Raman and infrared investigations of glass and glass-ceramics with composition 2Na2O·1CaO·3SiO2

Precursor glass and glass-ceramics with molar composition 2Na2O·1CaO·3SiO2 are studied by infrared, conventional, and microprobe Raman techniques. The Gaussian deconvoluted Raman spectrum of the glass presents bands at 625 and 660 cm-1, attributed to bending vibrations of Si-O-Si bonds, and at 860, 920, 975, and 1030 cm-1, attributed to symmetric stretching vibrations of SiO4 tetrahedra with 4, 3, 2, and 1 nonbridging oxygens, respectively. The Raman microprobe spectrum of a highly crystallized sample presents two narrow and intense bands at about 590 and 980 cm-1, associated with vibrations of SiO4 tetrahedra with two nonbridging oxygens, in agreement with the predicted chain-like structure of crystalline metasilicates. Scanning electron microscopy shows that the crystals distributed in partially crystallized samples have a spherical shape, built up by radially oriented needle-like single crystals. The Raman microprobe spectra of these spherulites show that they still contain residual amorphous material. A comparison of Raman and infrared spectra of amorphous and highly crystallized samples is presented.

Estudo da regeneração de aditivos para catalisadores de craqueamento aluminofosfatos (ALPO s)e silicoaluminofosfatos (SAPO s)

Heterogeneous catalysts such as aluminophosphate and silicoaluminophosphate, molecular sieves with AEL of ALPO-11 and SAPO-11, were synthesized by the hydrothermal method with the following molar composition: 2.9 Al +3.2 P + 3.5 DIPA +32.5 H20 (ALPO-11); 2.9 Al +3.2 P + 0.5 Si + 3.5 DIPA +32.5 H20 (SAPO-11) starting from silica (only in the SAPO-11), pseudoboehmite, orthophosphoric acid (85%) and water, in the presence of a di-isopropylamine organic template. The crystallization process occurred when the reactive hydrogel was charged into a vessel and autoclaved at 170ºC for a period of 48 hours under autogeneous pressure. The obtained materials were washed, dried and calcined to remove the molecular sieves of DIPA. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (FT-IR), thermo gravimetric differential thermal analysis (TG/DTA) and nitrogen adsorption (BET). The acidic properties were determined using adsorption of n-butylamine followed by programmed thermodessorption. This method revealed that ALPO-11 has weaker acid sites due to structural defects, while SAPO-11 shows an acidity that ranges from weak to moderate. However, a small quantity of strong acid sites could be detected there. The deactivation of the catalysts was conducted by the cracking of the n-hexane in a fixed bed continuous flow microrreator coupled on line to a gas chromatograph. The main products obtained were: ethane, propane, isobutene, n-butane, n-pentane and isopentane. The Vyazovkin (model-free) kinetics method was used to determine the regeneration and removal of the organic template

Pre-resonant Raman effect of CrO2- 4 in a metasilicate glass

Pre-resonant Raman effect of chromate ion, CrO2- 4, was observed in a metasilicate glass with molar composition 2Na2O · 1CaO · 3SiO2 containing 1.0 wt% of Cr2O3. Raman spectra were measured by the conventional 90° scattering geometry and by the microprobe Raman spectroscopic techniques. The presence of chromate ions in the glass is favoured by the glass composition and oxidizing conditions during the glass melting, and they are responsible for optical absorption bands at 370 and 250 nm. Raman spectrum of the undoped glass presents bands at 625, 860 and 980 cm-1, and the presence of chromate ions gives rise to additional bands at 365, 850 and a shoulder at 890 cm-1. An enhancement of the 850 cm-1 Raman band is observed with decreasing laser exciting wavelength. The exciting frequency dependence of the intensity of this band is discussed in terms of theoretical models given in the literature.

Transparent Er3+-activated lead fluorogermanate glass ceramics

Transparent glass ceramics containing β-PbF2:Er 3+ nanocrystals were obtained through appropriate thermal treatments of a glass of molar composition 60PbGeO3-10PbF2-30CdF 2 doped with 0.5 mol% Er3+. Their optical properties, as well as upconversion processes among erbium ions in the glass and glass ceramic matrix were studied. From absorption spectra, Judd-Ofelt parameters and radiative transition rates for several excited levels were calculated. Emission spectra in the visible and NIR regions were collected, and stimulated emission cross sections were obtained by McCumber theory for the 4F 13/2→4I15/2 transition at 1.5 μm. Red and green upconversion emissions were measured in glass and glass ceramics upon excitation at 980 nm; lifetimes were measured in order to assess the upconversion mechanisms.

