Flow analysis-hydride generation-gas phase derivative molecular absorption spectrophotometric determination of antimony in antileishmanial drugs

In the present work, the development of a method based on the coupling of flow analysis (FA), hydride generation (HG), and derivative molecular absorption spectrophotometry (D-EAM) in gas phase (GP), is described in order to determine total antimony in antileishmanial products. Second derivative order (D²224nm) of the absorption spectrum (190 - 300 nm) is utilized as measurement criterion. Each one of the parameters involved in the development of the proposed method was examined and optimized. The utilization of the EAM in GP as detection system in a continuous mode instead of atomic absorption spectrometry represents the great potential of the analytic proposal.

UV-visible scanning spectrophotometry and chemometric analysis as tools for carotenoids analysis in cassava genotypes (Manihot esculenta Crantz)

In this study, the metabolomics characterization focusing on the carotenoid composition of ten cassava (Manihot esculenta) genotypes cultivated in southern Brazil by UV-visible scanning spectrophotometry and reverse phase-high performance liquid chromatography was performed. Cassava roots rich in -carotene are an important staple food for populations with risk of vitamin A deficiency. Cassava genotypes with high pro-vitamin A activity have been identified as a strategy to reduce the prevalence of deficiency of this vitamin. The data set was used for the construction of a descriptive model by chemometric analysis. The genotypes of yellow-fleshed roots were clustered by the higher concentrations of cis--carotene and lutein. Inversely, cream-fleshed roots genotypes were grouped precisely due to their lower concentrations of these pigments, as samples rich in lycopene (redfleshed) differed among the studied genotypes. The analytical approach (UV-Vis, HPLC, and chemometrics) used showed to be efficient for understanding the chemodiversity of cassava genotypes, allowing to classify them according to important features for human health and nutrition.

Performance characteristics of UV and visible spectrophotometry methods for quantitative determination norfloxacin in tablets

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

Watson–Crick and Sugar-Edge Base Pairing of Cytosine in the Gas Phase: UV and Infrared Spectra of Cytosine·2-Pyridone

While keto-amino cytosine is the dominant species in aqueous solution, spectroscopic studies in molecular beams and in noble gas matrices show that other cytosine tautomers prevail in apolar environments. Each of these offers two or three H-bonding sites (Watson–Crick, wobble, sugar-edge). The mass- and isomer-specific S1 ← S0 vibronic spectra of cytosine·2-pyridone (Cyt·2PY) and 1-methylcytosine·2PY are measured using UV laser resonant two-photon ionization (R2PI), UV/UV depletion, and IR depletion spectroscopy. The UV spectra of the Watson–Crick and sugar-edge isomers of Cyt·2PY are separated using UV/UV spectral hole-burning. Five different isomers of Cyt·2PY are observed in a supersonic beam. We show that the Watson–Crick and sugar-edge dimers of keto-amino cytosine with 2PY are the most abundant in the beam, although keto-amino-cytosine is only the third most abundant tautomer in the gas phase. We identify the different isomers by combining three different diagnostic tools: (1) methylation of the cytosine N1–H group prevents formation of both the sugar-edge and wobble isomers and gives the Watson–Crick isomer exclusively. (2) The calculated ground state binding and dissociation energies, relative gas-phase abundances, excitation and the ionization energies are in agreement with the assignment of the dominant Cyt·2PY isomers to the Watson–Crick and sugar-edge complexes of keto-amino cytosine. (3) The comparison of calculated ground state vibrational frequencies to the experimental IR spectra in the carbonyl stretch and NH/OH/CH stretch ranges strengthen this identification.

