A sensitive spectrofluorimetric method for the quantification of melamine residue in milk powder using the Mannich reaction in aqueous solutions.

The objective of this study was to develop a spectrofluorimetric method for the quantitative determination of melamine. The method was based on the complexation of melamine with a mixture of formaldehyde and chemicals including a ketone group, as described by the Mannich reaction. The complex was determined by spectrofluorimetric measurement as it is characterized by specific spectroscopic properties that are related to the chromophore of the ketone compounds. 1,3-Diphenylpropane-1,3-dione (DPPD) was tested as a ketone compound. The fluorescence spectrum of the complex presented a maximum of absorption at 325 nm.A quenching of the fluorescence occurred when melamine was added into the solution. The kinetic of fluorescence quenching was followed to determine quantitatively the melamine concentration. An internal standard was added to quantify melamine. The method was tested to determine the level of melamine in contaminated milk powder. The recovery value was 97% and the limit of detection was 0.007 µg mL(-1.)

Remediation of 4-nonylphenol in aqueous solution by using free radicals generated by the oxidative reactions.

INTRODUCTION: This study relates to use of zerovalent iron to generate hydroxyl free radicals and undergo subsequent oxidation to destroy 4-nonylphenol (NP) by mild process in aqueous solution and activation of oxygen gas (O2) at room temperature. This technology is based on a novel oxidative mechanism mediated by zerovalent iron rather than commonly used reduction mechanism. MATERIALS AND METHODS: A laboratory scale device consisting of a 250 ml pyrex serum vials fixed to a Vortex agitator was used. Different amounts of zerovalent iron powder (ZVI; 1, 10, and 30 g/l) at pH 4 and room temperature with bubbling of oxygen gas were investigated. RESULTS AND CONCLUSION: Experiments showed an observed degradation rate k (obs) directly proportional to the amount of iron. 4-Nonylphenol degradation reactions demonstrated first-order kinetics with a half-life of about 10.5 ± 0.5 and 3.5 ± 0.2 min when experiments were conducted at [ZVI] = 1 and 30 g/l respectively. Three analytical techniques were employed to monitor 4-nonylphenol degradation and mineralization: (1) spectrofluorimetry; (2) high-performance liquid chromatography; (3) total organic carbon meter (TOC meter). Results showed a complete disappearance of 4-nonylphenol after 20 min of contact with ZVI. The intermediate by-products of the reaction were not identified but the disappearance of NP was monitored by the three above-mentioned techniques.

Effect of the acyl group and the dodecylsulfonate chain on the inclusion of pyrene inside the cavity of beta-cyclodextrin.

The solubilization of pyrene in aqueous solution of beta-cyclodextrin (beta-CD) or its derivatives such as beta-CD-hexanoyl, beta-CD-benzoyl and beta-CD-dodecylsulfonate was investigated by spectrophotometry. Linear and non-linear regression methods were used to estimate the association constants (K(1)). A 1:1 stoichiometric ratio and different effects of the hexanoyl, benzoyl and dodecylsulfonate groups on the association constant were observed for the binary inclusion complex between pyrene and beta-CD. The formation constant was shown to decrease when beta-CD was modified by a dodecylsulfonate chain. The value of K(1) was 190+/-10 L mol(-1) for the [pyrene/beta-CD] complex and 145 L mol(-1) for the [pyrene/beta-CD-dodecylsulfonate] complex. Partitioning of the pyrene molecules between the dodecylsulfonate chains and cyclodextrin cavities can explain the decrease in the association constant value. In the cases of beta-CD-hexanoyl and beta-CD-benzoyl derivatives, no association constants were detected. Results suggest that the high hydrophobicity of the hexanoyl and benzoyl groups prevents the inclusion of pyrene molecules inside the cyclodextrin cavity.