Enlightened sonochemistry

Sonochemistry and photochemistry are initiated by high-energy transient species, which may be prone to mutual interaction. Electronic excitation of solutes by energy transfer from high energy species generated in collapsing bubbles is already supported by experimental evidence. The rates of photochemical reactions can be affected by ultrasound-induced mixing of liquids caused by microstreaming near pulsating cavitation bubbles and shockwaves due to bubble collapse. This may not only improve light absorption but also modify the pathway of reaction by increasing the contact between reagents. Finally, one may speculate about a potentially new chemistry of photoexcited solutes under the extreme conditions inside cavitation microreactors. This work reviews research on the excitation of solutes by sonoluminescence, the combined effects of ultrasound and light on liquid systems and the effect of ultrasound on photocatalytic reactions.     

Synthesis, thermal treatment and characterization of cobalt ferrite-based nanocomposites

We have used time-differential perturbed angular correlation (PAC) spectroscopy with ¹⁸¹Ta-probes to study the electric field gradient at Zr-sites in synthetic zircon and hafnon between room temperature and 1,200°C. PAC spectra are similar to those obtained from naturally occurring zircons. In particular, a change in slope of the quadrupole coupling vs. temperature is observed in the synthetic zircon at the same temperature as seen in natural zircons from the Mud Tank carbonatite (Australia). The synthetic hafnon data also shows this feature but at somewhat higher temperature. Low-temperature PAC spectra of both synthetic zircon and hafnon have a clearly reduced anisotropy. We believe that the cause for this is a electronic defect, possibly created during the β-decay of the probe parent nucleus.     

DTA and X-ray diffraction investigations of laser-irradiated CeO2 powders

The TG and DTA curves and diffractograms of powdered CeO₂ samples irradiated with a CO₂ laser beam with powers of 0.41–1.39 kW/cm² are presented. The laser treatment induced structural changes and probably generation of a metastable phase. X-ray diffraction coupled with thermal analysis was used to establish the structural modifications in the irradiated samples after heating.     

Utilization of an Hg(2+)-sensitive membrane-electrode in the complexometric determination of Bi(3+), Fe(3+) and Cr(3+)

The paper reports the results obtained in the complexometric determination of Bi(3+), Fe(3+) and Cr(3+) by using an Hg(2+)-sensitive membrane-electrode for the end-point indication. The determination of Bi(3+) and Fe(3+) is performed after addition of mercuric complexonate from which these cations release Hg(2+) by means of which the electrode senses the equivalence point. In the case of Cr(3+) an excess of complexone is added and the surplus is titrated with a standard solution of Hg(2+) in the presence of the Hg(2+)-sensitive membrane-electrode.     

Effect of time on the interfacial and foaming properties of beta-lactoglobulin/acacia gum electrostatic complexes and coacervates at pH 4.2

The electrostatic complexation between beta-lactoglobulin and acacia gum was investigated at pH 4.2 and 25 degrees C. The binding isotherm revealed a spontaneous exothermic reaction, leading to a DeltaHobs = -2108 kJ mol(-1) and a saturation protein to polysaccharide weight mixing ratio of 2:1. Soluble electrostatic complexes formed in these conditions were characterized by a hydrodynamic diameter of 119 +/- 0.6 nm and a polydispersity index of 0.097. The effect of time on the interfacial and foaming properties of these soluble complexes was investigated at a concentration of 0.1 wt % at two different times after mixing (4 min, referred as t approximately 0 h and t = 24 h). At t approximately 0 h, the mixture is mainly made of aggregating soluble electrostatic complexes, whereas after 24 h these complexes have already insolubilize to form liquid coacervates. The surface elasticity, viscosity and phase angle obtained at low frequency (0.01 Hz) using oscillating bubble tensiometry revealed higher fluidity and less rigidity in the film formed at t approximately 0 h. This observation was confirmed by diminishing bubble experiments coupled with microscopy of the thin film. It was thicker, more homogeneous and contained more water at t approximately 0 h as compared to t = 24 h (thinner film, less water). This led to very different gas permeability's of Kt approximately 0 h = 0.021 cm s(-1) and Kt=24 h) = 0.449 cm s(-1), respectively. Aqueous foams produced with the beta-lactoglobulin/acacia gum electrostatic complexes or coacervates exhibited very different stability. The former (t approximately 0 h) had a stable volume, combining low drainage rate and mainly air bubble disproportionation as the destabilization mechanism. By contrast, using coacervates aged for 24 h, the foam was significantly less stable, combining fast liquid drainage and air bubble destabilization though fast gas diffusion followed by film rupture and bubble coalescence. The strong effect of time on the air/water interfacial properties of the beta-lactoglobulin/acacia gum electrostatic complexes can be understood by their reorganization at the interface to form a coacervate phase that is more fluid/viscous at t approximately 0 h vs rigid/elastic at t = 24 h.     

4-Methylpyrimidinium ylides. Part 7: 3+2 Dipolar cycloadditions to non-symmetrical substituted alkenes and alkynes

The ability of 4-methylpyrimidinium ylides (as 1,3-dipoles) to react with activated non-symmetrical substituted dipolarophiles (alkenes and alkynes) is presented. 4-Methylpyrimidinium ylides did not react with alkenes. With alkynes the reactions are regiospecific, a single regioisomer being obtained. A possible mechanism for the reaction pathway is proposed. For the first time in the pyrimidinium ylides series both isomers resulting from bonding to the 2-and 6-positions of the heterocycle ring were obtained. The appropriate conditions in order to increase the selectivity of one of the isomers were determined.     

