Infrared and MAS NMR spectroscopic studies of Al18B4O33

The IR spectrum and B-11 and Al-27 MAS NMR spectra of Al18B4O33 are presented and discussed in relation to the possible existence of boron atoms substituting for aluminum atoms. The IR spectrum shows that the strong vibrations of the BO3 groups are present in the 1 500 similar to1 200 cm(-1) region, and very weak bands of BO4 units art present in the region from 1 000 to 1 100 cm(-1). B-11 MAS NMR spectrum indicates that the strong signal for BOB units appears in the region from delta +5 to delta +20, and the very weak signal for BO4 units is at about delta -1, while Al-27 MAS NMR spectrum shows five peaks at about delta +62, +42.1, +14, -4.7 and -6.4, originating from AlO4, AlO4, AlO5, AlO6 and AlO6, respectively, These results reveal that there are minor BO4 units in Al18B4O33, indicating that a small amount of B atoms substitute for Al atoms in the 4-fold coordination.

Investigation of thermal unfolding process of cyanic adduct of horseradish peroxidase by Fourier transform infrared and circular dichroism spectrometry

Detailed circular dichroism(CD) and Fourier transform infrared (FTIR) studies have been carried out to monitor thermal unfolding of horseradish peroxidase isoenzyme C(HRP) inhibited by CN(HRP-CN). The results suggest that HRP-CN is quite different from native HRP with different spin states of Fe of heme and different coordinated states. Cyanide becomes the sixth ligand of Fe(I) of heme and the hydrogen-binding network is destroyed partly at the same time, which cause the drastic decrease of thermal stability of HRP. The FTIR and Soret-CD spectra analysis demonstrate that during the heating process there is an intermediate state(I') which has both partly destroyed secondary and tertiary structures of native HRP, then it is the appearance of protein aggregation state(A) after fully unfolding. The unfolding pathway thus can be shown as follows: I -->I'-->U -->A.

The active sites in different TS-1 zeolites for propylene epoxidation studied by ultraviolet resonance Raman and ultraviolet visible absorption spectroscopies

The titanium species in four kinds of titanium-containing MFI zeolites have been studied by ultraviolet (UV)-Raman and ultraviolet visible (UV-Vis) absorption spectroscopies and by the epoxidation of propylene with diluted H2O2 solution (30%). UV-Raman spectroscopy is proved to be a suitable means to estimate qualitatively the framework titanium in TS-l zeolites. Based on the comparison of the relative intensity ratio I-1125/I-380 of UV-Raman spectra, the TS-1(conv.) sample synthesized hydrothermally by the conventional procedure shows the highest amount of framework titanium. UV-Vis spectroscopy reveals that besides minor anatase. titanium species are mainly tetrahydrally coordinated into the framework for TS-l(conv.) or the Ti-ZSM-5 sample prepared by gas-solid reaction between deboronated B-ZSM-5 and TiCl4 vapor at elevated temperatures. For the TS-1(org.) and TS-1(inorg.) samples synthesized hydrothermally using tetrapropylammonium bromide (TPABr) as template and tetrabutylorthotitanite (TBOT) and TiCl3 as titanium source, respectively, the presence of mononuclear and isolated TiOx species which are proposed to bond to the zeolite extraframework is observed. In addition to the framework titanium species, these isolated TiOx species are assumed to be also active for propylene epoxidation.

Quantitative studies of the optical and UV spectra of Galactic early B supergiants - I. Fundamental parameters

Aims. We undertake an optical and ultraviolet spectroscopic analysis of a sample of 20 Galactic B0-B5 supergiants of luminosity classes Ia, Ib, Iab, and II. Fundamental stellar parameters are obtained from optical diagnostics and a critical comparison of the model predictions to observed UV spectral features is made.

Forensic analysis of architectural finishes using Fourier transform infrared and Raman spectroscopy, Part I: The resin bases

The ability of Raman spectroscopy and Fourier transform infrared (FT-IR) microscopy to discriminate between resins used for the manufacture of architectural finishes was examined in a study of 39 samples taken from a commercial resin library. Both Raman and FT-IR were able to discriminate between different types of resin and both split the samples into several groups (six for FT-IR, six for Raman), each of which gave similar, but not identical, spectra. In addition, three resins gave unique Raman spectra (four in FTIR). However, approximately half the library comprised samples that were sufficiently similar that they fell into a single large group, whether classified using FT-IR or Raman, although the remaining samples fell into much smaller groups. Further sub-division of the FT-IR groups was not possible because the experimental uncertainty was of similar magnitude to the within-group variation. In contrast, Raman spectroscopy was able to further discriminate between resins that fell within the same groups because the differences in the relative band intensities of the resins, although small, were larger than the experimental uncertainty.

