Thermal behaviour of diclofenac sodium: decomposition and melting characteristics

The thermal behaviour and melting characteristics of diclofenac sodium were investigated using various instrumental techniques--differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier-transform infrared (FT-IR) spectroscopy and thin layer chromatography (TLC). DSC analysis of diclofenac sodium performed under dynamic flow of either synthetic air or helium or nitrogen did not produce any sharp endothermic peak characteristic of melting peak of a pure substance. Both the rate of scanning of the sample and the environmental atmospheric condition significantly affected the thermographic profile of diclofenac sodium. An exothermic peak prior to an endothermic peak corresponding to melting of the substance appeared when heated under dynamic flow of synthetic air suggesting oxidation (decomposition) of diclofenac sodium before reaching its melting point. In fact, at a scanning rate of 1 degree C/min only the exothermic peak appeared in the thermogram, suggesting complete decomposition prior to melting under the dynamic flow of synthetic air. DSC, FT-IR and TLC data obtained from samples heated under the dynamic flow of either helium or nitrogen revealed formation of a related compound, 1-(2,6-dichlorophenyl)-indolin-2-one, an indol-cyclic amide, as a result of an intramolecular cyclization reaction during the heating process. TGA data demonstrated a loss of 11.4-20.2% of the mass of diclofenac sodium when heated under various environmental conditions, and also supported the oxidative nature of degraded product(s) when the thermal process occurred slowly under a dynamic flow of synthetic air.     

Biamperometric end-point detection with quinhydrone electrodes in coulometric neutralization titrations in nonaqueous media

Some new possibilities for continuous coulometric titration of bases, alone and in mixture, as well as of mineral acids, alone and in mixture, were investigated with acetic anhydride-anhydrous acetic acid as solvents. The titration end point was determined biamperometrically. It was established that quinhydrone electrodes with platinum, palladium, and gold as the metal phase can be equally satisfactorily applied to the end-point determination of both the titrations of bases or acids alone, and of their two-component mixtures. Amounts of 6–10 μequiv. of bases, i.e., 20–47 μequiv. of mineral acids, were determined with the maximal average deviation of 1.4%. Results of biamperometric determinations of bases are compared to those of catalytic thermometric determinations, while those of acids are compared with the results of photometric titrations. The agreement between the methods is satisfactory.     

Certification of the methylmercury content in SRM 2977 mussel tissue (organic contaminants and trace elements) and SRM 1566b oyster tissue

The methylmercury content in two new marine bivalve mollusk tissue Standard Reference Materials (SRMs) has been certified using results of analyses from the National Institute of Standards and Technology (NIST) and two other laboratories. The certified concentrations of methylmercury were established based on the results from four and six different (independent) analytical methods, respectively, for SRM 1566b Oyster Tissue (13.2 +/- 0.7 microg/kg) and SRM 2977 Mussel Tissue (organic contaminants and trace elements) (36.2 +/- 1.7 microg/kg). The certified concentration of methylmercury in SRM 1566b is among the lowest in any certified reference material (CRM).     

Comparison of procedures for measurements of dissolved gaseous mercury in seawater performed on a Mediterranean cruise

A comparison of manual procedures for measurements of dissolved gaseous mercury (DGM) in seawater was accomplished. The experiments were performed on board the Italian research vessel Urania during July 2000 as a subtask in the CNR "Med-Oceanor Project 2000". Water samples for DGM were collected by Go-Flo bottles and subsequently analysed for DGM on board the ship. Determinations of DGM were made in parallel by two groups using different analytical routines. The two sets of data obtained compare favourably. Based on the fieldwork and an additional laboratory study, analytical procedures are discussed and an optimised method to determine DGM is presented. In addition, a method for automated in situ measurements of DGM positioned in the water body was tested. This method has the potential to simplify studies of DGM dynamics, that is variation in concentration as a function of water temperature and solar radiation etc.     

Spectroscopic evidence of beta-turn in N-glycated peptidomimetics related to leucine-enkephalin

The conformational differences caused by N-glycation of the amide bond in endogenous opioid pentapeptide leucine-enkephalin (Tyr-Gly-Gly-Phe-Leu) have been explored in solution using FTIR spectroscopy, NMR and molecular modelling. The compounds studied include protected and unprotected enkephalin analogues N-alkylated at the second (Gly2) amino acid residue with a 6-deoxy-D-galactose moiety (1-3). Comparison of the amide I component bands in the FTIR spectra, measured in trifluoroethanol (TFE), CHCl3 and DMSO, revealed significant differences in the intensity as well as shifts in component band frequencies for glycopeptides 1-3. We found that only the FTIR spectrum of the fully protected compound 1 indicated the presence of a higher population of beta-turns, while the spectra of the partially protected and unprotected glycopeptides 2 and 3 reflected the dominance of unordered or open structures, with some low population of turns. The observed NOE connectivities in CDCl3 for both isomers of the fully protected compound 1, the all-trans one and another with Tyr1-Gly2 peptide bond in cis conformation, indicate the presence of a beta-like turn conformation. Molecular dynamics simulations of the glycopeptide 1 obtained by unconstrained energy minimization of trans- and cis-1 shows that one of trans form conformations is consistent with beta-turn whereas cis isomer has revealed less-compact turn.     

Operation of a proficiency testing scheme of trace elements in sewage sludge with reference values

A proficiency test (PT) was carried out to investigate the quality of laboratory results measuring trace elements in sewage sludge. The scheme relied on reference values, established through flame atomic absorption spectroscopy and instrumental neutron activation analysis. Within the framework of the project, ”Proficiency testing in Central and Eastern European Countries”, the measurements were done in parallel using induced coupled plasma mass spectrometry. This paper discusses the design of the PTS, the metrological concepts behind it and the way in which it was operated. The discussion includes the estimation of measurement uncertainty of the reference values obtained, homogeneity testing and its uncertainty evaluation, as well as all relevant quality assurance aspects. From the results, it can be concluded that all measurement methods involved agree within their respective uncertainties. Furthermore, it can be concluded that it is feasible to operate a proficiency test of trace elements in sewage sludge using reference values. The agreement between the reference values and the consensus values is satisfactory.     

Phase behavior in thin films of cylinder-forming block copolymers

We have experimentally determined a phase diagram for cylinder-forming polystyrene-block-polybutadien-block-polystyrene triblock copolymer in thin films. The phase behavior can be modeled in great detail by dynamic density functional theory. Deviations from the bulk structure, such as wetting layer, perforated lamella, and lamella, are identified as surface reconstructions. Their stability regions are determined by an interplay between surface fields and confinement effects.     

Transform-Limited Pulses Are Not Optimal for Resonant Multiphoton Transitions

Maximizing nonlinear light-matter interactions is a primary motive for compressing laser pulses to achieve ultrashort transform limited pulses. Here we show how, by appropriately shaping the pulses, resonant multiphoton transitions can be enhanced significantly beyond the level achieved by maximizing the pulse's peak intensity. We demonstrate the counterintuitive nature of this effect with an experiment in a resonant two-photon absorption, in which, by selectively removing certain spectral bands, the peak intensity of the pulse is reduced by a factor of 40, yet the absorption rate is doubled. Furthermore, by suitably designing the spectral phase of the pulse, we increase the absorption rate by a factor of 7.