A synthesis method was developed capable of obtaining pristine gold nanoparticles (AuNPs) using the lowest possible amount of auxiliary compounds. An aqueous solution of HAuCl4.3H2O was irradiated, in the absence of any stabilizing species, with the 532-nm radiation of a Nd:YAG laser. Spherical shaped AuNPs were produced by this method with sizes below 10 nm. The crystalline structures were stable for up to 28 days. A mechanism for this process is also proposed based on the initial cleavage of water molecules by the laser irradiation followed by the formation of hydrogen peroxide that reduces the gold species AuIII. The resulting species of these reactions (H2 and O2) were identified by mass spectrometry. This new method suggests that laser irradiation is a feasible alternative to produce ready-to-use AuNPs, for drug delivery, diagnostics or bio-imaging.

This paper reports the effect of the SWy-1 montmorillonite content on the kinetic thermal degradation of poly(2-hydroxyethyl methacrylate) (PHEMA)/SWy-1 nanocomposites prepared by in situ photopolymerization, using thermogravimetry analysis (TGA). 2-Hydroxyethyl methacrylate was photopolymerized in the presence of SWy-1 clay mineral using 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H-thioxanthen-2-yloxy)-N,N,N-trimethyl-1-propanium chloride (QTX) and triethanolamine as the photoinitiating system. X-Ray diffraction analysis indicates that the PHEMA/SWy-1 nanocomposites present an intercalated structure. The isoconversional Flynn-Wall-Ozawa method was used to estimate activation energies and pre-exponential factors for the thermal decomposition. All nanocomposites exhibited improvement in their thermal stability, mainly due to the large interaction between the PHEMA intercalated in the SWy-1 structure. The activation energies for PHEMA/SWy-1 nanocomposites increased when increasing the clay content. The SWy-1 clay mineral acts as a better insulator, mass transport barrier and as a "crosslinking agent", increasing the activation energies for the decomposition of the polymer present in the nanocomposites.

O objetivo deste trabalho é correlacionar o grau de conversão de copolímeros de 2,2-bis[4-(2-hidróxi-3-metacriloiloxipropóxi) fenil]propano (BisGMA) e dimetacrilato de trietilenoglicol (TEGDMA) (copolímeros TB) obtidos por fotopolimerização, usando o sistema fotoiniciador canforquinona/etil 4-dimetilaminobenzoato (CQ/EDB), com a eluição de monômeros e a absorção de água. A eluição de monômeros foi avaliada a partir da imersão dos polímeros em etanol/água e análise por CLAE (cromatografia líquida de alto rendimento). A absorção de água de saliva artificial foi determinada gravimetricamente. Os resultados mostram que a composição dos copolímeros TB influencia a cinética de polimerização, a quantidade de monômeros eluídos, o grau de conversão e a quantidade de água adsorvida. Uma boa correlação foi encontrada entre estas propriedades.

The aim of this work was to correlate the degree of conversion with residual monomer release and water absorption of 2,2-bis[4-(2-hydroxy-3-methacryloyloxypropoxy) phenyl]propane (BisGMA) and triethyleneglycol dimethacrylate (TEGDMA) (TB copolymers) obtained by photopolymerization, using canforquinone/ethyl 4-dimethylaminobenzoate (CQ/EDB) photoinitiator. The monomer release from the copolymers was evaluated by immersion in ethanol/water and HPLC (high performance liquid chromatography) analysis. Water absorption from artificial saliva was determined by mass variation. The results show that the composition of the TB copolymers influences the polymerization kinetics, the amount of the released monomers, the degree of conversion and the amount of adsorbed water. A clear correlation can be found between these properties.