Forensic analysis of architectural finishes using fourier transform infrared and raman spectroscopy, part II:White paint

White household paints are commonly encountered as evidence in the forensic laboratory but they often cannot be readily distinguished by color alone so Fourier transform infrared (FT-IR) microscopy is used since it can sometimes discriminate between paints prepared with different organic resins. Here we report the first comparative study of FT-IR and Raman spectroscopy for forensic analysis of white paint. Both techniques allowed the 51 white paint samples in the study to be classified by inspection as either belonging to distinct groups or as unique samples. FT-IR gave five groups and four unique samples; Raman gave seven groups and six unique samples. The basis for this discrimination was the type of resin and/ or inorganic pigments/extenders present. Although this allowed approximately half of the white paints to be distinguished by inspection, the other half were all based on a similar resin and did not contain the distinctive modifiers/pigments and extenders that allowed the other samples to be identified. The experimental uncertainty in the relative band intensities measured using FT-IR was similar to the variation within this large group, so no further discrimination was possible. However, the variation in the Raman spectra was larger than the uncertainty, which allowed the large group to be divided into three subgroups and four distinct spectra, based on relative band intensities. The combination of increased discrimination and higher sample throughput means that the Raman method is superior to FT-IR for samples of this type. © 2005 Society for Applied Spectroscopy.

The feasibility of using near infrared and Raman spectroscopic techniques to detect fraudulent adulteration of chili powders with Sudan dye

Chili powder is a globally traded commodity which has been found to be adulterated with Sudan dyes from 2003 onwards. In this study, chili powders were adulterated with varying quantities of Sudan I dye (0.1-5%) and spectra were generated using near infrared reflectance spectroscopy (NIRS) and Raman
spectroscopy (on a spectrometer with a sample compartment modified as part of the study). Chemometrics were applied to the spectral data to produce quantitative and qualitative calibration models and prediction statistics. For the quantitative models coefficients of determination (R2) were found to be
0.891-0.994 depending on which spectral data (NIRS/Raman) was processed, the mathematical algorithm used and the data pre-processing applied. The corresponding values for the root mean square error of calibration (RMSEC) and root mean square error of prediction (RMSEP) were found to be 0.208-0.851%
and 0.141-0.831% respectively, once again depending on the spectral data and the chemometric treatment applied to the data. Indications are that the NIR spectroscopy based models are superior to the models produced from Raman spectral data based on a comparison of the values of the chemometric
parameters. The limit of detection (LOD) based on analysis of 20 blank chili powders against each calibration model gave 0.25% and 0.88% for the NIR and Raman data, respectively. In addition, adopting a qualitative approach with the spectral data and applying PCA or PLS-DA, it was possible to discriminate
between adulterated chili powders from non-adulterated chili powders.

Infrared and Raman screening of seized novel psychoactive substances: A large scale study of >200 samples

The potential of IR absorption and Raman spectroscopy for rapid identification of novel psychoactive substances (NPS) has been tested using a set of 221 unsorted seized samples suspected of containing NPS. Both IR and Raman spectra showed large variation between the different sub-classifications of NPS and smaller, but still distinguishable, differences between closely related compounds within the same class. In initial tests, screening the samples using spectral searching against a limited reference library allowed only 41% of the samples to be fully identified. The limiting factor in the identification was the large number of active compounds in the seized samples for which no reference vibrational data were available in the libraries rather than poor spectral quality. Therefore, when 33 of these compounds were independently identified by NMR and mass spectrometry and their spectra used to extend the libraries, the percentage of samples identified by IR and Raman screening alone increased to 76%, with only 7% of samples having no identifiable constituents. This study, which is the largest of its type ever carried out, therefore demonstrates that this approach of detecting non-matching samples and then identifying them using standard analytical methods has considerable potential in NPS screening since it allows rapid identification of the constituents of the majority of street quality samples. Only one complete feedback cycle was carried out in this study but there is clearly the potential to carry out continuous identification/updating when this system is used in operational settings.

The vibrational spectra of natural and perdeuterated monochlorogallane, H2Ga([mu]-Cl)2GaH2, and an empirical harmonic potential function

The infrared and Raman spectra of monochlorogallane and its fully deuterated isotopomer are recorded and assigned on the basis of the dimeric structures. H2Ga(μ-Cl)2GaH2 and D2Ga(μ-Cl)2GaD2, conforming to D2 symmetry. The observed frequencies are corrected for anharmonicity and fitted to a potential function in which 19 of the 33 independent force constants are refined.

Theoretical investigation of geometric configurations and vibrational spectra in citric acid complexes

The performance of advanced electronic ceramics is directly related to the synthesis route employed. Sol-gel methods are widely used for this purpose. However, the physicochemical intermediate steps are still not well understood. Better understanding and control of these processes can improve the final quality of samples. In this work, we studied theoretically the formation of metal complexes between citric acid and lithium or barium metal cations with different citric acid/metal proportions, using Density Functional Theory electronic structure calculations. Infrared and Raman scattering spectra were simulated for the more stable geometric configurations. Using this methodology, we identified some features of complexes formed in the synthesis process. Our results show that the complexes can be distinguished by changes in the bands assigned to C=O, COH-, and COO- group vibrations. An estimate of the most stable complexes is made based on total energy.

