Poliuretanos obtenidos a partir de aceite de higuerilla modificado y poli-isocianatos de lisina: síntesis, propiedades mecánicas y térmicas y degradación in vitro

Biodegradable polyurethanes (PUR) were prepared from polyols derived from castor oil by transesterification of pentaerythritol-modified castor oil and lysine polyisocyanates (LDI and LTI). The polyurethanes obtained were characterized by Fourier transform infrared spectroscopy, thermogravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA). The mechanical behavior of the polyurethanes was measured by Shore A hardness and tensile testing (stress-strain curves). The biodegradable nature of the material was determined by contact angle, water absorption tests, and in vitro degradation in PBS solution. This study aims to examine the effect of the structure and functionality of diisocyanate on the mechanical properties and in vitro degradation of the material. The results were compared with homologous materials obtained from isophorone diisocyanate (IPDI) used in previous works. The objective was to evaluate candidate materials that can be potentially used in tissue engineering.

Interactions of chitosan/genipin hydrogels during drug delivery: a QSPR approach

A hydrogel comprised of chitosan crosslinked using the low-toxicity crosslinker genipin was prepared, and the absorption of glibenclamide by the hydrogel was investigated. Optimized structures and their molecular electrostatic potentials were calculated using the AM1 method, and the results were used to evaluate the molecular interactions between the three compounds. The quantitative structure-property relationship model was also used to estimate the activity of the chemicals on the basis their molecular structures. In addition, theoretical Fourier transform infrared spectra were calculated to analyze the intermolecular interactions in the proposed system. Finally, the hydrophilicity of the hydrogel and its influence on the absorption process were also estimated.

Estudo do teste de Scott via técnicas espectroscópicas: um método alternativo para diferenciar cloridrato de cocaína e seus adulterantes

Cocaine is usually seized mixed with a wide variety of adulterants such as benzocaine, lidocaine, caffeine, and procaine. The forensic identification of cocaine in these street drug mixtures is normally performed using colorimetric testing kits, but these tests may suffer from interferences, producing false-positive results. Here, we describe the use of analytical techniques including attenuated total reflection Fourier transform infrared (ATR-FTIR) and ultraviolet-visible (UV-VIS) spectroscopies to distinguish between cocaine and other adulterants (lidocaine, promethazine, powdered milk and yeast) that yield positive results on the Scott test using the thiocyanate cobalt reagent. A further 13 substances were also analyzed using the Scott test.

ANÁLISES FÍSICO-QUÍMICAS DE BIOFILMES DE SULFATO DE CONDROITOINA MODIFICADO

Numerous investigations are dedicated to the research and development of new polymer materials destined for innovation in pharmaceutical forms. The application of these technological resources has allowed the commercialization of new therapeutic systems for modified drug release. This investigation aimed to evaluate the association of modified chondroitin sulfate with an insoluble polymer, Eudragit® RS 30 D, widely available in the pharmaceutical market. Isolated films were prepared by the evaporation process using a Teflon® plate. The aqueous dispersions (4% m/v) of synthetic polymer received the addition of modified chondroitin sulfate at different ratios. The interactions of the polymer chains in the blends were physicochemically characterized by means of Fourier transform infrared spectroscopy, thermal analyses, differential scanning calorimetry, thermogravimetry and scanning electron microscopy combined with hydration and assays in alkaline pH. The results showed appropriate properties of the coating materials for solid oral forms intended for drug deliver in specific environments.

PARÂMETROS TERMODINÂMICOS DA CASCA DE LARANJA DESIDRATADA

The global energy scenario is currently a widely discussed topic, with growing concern about the future supplies. Thus, much attention has been dedicated to the utilization of biomass as an energy resource. In this respect, orange peel has become a material of great interest, especially to Brazil, which generates around 9.5 million tons of this waste per year. To this end, the authors studied the kinetics of the thermal processing of dried orange peel in inert and oxidizing atmosphere. The thermodynamic parameters were determined by the Ozawa-Flynn-Wall method for the global process observed during heating from the 25°C up to 800°C. The thermal analysis in air and nitrogen showed 3-2 stages of mass loss, respectively, with approximately 20% residual mass under a nitrogen atmosphere. The increase in the values of activation energy for the conversion points between 20% and 60% for thermal effects in air and nitrogen atmosphere was observed. The activation energy obtained in an oxidizing atmosphere was higher than that obtained under a nitrogen atmosphere. The fourier-transform infrared spectroscopy and X-ray diffraction analysis showed that the material has a high level of complexity with the presence of alkali and alkaline earth groups as well as phosphate, plus substances such as pectin, cellulose and lignin.