Síntese e caracterização de argila esmectita Zn-estevensita

Argila do grupo das esmectitas foi obtida com êxito em baixa temperatura de processamento por via hidrotérmica utilizando como precursores metassilicato de sódio, nitrato de zinco e uréia. Durante a etapa de síntese a composição molar da mistura reacional e a temperatura permaneceram constantes, variando-se o tempo de reação. As amostras sintetizadas foram caracterizadas por difração de raios X, microscopia eletrônica de varredura, espectroscopia de refletância difusa no infravermelho com transformada de Fourier, análise térmica diferencial e gravimétrica, análise de adsorção gasosa de nitrogênio pelo método BET e capacidade de troca de cátions. Os resultados evidenciam que com a metodologia empregada obtêm-se Zn-estevensita apresentando uma área superficial total na faixa de 171,6 a 203,4 m²/g e boa cristalinidade; sendo esta a única fase presente no produto sintetizado após reação estática a 90 ºC por um período de 44 a 138 h, indicando ser o aumento no tempo de síntese um parâmetro importante para o processo de cristalização da argila.

Substituição isomórfica de íons gálio em zeólitas de estrutura mfi para modificação da acidez do catalisador e controle da desativação na desidratação do glicerol

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Photo- and electroluminescence in a series of PPV type terpolymers containing fluorene, thiophene and phenylene units

The emissive properties of terpolymers with fluorene, thiophene and phenylene groups, forming alternating PPV type structures, are discussed in terms of their composition, photo- and electroluminescence properties. The fluorene groups were inserted in each phenylene-vinylene and thiophene-vinylene units, and their concentration did not vary, representing 50% of the molar composition. The ratio of thiophene-vinylene/phenylene-vinylene varied in the range 25,50 and 75%. Photo- and electroluminescence properties were strongly dependent on the thiophene-vinylene content and were compared with the fluorene-vinylene-thiophene and fluorene-vinylene-phenylene parent copolymers. (C) 2012 Elsevier B.V. All rights reserved.

Control of ordered structure and morphology of large-pore periodic mesoporous organosilicas by inorganic salt

Highly ordered rodlike periodic mesoporous organosilicas (PMO) were successfully synthesized using 1.2-bis(trimethoxysilyl)ethane as an precursor and triblock copolymer P123 as a template at low acid concentration and in the presence of inorganic salts (KCl). The role of acid and salt as well as the effects of synthesis temperature and reactant mole ratio in the control of morphology and the formation of ordered mesostructure was systematically examined. It was found that the addition of inorganic salt can dramatically expand the range of the synthesis parameters to produce highly ordered PMO structure and improve the quality of PMO materials. The morphology of PMOs was significantly dependent on the induction time for precipitation. The uniform PMO rods can only be synthesized in a narrow range of acid and salt concentrations. The results also show that the optimized salt concentration (I M) and low acidity (0.167 M) were beneficial to the formation of not only highly ordered mesostructure but also rodlike morphology. Increasing acidity resulted in fast hydrolysis reaction and short rod or plate-like particles. Highly ordered rod can also be prepared at low temperature (35 degrees C) with high salt amount (1.5 M) or high temperature (45 degrees C) with low salt amount (0.5 M). Optimum reactant molar composition at 40 degrees C is 0.035P123:8KCl:1.34HCI:444H(2)O:1.0bis(trimethoxysilyl)ethane. Lower or higher SiO2/PI23 ratio led to the formation of uniform meso-macropores or pore-blocking effect. (c) 2005 Elsevier Inc. All rights reserved.

Chemical composition of the small coastal lagoons of the Mediterranean Spanish littoral