Quantificação de polifosfatos no bacalhau. Validação de um método de análise

O bacalhau (Gadus morhua) faz parte da dieta alimentar dos portugueses há vários séculos, sendo atualmente, um dos maiores consumidores deste peixe a nível mundial. Após o processo de salga, esta espécie possui características únicas como a consistência, cheiro, paladar e cor amarela. É precisamente devido à coloração do peixe que alguns produtores da Islândia, Noruega e Dinamarca requisitaram às autoridades da União Europeia (UE) a aprovação da utilização de polifosfatos no processo de salga húmida do bacalhau. Os polifosfatos são aditivos alimentares bastante usados no processamento do pescado pois previnem a oxidação dos lípidos e proteínas do músculo do bacalhau, evitando assim a indesejada mudança de cor do peixe. Apesar dos esforços da Associação dos Industriais do Bacalhau (AIB) e do governo português para a rejeição da proposta nórdica, tal não se verificou. Deste modo, no início do próximo ano já será possível a venda na UE de bacalhau com fosfatos. A quantificação do teor de fosfatos no bacalhau é geralmente efetuada por Espetrofotometria de absorção molecular no ultravioleta-visível (UV-Visível). Esta quantificação é baseada no método de determinação do fósforo total, através da hidrólise dos fosfatos a ortofosfatos com posterior medição da cor amarela, gerada pela reação destes com uma solução de molibdato-vanadato. O objetivo desta dissertação foi a validação de um método de análise para a quantificação dos polifosfatos no bacalhau. O método validado foi o descrito na norma NP 4495 para produtos de pesca e aquicultura. O desenvolvimento deste trabalho foi realizado em laboratório acreditado para águas e produtos alimentares (Equilibrium - Laboratório de Controlo de Qualidade e de Processos Lda, L0312). Foi ainda determinada a influência do teor de cloreto de sódio na quantificação dos polifosfatos e o teor de humidade, uma vez que este pode afetar o produto durante a sua comercialização. No processo de validação do método foram estudados diversos parâmetros, tais como a seletividade, linearidade, sensibilidade, limite de quantificação e precisão. Pela análise dos resultados obtidos conclui-se que o método para determinação de fosfatos no bacalhau se encontra validado, uma vez que satisfaz todas as especificações determinadas para cada parâmetro de validação avaliado.

Narcolepsy and familial advanced sleep-phase syndrome: molecular genetics of sleep disorders.

Sleep disorders are very prevalent and represent an emerging worldwide epidemic. However, research into the molecular genetics of sleep disorders remains surprisingly one of the least active fields. Nevertheless, rapid progress is being made in several prototypical disorders, leading recently to the identification of the molecular pathways underlying narcolepsy and familial advanced sleep-phase syndrome. Since the first reports of spontaneous and induced loss-of-function mutations leading to hypocretin deficiency in human and animal models of narcolepsy, the role of this novel neurotransmission pathway in sleep and several other behaviors has gained extensive interest. Also, very recent studies using an animal model of familial advanced sleep-phase syndrome shed new light on the regulation of circadian rhythms.

Hydrogen bonding in the gas-phase: the molecular structures of 2‑hydroxybenzamide (C7H7NO2) and 2‑methoxybenzamide (C8H9NO2), obtained by gas-phase electron diffraction and theoretical calculations

The structures of 2-hydroxybenzamide(C7H7NO2) and 2-methoxybenzamide (C8H9NO2) have been determined in the gas-phase by electron diffraction using results from quantum chemical calculations to inform restraints used on the structural parameters. Theoretical methods (HF and MP2/6-311+G(d,p)) predict four stable conformers for both 2-hydroxybenzamide and 2-methoxybenzamide. For both compounds, evidence for intramolecular hydrogen bonding is presented. In 2-hydroxybenzamide, the observed hydrogen bonded fragment is between the hydroxyl and carbonyl groups, while in 2-methoxybenzamide, the hydrogen bonded fragment is between one of the hydrogen atoms of the amide group and the methoxy oxygen atom.