TUNGSTOPHOSPHORIC ACID HETEROGENIZED ONTO NH4ZSM5 AS AN EFFICIENT AND RECYCLABLE CATALYST FOR THE PHOTOCATALYTIC DEGRADATION OF DYES

Materials based on tungstophosphoric acid (TPA) immobilized on NH4ZSM5 zeolite were prepared by wet impregnation of the zeolite matrix with TPA aqueous solutions. Their concentration was varied in order to obtain TPA contents of 5%, 10%, 20%, and 30% w/w in the solid. The materials were characterized by N2 adsorption-desorption isotherms, XRD, FT-IR, 31P MAS-NMR, TGA-DSC, DRS-UV-Vis, and the acidic behavior was studied by potentiometric titration with n-butylamine. The BET surface area (SBET) decreased when the TPA content was raised as a result of zeolite pore blocking. The X-ray diffraction patterns of the solids modified with TPA only presented the characteristic peaks of NH4ZSM5 zeolites, and an additional set of peaks assigned to the presence of (NH4)3PW12O40. According to the Fourier transform infrared and 31P magic angle spinning-nuclear magnetic resonance spectra, the main species present in the samples was the [PW12O40]3- anion, which was partially transformed into the [P2W21O71]6- anion during the synthesis and drying steps. The thermal stability of the NH4ZSM5TPA materials was similar to that of their parent zeolites. Moreover, the samples with the highest TPA content exhibited band gap energy values similar to those reported for TiO2. The immobilization of TPA on NH4ZSM5 zeolite allowed the obtention of catalysts with high photocatalytic activity in the degradation of methyl orange dye (MO) in water, at 25 ºC. These can be reused at least three times without any significant decrease in degree of degradation.

UTILIZAÇÃO DO COMPÓSITO NANOESTRUTURADO SIO2/TIO2NA FOTODEGRADAÇÃO DE CORANTES TÊXTEIS COM LUZ SOLAR NATURAL

SiO2/TiO2 nanostructured composites with three different ratios of Si:Ti were prepared using the sol-gel method. These materials were characterized using energy dispersive X-ray fluorescence, Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, photoluminescence, Raman with Fourier transform infrared spectroscopy, and the specific surface area. The band gaps of materials were determined by diffuse reflectance spectra, and the values of 3.20 ± 0.01, 2.92 ± 0.02, and 2.85 ± 0.01 eV were obtained as a result of the proportional increases in the amount of Ti within the composite. The materials exhibit only the anatase (TiO2) crystalline phase and have crystalline domains ranging from 4 to 5 nm. The photodegradation process of methylene blue, royal blue GRL, and golden yellow GL dyes were studied with respect to their contact times, pH variations within the solution, and the variations in the dye concentration of the solution in response to only sunlight. The maximum amount of time for the mineralization of dyes was 90 min. The kinetics of the process follows an apparently first order model, in which the obtained rate constant values were 5.72 × 10-2 min-1 for methylene blue, 6.44 × 10-2min-1 for royal blue GRL, and 1.07 × 10-1min-1 for golden yellow.

INFLUÊNCIA DO CATALISADOR EM SOLUÇÕES POLIMÉRICAS PARA O PREPARO DE GÉIS ORGÂNICOS DE RESORCINOL-FORMALDEÍDO

Resorcinol-formaldehyde (RF) organic gels have been extensively used to produce carbon aerogels. The organic gel synthesis parameters greatly affect the structure of the resulting aerogel. In this study, the influence of the catalyst quantity on the polymeric solution sol-gel process was investigated. Sodium carbonate was used as a basic catalyst. RF gels were synthesized with a resorcinol to formaldehyde molar ratio of 0.5, a resorcinol to catalyst (R/C) molar ratio equal to 50 or 300, and a resorcinol to solvent ratio of 0.1 g mL-1. The sol-gel process was evaluated in situ by Fourier transform infrared spectroscopy using a universal attenuated total reflectance sensor and measurements of the kinematic viscosity. The techniques showed the evolution of the sol-gel process, and the results showed that the lower catalyst quantity induced a higher gel point, with a lower viscosity at the gel point. Differential scanning calorimetry was used to investigate the thermal behavior of the RF dried gel, and results showed that the exothermic event related to the curing process was shifted to higher temperatures for solutions containing higher R/C ratios.

