17O NMR spectroscopic characterization and the mechanism of formation of alkyl hydrotrioxides (ROOOH) and hydrogen trioxide (HOOOH) in the low-temperature ozonation of isopropyl alcohol and isopropyl methyl ether: water-assisted decomposition

Low-temperature ozonation of isopropyl alcohol (1a) and isopropyl methyl ether (1b) in [D6]acetone, methyl acetate, and tert-butyl methyl ether at -78 degrees C produced the corresponding hydrotrioxides, Me2C(OH)(OOOH) (2a) and Me2C(OMe)(OOOH) (2b), along with hydrogen trioxide (HOOOH). All the polyoxides investigated were characterized for the first time by 17O NMR spectroscopy of highly 17O-enriched species. The assignment was confirmed by GIAO/MP2/6-31++G* calculations of 17O NMR chemical shifts, which were in excellent agreement with the experimental values. Ab initio density functional (DFT) calculations at the B3LYP/ 6-31G*+ZPE level have clarified the transition structure (TS1, deltaE = 7.4 and 10.6 kcalmol(-1), relative to isolated reactants and the complex 1a-ozone, respectively) for the ozonation of 1a: this, together with the formation of HOOOH and some other products, indicates the involvement of radical intermediates (R*, *OOOH) in the reaction. The activation parameters for the decomposition of the hydrotrioxides 2a and 2b (Ea, = 23.5+/-1.5 kcalmol(-1), logA = 16+/-1.8) were typical for a homolytic process in which cleavage of the ROOOH molecule occurs to yield a radical pair [RO* *OOH] and represents the lowest available energy pathway. Significantly the lower activation parameters for the decomposition of HOOOH (Ea = 16.5+/-2.2 kcalmol(-1), logA = 9.5+/-2.0) relative to those expected for the homolytic scission of the HO-OOH bond [bond dissociation energy (BDE) = 29.8 kcalmol(-1), CCSD(T)/6-311++G**] are in accord with the proposal that water behaves as a bifunctional catalyst and therefore participates in a "polar" (non-radical) decomposition process of this polyoxide. A relatively large acceleration of the decomposition of the hydrotrioxide 2a in [D6]acetone, accompanied by a significant lowering of the activation energies, was observed in the presence of a large excess of water. Thus intramolecular 1,3-proton transfer probably also involves the participation of water and is similar to the mechanism proposed for the decomposition of HOOOH. This hypothesis was further substantiated by the B3LYP/6-31++ G*+ZPE calculations for the participation of water in the decomposition of CH3OOOH, which revealed two stationary points on the potential energy surface corresponding to a CH3OOOH-HOH complex and a six-membered cyclic transition state TS2. The energy barriers were comparable with those calculated for HOOOH, that is, deltaE = 15.0 and 21.5 kcalmol(-1) relative to isolated reactants and the CH3OOOH-HOH complex, respectively.     

Mechanism of formation of hydrogen trioxide (HOOOH) in the ozonation of 1,2-diphenylhydrazine and 1,2-dimethylhydrazine: an experimental and theoretical investigation

Low-temperature (-78 degrees C) ozonation of 1,2-diphenylhydrazine in various oxygen bases as solvents (acetone-d(6), methyl acetate, tert-butyl methyl ether) produced hydrogen trioxide (HOOOH), 1,2-diphenyldiazene, 1,2-diphenyldiazene-N-oxide, and hydrogen peroxide. Ozonation of 1,2-dimethylhydrazine produced besides HOOOH, 1,2-dimethyldiazene, 1,2-dimethyldiazene-N-oxide and hydrogen peroxide, also formic acid and nitromethane. Kinetic and activation parameters for the decomposition of the HOOOH produced in this way, and identified by (1)H, (2)H, and (17)O NMR spectroscopy, are in agreement with our previous proposal that water participates in this reaction as a bifunctional catalyst in a polar decomposition process to produce water and singlet oxygen (O(2), (1)delta(g)). The possibility that hydrogen peroxide is, besides water, also involved in the decomposition of hydrogen trioxide is also considered. The half-life of HOOOH at room temperature (20 degrees C) is 16 +/- 1 min in all solvents investigated. Using a variety of DFT methods (restricted, broken-symmetry unrestricted, self-interaction corrected) in connection with the B3LYP functional, a stepwise mechanism involving the hydrotrioxyl (HOOO(*)) radical is proposed for the ozonation of hydrazines (RNHNHR, R = H, Ph, Me) that involves the abstraction of the N-hydrogen atom by ozone to form a radical pair, RNNHR(*) (*)OOOH. The hydrotrioxyl radical can then either abstract the remaining N(H) hydrogen atom from the RNNHR(*) radical to form the corresponding diazene (RN=NR), or recombines with RNNHR(*) in a solvent cage to form the hydrotrioxide, RN(OOOH)NHR. The decomposition of these very labile hydrotrioxides involves the homolytic scission of the RO-OOH bond with subsequent "in cage" formation of the diazene-N-oxide and hydrogen peroxide. Although 1,2-diphenyldiazene is unreactive toward ozone under conditions investigated, 1,2-dimethyldiazene reacts with relative ease to yield 1,2-dimethyldiazene-N-oxide and singlet oxygen (O(2), (1)delta(g)). The subsequent reaction sequence between these two components to yield nitromethane as the final product is discussed. The formation of formic acid and nitromethane in the ozonolysis of 1,2-dimethylhydrazine is explained as being due to the abstraction of a methyl H atom of the CH(3)NNHCH(3)(*) radical by HOOO(*) in the solvent cage. The possible mechanism of the reaction of the initially formed formaldehyde methylhydrazone (and HOOOH) with ozone/oxygen mixtures to produce formic acid and nitromethane is also discussed.     

