Avaliação eletroforética, cromatográfica e molecular da Hb D Los Angeles no Brasil

A variante de hemoglobina (Hb) D mais comum, Hb D Los Angeles ou D Punjab, é originada de uma transversão GAA->CAA no códon 121 da globina beta; essa mutação resulta na substituição do ácido glutâmico por glutamina na proteína. É a terceira variante de hemoglobina mais freqüente da população brasileira. Como as hemoglobinas D apresentam migração similar à hemoglobina S em pH alcalino, e com a hemoglobina A em pH ácido, são necessários vários testes para o correto diagnóstico. No presente estudo objetivou-se relacionar os diferentes procedimentos laboratoriais de rotina diagnóstica, além da análise molecular, para estabelecer o perfil de Hb D Los Angeles no Brasil. Foram analisados 47 indivíduos da população brasileira com provável Hb D Los Angeles, por vários procedimentos eletroforéticos em diferentes condições de pH, além da cromatografia líquida de alta pressão, e testes moleculares para confirmação da mutação. Foram encontrados quatro tipos de combinações de hemoglobinas: 42 indivíduos portadores de hemoglobina AD Los Angeles, dois indivíduos com doença de Hb S/D Los Angeles, dois indivíduos com Hb D Los Angeles e talassemia beta e um indivíduo com Hb D Los Angeles e Hb Lepore. Os indivíduos heterozigotos para D Los Angeles são assintomáticos, entretanto, em associação com outras variantes e talassemias podem apresentar graus variáveis de manifestações clínicas. Os resultados apresentados enfatizaram a necessidade da associação de várias metodologias para a identificação da Hb D Los Angeles, além de auxiliar na elucidação de combinações raras.

SMase II, a new sphingomyelinase D from Loxosceles laeta venom gland: Molecular cloning, expression, function and structural analysis

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

Color tunability of intense upconversion emission from Er3+-Yb3+ co-doped SiO2-Ta2O5 glass ceramic planar waveguides

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

Waveguides and gratings fabrication in zirconium-based organic/inorganic hybrids

Sol-gel derived poly(oxyethylene)/siloxane organic/inorganic di-ureasil hybrids containing different amounts of methacrylic acid (McOH, CH(2)=C(CH(3))COOH)) modified zirconium oxo-clusters (Zr-OMc) were processed as thin films deposited in glassy substrates via spin coating and as transparent and shape controlled monoliths. Channel monomode waveguides and diffraction gratings were UV patterned using the Talbot interferometer and the Lloyd mirror interferometer experimental setups. The time dependence of the diffraction gratings efficiency was studied for hybrids containing different amounts of Zr-OMc. Finally, the number of propagating modes and the refractive index gradient within the waveguide region, determined as a Gaussian section located below the patterned channel, was evaluated and modeled, a maximum index contrast of 2.43 X 10(-5) being estimated.

Optical Fiber Relative Humidity Sensor Based on a FBG with a Di-Ureasil Coating

In this work we proposed a relative humidity (RH) sensor based on a Bragg grating written in an optical fiber, associated with a coating of organo-silica hybrid material prepared by the sol-gel method. The organo-silica-based coating has a strong adhesion to the optical fiber and its expansion is reversibly affected by the change in the RH values (15.0-95.0%) of the surrounding environment, allowing an increased sensitivity (22.2 pm/%RH) and durability due to the presence of a siliceous-based inorganic component. The developed sensor was tested in a real structure health monitoring essay, in which the RH inside two concrete blocks with different porosity values was measured over 1 year. The results demonstrated the potential of the proposed optical sensor in the monitoring of civil engineering structures.

Coordenação local do Eu(III) em híbridos orgânicos/inorgânicos emissores de luz branca

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

Nanoscopic photoluminescence memory as a fingerprint of complexity in self-assembled alkyl/siloxane hybrids

A thermally activated photoluminescence memory effect, induced by a reversible order-disorder phase transition of the alkyl chains, is reported for highly organized bilayer alkyl/siloxane hybrids (see figure; left at room temperature, right at 120 degrees C). The emission energy is sensitive to the annihilation/formation of the hydrogen-bonded amide-amide array displaying a unique nanoscopic sensitivity (ca. 150 nm).