Ni(II), Cu(II), AND Zn(II) COMPLEXES DERIVED FROM A NEW SCHIFF BASE 2-((Z)-(3-METHYLPYRIDIN-2- YLEIMINO)METHYL)PHENOL AND SYNTHESIS OF NANO SIZED METAL OXIDE PARTICLES FROM THESE COMPOUNDS

Synthesis, spectral identification, and magnetic properties of three complexes of Ni(II), Cu(II), and Zn(II) are described. All three compounds have the general formula [M(L)2(H2O)2], where L = deprotonated phenol in the Schiff base 2-((z)-(3-methylpyridin-2-yleimino)methyl)phenol. The three complexes were synthesized in a one-step synthesis and characterized by elemental analysis, Fourier transform infrared spectroscopy, electronic spectra, X-ray diffraction (XRD), and room temperature magnetic moments. The Cu(II) and Ni(II) complexes exhibited room temperature magnetic moments of 1.85 B.M. per copper atom and 2.96 B.M. per nickel atom. The X-band electron spin resonance spectra of a Cu(II) sample in dimethylformamide frozen at 77 K (liquid nitrogen temperature) showed a typical ΔMS = ± 1 transition. The complexes ([M(L)2(H2O)2]) were investigated by the cyclic voltammetry technique, which provided information regarding the electrochemical mechanism of redox behavior of the compounds. Thermal decomposition of the complexes at 750 ºC resulted in the formation of metal oxide nanoparticles. XRD analyses indicated that the nanoparticles had a high degree of crystallinity. The average sizes of the nanoparticles were found to be approximately 54.3, 30.1, and 44.4 nm for NiO, CuO, and ZnO, respectively.

2-(4-IODO-2,5-DIMETOXIFENIL)-N-[(2-METOXIFENIL)METIL]ETAMINA OU 25I-NBOME: CARACTERIZAÇÃO QUÍMICA DE UMA DESIGNER DRUG

Drug trafficking and the introduction of new drugs onto the illicit market are one of the main challenges of the forensic community. In this study, the chemical profile of a new designer drug, 2-(4-iodine-2,5-dimethoxyphenyl)-n-[(2-methoxyphenyl)methyl]etamine or 25I-NBOMe was explored using thin layer chromatography (TLC), ultraviolet-visible spectrophotometry (UV-Vis), attenuated total reflection with Fourier transform infrared spectroscopy(ATR-FTIR), gas chromatography mass spectrometry (GC-MS) and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR MS). First, the TLC technique was effective for identifying spots related to 25C-, 25B- and 25I-NBOMe compounds, all with the same retention factor, Rf ≈ 0.50. No spot was detected for 2,5-dimethoxy-4-bromoamphetamine, 2,5-Dimethoxy-4-chloroamphetamine or lysergic acid diethylamide compounds. ATR-FTIR preserved the physical-chemical properties of the material, whereas GC-MS and ESI-MS showed better analytical selectivity. ESI(+)FT-ICR MS was used to identify the exact mass (m/z428.1706 for the [M + H]+ ion), molecular formula (M = C18H22INO3), degree of unsaturation (DBE = 8) and the chemical structure (from collision induced dissociation, CID, experiments) of the 25I-NBOMe compound. Furthermore, the ATR-FTIR and CID results suggested the presence of isomers, where a second structure is proposed as an isomer of the 25I-NBOMe molecule.

Avaliação por espestroscopia no infravermelho da microestrutura de poliuretano baseado em resina polibutadiênica hidroxilada

Este trabalho apresenta uma avaliação da microestrutura ou seja, dos teores dos isômeros 1,4-cis, 1,4-trans e 1,2-vinil do segmento flexível de um poliuretano (PU) preparado a partir de resina polibutadiênica hidroxilada (PBLH), por meio da análise no infravermelho empregando-se a técnica de pastilha com brometo de potássio.