Thermodynamic and kinetic data for adduct formation, cis-trans isomerization and redox reactions of ML4 complexes: a case study with rhodium- and iridium-tropp complexes in d8, d9 and d10 valence electron configurations (tropp=dibenzotropylidene phosphanes)

The formation of adducts of the square-planar 16-electron complexes trans-[M(tropp(ph))(2)](+) and cis-[M(tropp(ph))(2)](+) (M=Rh, Ir; tropp(Ph)=5-diphenylphosphanyldibenzo[a,d]cycloheptene) with acetonitrile (acn) and Cl(-), and the redox chemistry of these complexes was investigated by various physical methods (NMR and UV-visible spectroscopy, square-wave voltammetry), in order to obtain some fundamental thermodynamic and kinetic data for these systems. A trans/cis isomerization cannot be detected for [M(tropp(ph))(2)](+) in non-coordinating solvents. However, both isomers are connected through equilibria of the type trans-[M(tropp(ph))(2)](+)+L<==>[ML(tropp(ph))(2)](n)<==>cis-[M(tropp(ph))(2)](+)+L, involving five-coordinate intermediates [ML(tropp(ph))(2)](n) (L=acn, n=+1; L=Cl(-), n=0). Values for K(d) (K(f)), that is, the dissociation (formation) equilibrium constant, and k(d) (k(f)), that is, the dissociation (formation) rate constant, were obtained. The formation reactions are fast, especially with the trans isomers (k(f)>1x10(5) m(-1) s(-1)). The reaction with the sterically more hindered cis isomers is at least one order of magnitude slower. The stability of the five-coordinate complexes [ML(tropp(ph))(2)](n) increases with Ir>Rh and Cl(-)>acn. The dissociation reaction has a pronounced influence on the square-wave (SW) voltammograms of trans/cis-[Ir(tropp(ph))(2)](+). With the help of the thermodynamic and kinetic data independently determined by other physical means, these reactions could be simulated and allowed the setting up of a reaction sequence. Examination of the data obtained showed that the trans/cis isomerization is a process with a low activation barrier for the four-coordinate 17-electron complexes [M(tropp(ph))(2)](0) and especially that a disproportionation reaction 2 trans/cis-[M(tropp(ph))(2)](0)-->[M(tropp(ph))(2)](+)+[M(tropp(ph))(2)](-) may be sufficiently fast to mask the true reactivity of the paramagnetic species, which are probably less reactive than their diamagnetic equilibrium partners.     

Thermal studies of pre-formulates of metronidazole obtained by spray drying technique

Compatibility studies between active drugs and excipients are substantial in the pharmaceutical technology. The objective of the present work was to develop pre-formulated mixtures of metronidazole (MT) obtained by spray drying (SPDR) and their thermoanalytical characterization. Dynamic and isothermal TG, conventional DSC and DSC coupled to a photovisual system were used. DSC experiments with both techniques confirmed the homogeneity of the conventional and pre-formulated mixtures. The TG data made possible the comparison the thermal stability of the different mixtures. Similar thermal stabilities were found of the conventional and pre-formulated mixtures, with slower particles sizes of MT.     

Organotin and tin(IV) derivatives of dimethyldithioarsinic acid

Organotin derivatives of dimethyldithioarsinic (dithocacodylic) acid have been obtained from the appropriate organotin chloride and the sodium salt of the latter. Tin(IV) chloride and NaS₂AsMe₂ · 2 H₂O yielded only two products, namely Cl₂Sn(S₂AsMe₂)₂ and Sn (S₂AsMe₂)₄, regardless of the reagent ratio. Spectroscopic characterization of the compounds (infrared and¹H NMR) provides structural information suggesting that the dimethyldithioarsinato group behaves as monodentate (or anisobidentate) ligand in Me₂Sn(S₂AsMe₂)₂, Bu₂Sn-(S₂AsMe₂)₂ and Cy₃Sn(S₂AsMe₂), as bidentate in Ph₂Sn(S₂AsMe₂)₂, Ph₃Sn(S₂AsMe₂) and Cl₂As(S₂AsMe₂)₂, whereas Sn(S₂AsMe₂)₄ contains both mono- and bidentate ligands, presumably in a six-coordinate structure.     

PMR-Spektren einiger Alkoxy-9-chlor-6-nitroacridine

The spectra of some 9-chloro-6-nitroacridines with methoxy substituents in position 1,4; 2,4; 3,4; 2,3; and ethoxy substituents in positions 1, 2, 3, were recorded. The influence of electron releasing alkoxy groups and electron withdrawing nitro groups on chemical shifts of protons in the 9-chloroacridinic cycle was discussed and PMR parameters were determined, comparatively with those of acridine and 9-chloroacridine. Good agreement between calculated and experimental values is observed. The spectrum of 9-chloro-1,2,3-triethoxyacridine shows for the four protons of the ringC. (H-5, H-6, H-7, H-8) anAMNX coupling pattern whose parameters were determined.