About sixty small water bodies (coastal lagoons, marshes, salt pans, channels, springs, etc.) of the Spanish Mediterranean coast were sampled seasonally for one year (1979-1980), in order to study different aspects of their chemical composition. The concentrations of major ions (alkalinity, Cl-, Ca2+, Mg2+, Na+, and K+), nutrients (N.NO-3, N.NO2-, TRP and Si), oxygen and pH were determined for this purpose. The salt concentrations measured range between 0.4 and 361.3 g l-1. The samples have been divided into four classes of salinity (in g l-1): Cl, S < 5; C2, 5 40. Within these classes, the pattern of ionic dominance recorded is remarkably constant and similar to that found in most coastal lagoons (Cl- > So42- > Alk., for the anions, and Na+ > Mg2+ > Ca2+ > K+, for the cations), although other models occur especially in the first class. The dominance of Na+ and Cl-, as well as the molar ratios Mg2+/Ca2+ and Cl- / SO42- ,clearly increase from class Cl to class C4. The hyperhaline waters include different subtypes of the major brine type"c",, of EUGSTER & HARDIE (1978), the Na+ - (Mg2+) - Cl- - (SO42-) being the most frequent. Nutrient concentrations fall within a wide range (N.NO3 from 0.1 to 1100 mg-at 1-1; PRT from 0.01 to 23.56 mg-at l-1 and Si from 1.0 to 502.0 mg-at l-1). The oxygen values are very variable too, ranging between 0 and 14.4 ml l-1. Four different patterns of nutrient distribution have been distinguished based on the mean concentrations of N.NO3-, and TRP (mean values in mg-at l-1): A, N.NO3- < 10, TRP > l ; B, N.NO3- > 100, TRP < 1; C, 10 < N.NO3- < 100, TRP < 1; C, D, N.NO3- < 10, TRP < 1. As a rule, lagoons of low salinity (C1 and C2 classes) display the nutrient pattern C, and lagoons of high salinity (C3 and C4) show the nutrient pattern D. Model A only appears in waters of very low salinity, whereas model B does not seem to be related to salinity.

Aggregation behavior of aqueous dioctadecyldimethylammonium bromide/monoolein mixtures: A multitechnique investigation on the composition and temperature

A recently described non-viral gene delivery system [dioctadecyldimethylammonium bromide (DODAB)/monoolein (MO)] has been studied in detail to improve knowledge on the interactions between lamellar (DODAB) and non-lamellar-forming (MO) lipids, as a means to enhance their final cell transfection efficiency. Indeed, the morphology, fluidity, and size of these cationic surfactant/neutral lipid mixtures play an important role in the ability of these systems to complex nucleic acids. The different techniques used in this work, namely dynamic light scattering (DLS), fluorescence spectroscopy, differential scanning calorimetry (DSC), cryogenic transmission electron microscopy (cryo-TEM), light microscopy (LM), and surface pressure-area isotherms, allowed fully characterization of the phase behavior and aggregate morphology of DODAB/MO mixtures at different molar ratios. Overall, the results indicate that the final morphology of DODAB/MO aggregates depends on the balance between the tendency of DODAB to form zero-curvature bilayer structures and the propensity of MO to form non-bilayer structures with negative curvature. These results also show that in the MO-rich region, an increase in temperature has a similar effect on aggregate morphology as an increase in MO concentration. (C) 2012 Elsevier B.V. All rights reserved.

Variations in Structure Explain the Viscometric Behavior of AOT Microemulsions at Low Water/AOT Molar Ratios

The viscosity of AOT/water/decane water-in-oil microemulsions exhibits a well-known maximum as a function of water/AOT molar ratio, which is usually attributed to increased attractions among nearly spherical droplets. The maximum can be removed by adding salt or by changing the oil to CCl4. Systematic small-angle X-ray scattering (SAXS) measurements have been used to monitor the structure of the microemulsion droplets in the composition regime where the maximum appears. On increasing the droplet concentration, the scattering intensity is found to scale with the inverse of the wavevector, a behavior which is consistent with cylindrical structures. The inverse wavevector scaling is not observed when the molar ratio is changed, moving the system away from the value corresponding to the viscosity maximum. It is also not present in the scattering from systems containing enough added salt to essentially eliminate the viscosity maximum. An asymptotic analysis of the SAXS data, complemented by some quantitative modeling, is consistent with cylindrical growth of droplets as their concentration is increased. Such elongated structures are familiar from related AOT systems in which the sodium counterion has been exchanged for a divalent one. However, the results of this study suggest that the formation of non-spherical aggregates at low molar ratios is an intrinsic property of AOT.

Composition Space Analysis in the Development of Copper Molybdate Hybrids Decorated by a Bifunctional Pyrazolyl/1,2,4-Triazole Ligand