Estudo do comportamento térmico dos compostos de Ag+ e Pb2+ com o ligante 1,4-bis(3-carbóxi-3-oxo-prop-1-enil)benzeno

Este trabalho reporta o estudo de compostos binários do dicarboxilato 1,4-bis(3-carbóxi-3-oxo-prop-1-enil)benzeno, C6H4(-CH=CH-CO-COO-)2 , com os cátions metálicos Ag+ e Pb2+, obtidos a partir de soluções aquosas do ligante e dos nitratos dos cátions metálicos, em proporções estequiométricas. Para a caracterização e o estudo do processo de decomposição térmica desses compostos foram empregadas Espectrofotometria de Absorção na Região do Infravermelho com Transformada de Fourier (FT-IR), Análise Elementar (C, H), Complexometria com EDTA, Termogravimetria (TG) e Calorimetria Exploratória Diferencial (DSC).

Determination of sulfur in diesel using ATR/FTIR and multivariate calibration

The aim of this present work was to provide a more fast, simple and less expensive to analyze sulfur content in diesel samples than by the standard methods currently used. Thus, samples of diesel fuel with sulfur concentrations varying from 400 and 2500 mgkg-1 were analyzed by two methodologies: X-ray fluorescence, according to ASTM D4294 and by Fourier transform infrared spectrometry (FTIR). The spectral data obtained from FTIR were used to build multivariate calibration models by partial least squares (PLS). Four models were built in three different ways: 1) a model using the full spectra (665 to 4000 cm-1), 2) two models using some specific spectrum regions and 3) a model with variable selected by classic method of variable selection stepwise. The model obtained by variable selection stepwise and the model built with region spectra between 665 and 856 cm-1 and 1145 and 2717 cm-1 showed better results in the determination of sulfur content.

Escolha de ginecologia e obstetrícia por graduandos da Universidade de Brasília: um estudo de influências numa série histórica

Analisa-se a escolha de residência médica em Ginecologia e Obstetrícia (GO) em função de características pessoais dos graduandos, eventos curriculares e contexto temporal da instituição. O estudo incluiu 792 egressos do curso de Medicina da Universidade de Brasília, formados no período 1994-2006. Os dados abrangeram descritores demográficos e de aprendizagem, preferência inicial por carreira, monitorias, rendimento acadêmico, estágio seletivo no internato e inscrição para residência médica ao término do curso. Análises de contingência e de regressão logística foram realizadas com os egressos agrupados segundo a escolha ou não de GO. No conjunto, 8% dos egressos escolheram GO, dentre os quais 33% manifestaram atração inicial pela área. Não houve tendência temporal consistente na escolha ou na atração inicial, mas no qüinqüênio 1997-2001 a proporção de escolha foi menor do que a de atração inicial, em correspondência a mudanças na ambiência do curso. A análise de regressão logística identificou seis fatores preditivos da escolha: estágio seletivo, monitoria e incremento de rendimento em GO, preferência inicial, sexo feminino e época de graduação. Em conclusão, fatores associados à escolha de GO numa série histórica de 13 anos incluíram características pessoais, eventos curriculares e fase da conjuntura institucional.

Indicadores da escolha de pediatria por graduandos da universidade de Brasília: estudo longitudinal em série histórica

Os autores analisaram a escolha de residência médica em Pediatria dentre 877 egressos do curso de Medicina da Universidade de Brasília, formados no período 1994-2007. Os dados abrangeram descritores demográficos e de aprendizagem, preferência inicial por carreira, monitoria, rendimento acadêmico, estágio seletivo no internato e inscrição para residência médica. Efetuaram-se análises de contingência e de regressão logística agrupando-se os egressos por escolha de Pediatria ou não. Do total, 9,7% escolheram Pediatria, dentre os quais 44,7% mostraram atração inicial e 45,9% expressaram interesse pela área já na fase clínica. No período 2002-2007, houve declínio significante da escolha, em conexão com menor procura por monitoria e estágio seletivo na área, mas sem tendência temporal na atração inicial. A regressão logística identificou cinco fatores preditivos, nesta ordem decrescente de magnitude de efeito na escolha: estágio seletivo, rendimento global, estilo de aprendizagem reflexivo, ordem de preferência inicial e época da graduação. Os efeitos independentes de sexo e monitoria não foram significantes. Concluindo, os fatores preditivos da escolha de Pediatria incluíram indicadores pessoais e curriculares em vertentes distintas de interesse e influência, num quadro de queda recente da opção pela área.