O espectro de absorção de DPH, em concentração fixa, não varia com o teor de água em solvente orgânico. Tem-se a banda de monômeros igual àquela em etanol puro. A absorção não muda até o limite de 54 e 46% de água em etanol e DMSO, respectivamente, para [DPH] = 5,0 × 10-6 mol L-1 a 30 °C. Entretanto, em misturas com água muito abaixo desses conteúdos críticos, observou-se um decaimento intenso de fluorescência enquanto a absorção manteve-se constante. Propõe-se que moléculas de água atuam como supressores dos estados excitados e a constante de supressão de Stern-Volmer através de intensidade relativas, resultou em 7,4 × 10-2 (água/etanol) e 2,6 × 10-2 L mol-1 (água/DMSO). Os tempos de vida do DPH na ausência e presença do supressor forneceram constantes de 7,1 × 10-2 L mol-1 em água/etanol, indicando supressão dinâmica. Em investigações de ambientes com esta sonda, este processo deve ser considerado tendo em vista o risco de erros de interpretação.

The absorption spectra of DPH at fixed concentration do not change with water content in organic solvents. It exhibits monomer bands, such as those obtained in ethanol. The absorption did not change for solutions up to 54 and 46% of water in ethanol and DMSO, respectively, for [DPH] = 5.0 × 10-6 mol L-1 at 30 °C. However, at the same experimental conditions, a gradual sharp decay of the DPH fluorescence is observed. It is proposed that water molecules below these water concentration limits act as quenchers of the excited states of DPH. Stern-Volmer quenching constants by intensities measurements are 7.4 × 10-2 (water/ethanol) and 2.6 × 10-2 L mol-1 (water/DMSO). DPH lifetime measurements in the absence and presence of water resulted in 7.1 × 10-2 L mol-1 in water/ethanol, which pointed out that the process is a dynamic quenching by water molecules. For experiments using DPH as probe, this process can affect data, leading to misunderstanding interpretation.

O mecanismo geral para a fotodegradação do polietilenoglicol (PEG) usando o sistema H2O2/UV foi determinado por GPC e HPLC, analisando o comportamento de moléculas modelo, como por exemplo os etilenoglicóis de baixa massa molar (tetra-, tri-, di-, e etilenoglicol). Após 30 min de irradiação, a massa molar ponderal média (Mw) do PEG degradado, analisada por GPC, cai para metade do seu valor inicial com um aumento concomitante na polidispersidade e número médio de quebra de cadeia (S). Essa queda acentuada caracteriza uma quebra de cadeia aleatória, formando oligômeros e etilenoglicóis de menor massa molar. A análise da fotodegradação de etilenoglicóis modelo por HPLC permitiu sugerir um mecanismo que envolve processos consecutivos, em que etilenoglicóis maiores originam menores, sucessivamente. A fotodegradação do etilenoglicol formou ácidos carboxílicos de baixa massa molar, como por exemplo os ácidos glicólico, oxálico e fórmico.

The general mechanism for the photodegradation of polyethyleneglycol (PEG) by H2O2/UV was determined studying the photooxidation of small model molecules, like low molecular weight ethyleneglycols (tetra-, tri-, di-, and ethyleneglycol). After 30 min of irradiation the average molar mass (Mw) of the degradated PEG, analysed by GPC, fall to half of its initial value, with a concomitant increase in polydispersitivity and number of average chain scission (S), characterizing a random chain scission process yielding oligomers and smaller size ethyleneglycols. HPLC analysis of the photodegradation of the model ethyleneglycols proved that the oxidation mechanism involved consecutive reactions, where the larger ethyleneglycols gave rise, successively, to smaller ones. The photodegradation of ethyleneglycol lead to the formation of low molecular weight carboxylic acids, like glycolic, oxalic and formic acids.

A flow injection spectrophotometric procedure exploiting merging zones is proposed for determining vitamin B2 (riboflavin) in pharmaceutical preparations. The determination is based on the red-colored complex formation between vitamin B2 and silver(I) which was measured at 520 nm. Vitamin B2 was determined in four pharmaceutical preparations in the 1.0 to 50.0 mg L-1 concentration range, with a detection limit of 0.5 mg L-1. The recovery from three samples ranged from 98.0 to 104.0 %. The analytical frequency was 42 h-1 and r.s.d. were lower than 1% for solutions containing 10.0, 30.0 and 50.0 mg L-1 vitamin B2 (n= 10). The results obtained in commercial formulations using the FIA procedure were in good agreement with those obtained by using a conventional fluorimetric procedure (r=0.9998) and also with the label values (r= 0.9997).