Photopatternable di-ureasil-zirconium oxocluster organic-inorganic hybrids as cost effective integrated optical substrates

Organic-inorganic hybrids containing methacrylic acid (McOH, CH(2)= C(CH(3))COOH)) modified zirconium tetrapropoxide, Zr(OPr(n))(4), classed as di-ureasil-zirconium oxo-cluster hybrids, have been prepared and structurally characterized by X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), Fourier transform infrared (FT-IR) and Raman (FT-Raman) spectroscopies, Si and C nuclear magnetic resonance (NMR), and atomic force microscopy (AFM). XRD and SAXS results have pointed out the presence of Si- and Zr-based nanobuilding blocks (NBBs) dispersed into the organic phase. Inter-NBBs correlation distances have been estimated for the pure di-ureasil and a model compound obtained. by hydrolysis/condensation of Zr(OPr(n))(4):McOH (molar ratio 1: 1): d(Si) approximate to 26 +/- 1 angstrom and d(Zr) approximate to 16 +/- 1 angstrom, respectively. In the case of the di-ureasil-zirconium oxo-cluster hybrids, these distances depend on the Zr relative molar percentage (rel. mol. Zr %) (d(Si) ranges from 18 to 25 angstrom and d(Zr) from 14 to 23 angstrom, as the rel. mol. Zr % increases from 5 to 75), suggesting that the Si- and Zr-based clusters are interconstrained. Complementary data from FT-IR, FT-Raman, (29)Si and (13)C NMR, and AFM support to a structural model where McOH-modified Zr-based NBBs (Zr-OMc) are present over the whole range of composition. At low Zr-OMc contents (rel. mol. Zr % <30) the clusters are well-dispersed within the di-ureasil host, whereas segregation occurs at the 0.1 mu m scale at high Zr-OMc concentration (rel. mol. Zr % = 50). No Zr-O-Si heterocondensation has been discerned. Monomode waveguides, diffractions gratings, and Fabry-Perot cavities have been written through the exposure of the hybrid monoliths to UV light. FT-Raman has shown that the chemical process that takes place under illumination is the polymerization of the methacrylate groups of the Zr-OMc NBBs. The guidance region in patterned channels is a Gaussian section located below the exposed surface with typical dimensions of 320 mu m wide and 88 mu m deep. The effective refractive index is 1.5162 (maximum index contrast on the order of 1 x 10(-4)) and the reflection coeficient of the Fabry-Perot cavity (formed by a grating patterned into a 0.278 cm channel) is 0.042 with a free spectral range value of 35.6 GHz.

Hyperossification in Miniaturized Toadlets of the genus Brachycephalus (Amphibia: Anura: Brachycephalidae): Microscopic Structure and Macroscopic Patterns of Variation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A New Species of Brachycephalus from the Atlantic Rain Forest in São Paulo State, Southeastern Brazil (Amphibia: Anura: Brachycephalidae)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Self-Structuring of Lamellar Bridged Silsesquioxanes with Long Side Spacers