UV optical absorption spectra analysis of beryl crystals from Brazil

The spectral decomposition analysis was applied to the optical absorption spectra of green and colorless beryl crystals from the Brazilian Eastern Pegmatitic province in the natural state, Submitted to heat treatment and irradiated with UV light The attributions of the lines were made taking into account highly accurate quantum mechanical calculations The deconvolution of the green beryl spectra revealed four lines, two of them around 12,000 cm(-1) (1 5eV) and two of them around 34,000 cm(-1) (4.2 eV) attributed to Fe(2+) and Fe(3+), respectively The deconvolution of the colorless beryl spectra without any treatment, after heating and for the same heat treatment followed by UV light irradiation revealed five lines The analysis of ratio relations showed that the lines at 36,400 cm(-1) (4.5 eV) and 41,400 cm(-1) (5 1 eV) belongs to a single defect attributed to a silicon dangling bond defect (=Si). Discussions and comparison with reported defects in quartz have supported the allocation of the lines at 61,000 cm(-1) (7.6 eV) and 43,800 cm(-1) (5 4 eV) to diamagnetic oxygen vacancy defect ( Si-Si ) and unrelaxed ( Si Si ) defect, respectively Finally, the line at 39.100 cm(-1) (4.8 eV), quite polarized along the c-axis, was attributed to a (Fe(2+) OH(-)) defect in the structural channels (C) 2009 Elsevier B V All rights reserved

Avaliação da remoção catalítica de compostos orgânicos monoaromáticos em água utilizando materiais nanoestruturados de sílica

Statistics of environmental protection agencies show that the soil has been contaminated with problems often resulting from leaks, spills and accidents during exploration, refining, transportation and storage oil operations and its derivatives. These, gasoline noteworthy, verified by releasing, to get in touch with the groundwater, the compounds BTEX (benzene, toluene, ethylbenzene and xylenes), substances which are central nervous system depressants and causing leukemia. Among the processes used in remediation of soil and groundwater contaminated with organic pollutants, we highlight those that use hydrogen peroxide because they are characterized by the rapid generation of chemical species of high oxidation power, especially the hydroxyl radical ( OH), superoxide (O2 -) and peridroxil (HO2 ), among other reactive species that are capable of transforming or decomposing organic chemicals. The pH has a strong effect on the chemistry of hydrogen peroxide because the formation of different radicals directly depends on the pH of the medium. In this work, the materials MCM-41 and Co-MCM-41 were synthesized and used in the reaction of BTEX removal in aqueous media using H2O2. These materials were synthesized by the hydrothermal method and the techniques used to characterize were: XRD, TG/DTG, adsorption/desorption N2, TEM and X-Ray Fluorescence. The catalytic tests were for 5 h of reaction were carried out in reactors of 20 mL, which was accompanied by the decomposition of hydrogen peroxide by molecular absorption spectrophotometry in the UV-Vis, in addition to removal of organic compounds BTEX was performed as gas chromatography with detection photoionization and flame ionization and by static headspace sampler. The characterizations proved that the materials were successfully synthesized. The catalytic tests showed satisfactory results, and the reactions containing BTEX + Co-MCM-41 + H2O2 at pH = 12.0 had the highest percentages of removal for the compounds studied

UV-visible absorption characteristics of TEOS-derived and Cr-doped silica sonogels aged in different pH solutions and heat treated up to 600 degrees C

Cr-doped xerogels were obtained by sol-gel process from the acid-catalyzed and ultrasound-stimulated hydrolysis of tetraethoxysilane (TEOS) with addition of CrCl3.6H(2)O in water solution during the liquid step of the process. The gels were aged immersed in different pH solutions for about 30 days, after that they were allowed to dry. The samples were annealed at temperatures ranging from 40 to 600degreesC and analyzed by UV-visible absorption spectroscopy. Cr3+ is the preferable oxidation state of the chromium ion in the gels annealed up to 250-300degreesC, in the case of aging in solutions of pH=5 and 11. A high UV absorption below similar to320 nm, due to the host gel, and different absorption bands, depending on the temperature, due to the chromium ion were observed in the xerogels at temperatures below similar to250degreesC, in the case of aging in solutions of pH=1 and 2. These absorption bands have not been assigned. Above 300degreesC up to 600degreesC, Cr5+, and possibly Cr6+, are the preferable oxidation states of the chromium ion independent of the pH of the aging solution, so the xerogels turn to a yellowish appearance in all cases.