In silico infrared and Raman spectroscopy under pressure: The case of CaSnO3 perovskite

The CaSnO3 perovskite is investigated under geochemical pressure, up to 25 GPa, by means of periodic ab initio calculations performed at B3LYP level with local Gaussian-type orbital basis sets. Structural, elastic, and spectroscopic (phonon wave-numbers, infrared and Raman intensities) properties are fully characterized and discussed. The evolution of the Raman spectrum of CaSnO3 under pressure is reported to remarkably agree with a recent experimental determination [J. Kung, Y. J. Lin, and C. M. Lin, J. Chem. Phys. 135, 224507 (2011)] as regards both wave-number shifts and intensity changes. All phonon modes are symmetry-labeled and bands assigned. The single-crystal total spectrum is symmetry-decomposed into the six directional spectra related to the components of the polarizability tensor. The infrared spectrum at increasing pressure is reported for the first time and its main features discussed. All calculations are performed using the CRYSTAL14 program, taking advantage of the new implementation of analytical infrared and Raman intensities for crystalline materials. (C) 2015 AIP Publishing LLC.

Influence of water immersion and ultraviolet weathering on mechanical and viscoelastic properties of polyphenylene sulfide-carbon fiber composites

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Comparative study over methods developed for quantification of darunavir in tablets by environmental friendly infrared and capillary electrophoretic techniques

Darunavir, a protease inhibitor used in the treatment of HIV infection, presents few methods for its determination in pharmaceuticals. Infrared (IR) spectroscopy offers the possibility of obtaining spectra relatively quickly, providing interesting information, analytically, qualitatively or quantitatively. Capillary electrophoresis (CE) performs separations of high efficiency in shorter time with reagents and samples in small quantity. These two methods are cost-benefitted when we evaluate the green level and the cost of analysis. Faster and cheaper methods without generating organic waste by IR and CE for the quantification of darunavir were developed and validated, focusing socioeconomic impact of analytical decisions. If the cost of acquisition, maintenance, production, analysis and conditioning of drugs and pharmaceuticals is high, consequently the price of this product in the market will be higher and it cannot be accessible to the patient. Treatment failure not only affects the quality of life of patients, but also contributes significantly to the economic burden of the health system. In this context there is a tool called Analysis of the Life Cycle, which comes to make us think in a multidimensional way focusing the whole, the parts and especially the interaction among the parts of a system.

Sublimation of water ice mixed with silicates and tholins: Evolution of surface texture and reflectance spectra, with implications for comets

The surfaces of many objects in the Solar System comprise substantial quantities of water ice sometimes mixed with minerals and/or organic molecules. The sublimation of the ice changes the structural and optical properties of these objects. We present laboratory data on the evolution of the structure and the visible and near-infrared spectral reflectance of icy surface analogues of cometary ices, made of water ice, complex organic matter (tholins) and silicates, as they undergo sublimation under low temperature (<-70°C) and pressure (10-⁵mbar) conditions inside the SCITEAS simulation chamber. As the water ice sublimated, we observed in situ the formation of a porous sublimation lag deposit, or sublimation mantle, at the top of the ice. This mantle is a network of filaments made of the non-volatile particles. Organics or phyllosilicates grains, able to interact via stronger inter-particulate forces than olivine grains, can form a foam-like structure having internal cohesiveness, holding olivine grains together. As this mantle builds-up, the band depths of the sub-surface water ice are attenuated until complete extinction under only few millimeters of mantle. Optically thick sublimation mantles are mainly featureless in the near infrared. The absorption bands of the minerals present in the mantle are weak, or even totally absent if minerals are mixed with organics which largely dominate the VIS–NIR reflectance spectrum. During sublimation, ejections of large fragments of mantle, triggered by the gas flow, expose ice particles to the surface. The contrast of brightness between mantled and ice-exposed areas depends on the wavelength range and the dust/ice ratio considered. We describe how the chemical nature of the non-volatiles, the size of their particles, the way they are mixed with the ice and the dust/ice mass ratio influence the texture, activity and spectro-photometric properties of the sublimation mantles. These data provide useful references for interpreting remote-sensing observations of comets and also icy satellites or trans-neptunian objects.

Optical and ultraviolet observations of a strong flare in the young, single K2 dwarf LQ Hya

We present high-resolution optical echelle spectra and IUE observations during a strong flare on 1993 December 22 in the very active, young, rapidly rotating, single K2 dwarf LQ Hya. The initial impulsive phase of the flare, which started sometime between 2:42 ut and 4:07 ut, was characterized by strong optical continuum enhancement and blueshifted emission lines with broad wings. The optical chromospheric lines reached their maximum intensity at ≈ 5:31 ut, by which time the blueshift vanished and the optical continuum enhancement had sharply decreased. Thereafter, the line emission slowly decreased and the lines redshift in a gradual phase that lasted at least two more hours. The Mg II lines behaved similarly. Quiescent C IV flux levels were not recovered until 21 h later, though a data gap and a possible second flare make the interpretation uncertain. In addition to the typically flare-enhanced emission lines (e.g., H α and H β), we observe He I D_3 going into emission, plus excess emission (after subtraction of the quiescent spectrum) in other He I and several strong neutral metal lines (e.g., Mg I b). Flare enhancement of the far-ultraviolet continuum generally agrees with an Si I recombination model. We estimate the total flare energy, and discuss the broad components, asymmetries and Doppler shifts seen in some of the emission lines.