A bitopic ligand, 4-(3,5-dimethylpyrazol-4-yl)-1,2,4-triazole (Hpz-tr) (1), containing two different heterocyclic moieties was employed for the design of copper(II)–molybdate solids under hydrothermal conditions. In the multicomponent CuII/Hpz-tr/MoVI system, a diverse set of coordination hybrids, [Cu(Hpz-tr)2SO4]·3H2O (2), [Cu(Hpz-tr)Mo3O10] (3), [Cu4(OH)4(Hpz-tr)4Mo8O26]·6H2O (4), [Cu(Hpz-tr)2Mo4O13] (5), and [Mo2O6(Hpz-tr)]·H2O (6), was prepared and characterized. A systematic investigation of these systems in the form of a ternary crystallization diagram approach was utilized to show the influence of the molar ratios of starting reagents, the metal (CuII and MoVI) sources, the temperature, etc., on the reaction products outcome. Complexes 2–4 dominate throughout a wide crystallization range of the composition triangle, while the other two compounds 5 and 6 crystallize as minor phases in a narrow concentration range. In the crystal structures of 2–6, the organic ligand behaves as a short [N–N]-triazole linker between metal centers Cu···Cu in 2–4, Cu···Mo in 5, and Mo···Mo in 6, while the pyrazolyl function remains uncoordinated. This is the reason for the exceptional formation of low-dimensional coordination motifs: 1D for 2, 4, and 6 and 2D for 3 and 5. In all cases, the pyrazolyl group is involved in H bonding (H-donor/H-acceptor) and is responsible for π–π stacking, thus connecting the chain and layer structures in more complicated H-bonding architectures. These compounds possess moderate thermal stability up to 250–300 °C. The magnetic measurements were performed for 2–4, revealing in all three cases antiferromagnetic exchange interactions between neighboring CuII centers and long-range order with a net moment below Tc of 13 K for compound 4.

Physical activity, body composition, exogenous estrogen use and their association with insulin-like growth factors

Obesity and physical inactivity are modifiable risk factors that are associated with several health issues; they are major factors in up to 30% of major cancers. Elevated levels of circulating insulin-like growth factor-I (IGF-I) have been associated with high body composition measurements and high cancer risk; exogenous estrogen use is associated with low circulating IGF-I levels and high cancer risk. The relationship between physical activity and circulating IGF levels is complex and findings of previous studies of their relationship remain inconsistent; however, these studies included vague definitions of physical activity. In this study, we used cross-sectional data from the Women's Health Initiative to determine the relationship between specific measures of physical activity (e.g., intensity, duration, and frequency) and circulating IGF-I levels, accounting for exogenous estrogen use and body composition. These data were collected from women enrolled at Women's Health Initiative clinical centers at Baylor College of Medicine and Wake Forest University School of Medicine. Multivariate linear regression analysis showed that circulating IGF-I and IGF-binding protein (BP) 3 levels were positively associated with frequency, duration, and intensity of physical activity. Circulating IGF-I levels and the molar IGF-I:IGF-BP3 ratio were significantly associated with frequency of walking, whereas circulating IGF-BP3 levels were significantly associated with strenuous physical activity, suggesting that different aspects of physical activity and their effects on fitness affect members of the IGF family differently. The results from our study support the recommendation of a regular exercise routine, particularly that of strenuous intensity, for postmenopausal women as a means to prevention of cancer.^

Chemical composition and age of metamorphic rocks from the Khavyven Highland, Eastern Kamchatka

Metamorphic rocks of the Khavyven Highland in eastern Kamchatka were determined to comprise two complexes of metavolcanic rocks that have different ages and are associated with subordinate amounts of metasediments. The complex composing the lower part of the visible vertical section of the highland is dominated by leucocratic amphibole-mica (+/-garnet) and epidote-mica (+/-garnet) crystalline schists, whose protoliths were andesites and dacites and their high-K varieties of island-arc calc-alkaline series. The other complex composing the upper part of the vertical section consists of spilitized basaltoids transformed into epidote-amphibole and phengite-epidote-amphibole green schists, which form (together with quartzites, serpentinized peridotites, serpentinites, and gabbroids) a sea-margin ophiolitic association. High LILE concentrations, high K/La, Ba/Th, Th/Ta, and La/Nb ratios, deep Ta-Nb minima, and low (La/Yb)_N and high 87Sr/86Sr ratios of the crystalline schists of the lower unit are demonstrated to testify to their subduction nature and suggest that their protolithic volcanics were produced in the suprasubduction environment of the Ozernoi-Valaginskii (Achaivayam-Valaginskii) island volcanic arc of Campanian-Paleogene age. The green schists of the upper unit show features of depleted MOR tholeiitic melts and subduction melts, which cause the deep Ta-Nb minima, and low K/La and 87Sr/86Sr ratios suggesting that the green schists formed in a marginal basin in front of the Ozernoi-Valaginskaya island arc. Recently obtained K-Ar ages in the Khavyven Highland vary from 32.4 to 39.3 Ma and indicate that metamorphism of the protolithic rocks occurred in Eocene under effect of collision and accretion processes of the arc complexes of the Ozernoi-Valaginskii and Kronotskii island arcs with the Asian continent and the closure of forearc oceanic basins in front of them. The modern position of the collision suture that marks the fossil subduction zone of the Ozernoi-Valaginskii arc and is spatially restricted to the buried Khavyven uplift in the Central Kamchatka Depression characterized by well-pronounced linear gravity anomalies.