Determination of Total Sulfur in Agricultural Samples by High-Resolution Continuum Source Flame Molecular Absorption Spectrometry

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

Determination of calcium by atomic absorption spectrophotometry applied to the preparation of alginate:chitosan complexes

Polysaccharicles, as alginate and chitosan, have been used to obtain modified release dosage forms. Alginate, due to its property of building gels during the complex formation with calcium ions, allows the building of capsules containing a core constituted by calcium alginate. This work had for objective to determine the appropriate calcium concentration for the preparation of alginate-chitosan capsules, by means of calcium quantification using atomic absorption spectrophotometry. The methodology of calcium quantification was validated through analysis of the limit of detection, precision, accuracy and recovery of the method. The capsules, containing or not the drug, were prepared by the complex coacervation/ionotropic gelification method. Calcium was quantified after samples mineralization and dilution in lantanium solution. The results showed that the amount of calcium incorporated into the capsules depends on the amount of calcium added to the medium, and this ratio increases until the concentration of 1.5% of initial calcium chloride and above this concentration there is a decrease in the proportion of calcium bonded. It was observed that the proportion of calcium that links to the polymer is inversely proportional to the amount of calcium added. The calcium amount incorporated depends on the concentration of the polymeric dispersions used as well as on the ratio between the two polymers.

A simple and fast method for assessment of the nitrogen-phosphorus-potassium rating of fertilizers using high-resolution continuum source atomic and molecular absorption spectrometry

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

Multivariate analyses of UV-Vis absorption spectral data from cachaca wood extracts: a model to classify aged Brazilian cachacas according to the wood species used

Multivariate analyses of UV-Vis spectral data from cachaca wood extracts provide a simple and robust model to classify aged Brazilian cachacas according to the wood species used in the maturation barrels. The model is based on inspection of 93 extracts of oak and different Brazilian wood species by a non-aged cachaca used as an extraction solvent. Application of PCA (Principal Components Analysis) and HCA (Hierarchical Cluster Analysis) leads to identification of 6 clusters of cachaca wood extracts (amburana, amendoim, balsamo, castanheira, jatoba, and oak). LDA (Linear Discriminant Analysis) affords classification of 10 different wood species used in the cachaca extracts (amburana, amendoim, balsamo, cabreuva-parda, canela-sassafras, castanheira, jatoba, jequitiba-rosa, louro-canela, and oak) with an accuracy ranging from 80% (amendoim and castanheira) to 100% (balsamo and jequitiba-rosa). The methodology provides a low-cost alternative to methods based on liquid chromatography and mass spectrometry to classify cachacas aged in barrels that are composed of different wood species.

Determination of chlorine in food samples via the AlCl molecule using high-resolution continuum source molecular absorption spectrometry in a graphite furnace

Determination of chlorine using the molecular absorption of aluminum mono-chloride (AlCl) at the 261.418 nm wavelength was accomplished by high-resolution continuum source molecular absorption spectrometry using a transversely heated graphite tube furnace with an integrated platform. For the analysis. 10 mu L of the sample followed by 10 mu L of a solution containing Al-Ag-Sr modifier, (1 g L-1 each), were directly injected onto the platform. A spectral interference due to the use of Al-Ag-Sr as mixed modifier was easily corrected by the least-squares algorithm present in the spectrometer software. The pyrolysis and vaporization temperatures were 500 degrees C and 2200 degrees C, respectively. To evaluate the feasibility of a simple procedure for the determination of chlorine in food samples present in our daily lives, two different digestion methods were applied, namely (A) an acid digestion method using HNO3 only at room temperature, and (B) a digestion method with Ag, HNO3 and H2O2, where chlorine is precipitated as a low-solubility salt (AgCl), which is then dissolved with ammonia solution. The experimental results obtained with method B were in good agreement with the certified values and demonstrated that the proposed method is more accurate than method A. This is because the formation of silver chloride prevented analyte losses by volatilization. The limit of detection (LOD, 3 sigma/s) for Cl in methods A and B was 18 mu g g(-1) and 9 mu g g(-1), respectively, 1.7 and 3.3 times lower compared to published work using inductively coupled plasma optical emission spectrometry, and absolute LODs were 2.4 and 1.2 ng, respectively. (C) 2012 Elsevier B.V. All rights reserved.