Diurea cross-linked bridged silsesquioxanes (BSs) C(10)C(11)C(10) derived from organosilane precursors, including decylene chains as side spacers and alkylene chains with variable length as central spacers (EtO)(3)Si- (CH(2))(10)-Y(CH(2))(n)-Y-(CH(2))(10)-Si(OEt)(3) (n = 7, 9-12; Y = urea group and Et = ethyl), have been synthesized through the combination of self-directed assembly and an acid-catalyzed sol gel route involving the addition of dimethylsulfoxide (DMSO) and a large excess of water. This new family of hybrids has enabled us to conclude that the length of the side spacers plays a unique role in the structuring of alkylene-based BSs, although their morphology remains unaffected. All the samples adopt a lamellar structure. While the alkylene chains are totally disordered in the case of the C(10)C(7)C(10) sample, a variable proportion of all-trans and gauche conformers exists in the materials with longer central spacers. The highest degree of structuring occurs for n = 9. The inclusion of decylene instead of propylene chains as side spacers leads to the formation of a stronger hydrogen-bonded urea-urea array as evidenced by two dimensional correlation Fourier transform infrared spectroscopic analysis. The emission spectra and emission quantum yields of the C(10)C(n)C(10) Cm materials are similar to those reported for diurea cross-linked alkylene-based BSs incorporating propylene chains as side spacers and prepared under different experimental conditions. The emission of the C(10)C(n)C(10) hybrids is ascribed to the overlap of two distinct components that occur within the urea cross-linkages and within the siliceous nanodomains. Time-resolved photoluminescence spectroscopy has provided evidence that the average distance between the siliceous domains and the urea cross-links is similar in the C(10)C(n)C(10) BSs and in oxyethylene-based hybrid analogues incorporating propylene chains as side spacers (diureasils), an indication that the longer side chains in the former materials adopt gauche conformations. It has also allowed us to demonstrate for the first time that the emission features of the urea-related component of the emission of alkylene-based BSs depend critically on the length of the side spacers.

Lanthanide-Containing Light-Emitting Organic-Inorganic Hybrids: A Bet on the Future

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

Full-color phosphors from amine-functionalized crosslinked hybrids lacking metal activator ions

Sol-gel derived hybrids that contain OCH2CH2 (polyethylene glycol, PEG) repeat units grafted onto a siliceous backbone by urea, -NHC(=O)NH-, or urethane, -NHC(=O)O-, bridges have been prepared. It is demonstrated that the white light PL of these materials results from an unusual convolution of a longer lived emission that originates in the NH groups of the urea/urethane bridges with shorter lived electron-hole recombinations occurring in the nanometer-sized siliceous domains. The PL efficiencies reported here (maximum quantum yields at room temperature of ≈ 0.20 ± 0.02 at a 400 nm excitation wavelength) are in the same range as those for tetramethoxysilane-formic acid, and APTES-acetic acid, sol-gel derived phosphors. The high quantum yields combined with the possibility of tuning the emission to colors across the chromaticity diagram present a wide range of potential applications for these hybrid materials.

Endophytic yeasts and filamentous fungi associated with southern Brazilian apple (Malus domestica) orchards subjected to conventional, integrated or organic cultivation

Endophytic fungi were isolated from leaves, flowers and fruit of healthy apple trees (Malus domestica, BORKH.) growing in southern Brazilian orchards under three different cultivation systems (conventional, integrated and organic), during two vegetative cycles. The greatest total number of endophytic isolates was obtained from the orchards under organic cultivation when compared to integrated and conventional cultivation systems. Filamentous fungi from the genera Colletotrichum, Xylaria and Botryosphaeria were the most frequent ones and the most representative yeast genera were Sporobolomyces, Rhodotorula, Debaryomyces and Cryptococcus. It is suggested that some isolates may be used as indicators of the different management systems. © 2005 Wiley-VCH Verlag GmbH & Co. KGaA.

Photoluminescence-structure relationships in ormosils for integrated optical devices

Planar waveguides with low losses in the infrared (from 0.6-1.1 dB/cm) were prepared with sol-gel derived poly(oxyethylene)/siloxane hybrid doped with zirconium(IV) n-propoxide (ZPO) and methacryloxypropyltrimethoxysilane (MAPTMS). The doped nanohybrids were characterized by small angle X-ray scattering, 29Si nuclear magnetic resonance and photoluminescence spectroscopy and compared with the undoped hybrid material. The results indicate an effective interaction between the zirconium particles and the siliceous nanodomains. © 2005 Materials Research Socicty.