribution for the structurally-related lyso 1-O-alkyl phosphatidylethanolamine, LPE (18:1e), which was localized closer to the centre of the lens. The data obtained in this study indicate that DESI-imaging is a powerful tool for determining the spatial distribution of human lens lipids. © 2010 American Society for Mass Spectrometry.

Thermal degradation products of poly(styrenesulfides) investigated by direct pyrolysis�mass spectrometry and flash pyrolysis�gas chromatography/mass spectrometry

The thermal degradation products of two sulfur polymers, poly(styrenedisulfide) (PSD) and poly(styrenetetrasulfide) (PST), were investigated in parallel by direct pyrolysis-mass spectrometry (DPMS) and by flash pyrolysis-GC/MS (Py-GC/MS). The time-scale of the two pyrolysis techniques is quite different, and therefore they were able to detect significantly different products in the pyrolysis of PSD and PST because of the thermal lability of sulfur-containing compounds. However, the results obtained are not contradictory, and satisfactory mechanisms for the thermal degradation of PSD and PST have been derived from the overall evidence available. Pyrolysis compounds containing sulfur, styrene, and a number of cyclic styrene sulfides and diphenyldithianes have been observed by DPMS. However, in flash pyrolysis-GC/MS, styrene, sulfur, only one cyclic styrene sulfide, and two isomers of diphenylthiophene have been detected. These thiophene derivatives were indeed absent among the compounds obtained by DPMS because they were the terminal (most thermally stable) species arising from further decomposition of the cyclic styrene sulfides formed in the primary thermal degradation processes of PSD and PST.

Thermal degradation processes in polysulfide copolymers investigated by direct pyrolysis mass spectrometry and flash pyrolysis-gas chromatography/mass spectrometry

This is the first report on the analysis of random block polysulfide copolymers containing different amounts of repeating units in the copolymer backbone, which has been studied by direct pyrolysis mass spectrometry (DPMS) and by pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). The homopolymers such as poly(ethylene sulfide) (PES), poly(styrene sulfide) (PSS), and two random copolymers, viz., poly(ethylene sulfide(x)-co-styrene sulfide(y)) [copolymer I (x = y = 0.5) and copolymer II (x = 0.74, y = 0.26)] were investigated by both DPMS and Py-GC/MS (except copolymer II) techniques. In the case of copolymer I, the thermal degradation products of SE1, SE2, S-2, and S2E (S = styrene sulfide, E = ethylene sulfide) were detected in DPMS, whereas the formation of SE1 and SE2 were observed by Py-GC/MS technique. However, for copolymer II, SE3 was also found along with SE1, SE2, S-2, and S2E in DPMS. The formation of additional product (SE3) observed in copolymer II could be due to an increase in the block length formed during copolymerization. Further, a comparative study on thermal degradation of PES, poly(ethylene disulfide) (PEDS), and poly(ethylene tetrasulfide) (PETS) were investigated by Py-GC/MS. The pyrolysis products detected by both DPMS and Py-GC/MS indicates that the thermal decomposition of these polymers yield cyclic sulfides through an intramolecular exchange or by backbiting processes. The linear products with thiol and vinyl groups were also observed by Py-GC/MS along with the cyclic products via carbon hydrogen transfer reaction.