Separation of enantiomers of butorphanol and cycloamine by capillary zone electrophoresis

Butorphanol tartrate is a synthetic opioid agonist-antagonist used as analgesic, possessing three chiral centres in the basic part of the molecule. Its chiral purity is routinely controlled only by optical rotation. A new capillary zone electrophoresis method, capable to separate the enantiomers of butorphanol and intermediate of its synthesis, cycloamine, was developed. Different electrolyte composition (type and concentration of carrier ion, pH, and organic solvent addition), and type and concentration of several chiral selectors (natural and modified cyclodextrins) were tested. Using the optimized conditions (acidic electrolyte with the addition of highly sulphated gamma-cyclodextrin) as low as 0.05% of undesirable enantiomers can be detected. Selected method characteristics, i.e., linearity (0-50 mg/l), precision (2.5% at 20 mg/l), and accuracy (101 +/- 2% at 20 mg/l) were evaluated. The optimized method was applied for the analysis of real batches of butorphanol and cycloamine. It was found that butorphanol tartrate manufactured by IVAX Pharmaceuticals contains less than 0.05% of undesirable enantiomer.     

Retention indices as identification tool in pyrolysis-capillary gas chromatography

Pyrolysis-capillary gas chromatography (Py-cGC) represents important method to identify the analytes in the mixture after thermal degradation. This combines high effective analyte separation on-line coupled with thermal degradation process that depends on analyte structure. System of retention indices has been used for identification of the analytes after on-line pyrolysis and chromatographic separation. The pyrolysate composition has been studied during thermal degradation of polymethylmethacrylate (PMMA) at different pyrolysis temperatures and chromatographic column conditions. Homologues series of n-alkanes have been used for calculation of pyrolysate Kováts retention indices (I) and compared with mass spectrometric (MS) data of pyrolysate model mixture. To identify PMMA thermal degradation products the high density polyethylene (HDPE) as additive standard producing triplets of the olefin homologous series during co-pyrolysis has been used. These homologous series enable to calculate programmed temperature retention indices (ITPGC) to identify the analytes present in the pyrolysate. Calculated I values were compared with published I values databases to identify analytes yielded at different pyrolysis temperatures.     

Investigation of vortex dynamics close to Bc2 in Cu2Mo6S8 quasi epitaxial thin films

The Ginzburg number of superconducting Chevrel phases M_xMo₆S₈ with small coherence length (10⁻³ to 10−5) is intermediate between those obtained for conventional low T_c materials (10⁻⁸) and those of high T_c (10⁻¹) indicating that these phases may display features in the dynamics of the vortices similar to those observed in high T_c superconductors. In this work we present a detailed study of I–V measurements close to the B_c2 line carried out on quasi epitaxial thin films of Cu₂Mo₆S₈. The non-linear I–V curves show a scaling behaviour making possible to determine a transition temperature between an unpinned vortex state and a vortex glass state. However, the temperature range of the unpinned vortex state is much wider than expected.     

Voltammetry of biologically active species and surfactants on new miniaturized and contractible (compressible) mercury electrodes

The adsorption of the polyether-antibiotic monensin from an aqueous solution on mercury was used to investigate the effect of the decreasing size of a stationary mercury drop electrode on the shape of the voltammetric desorption peak of the surfactant. The change of the i-E curve indicated an acceleration of the transport of the surfactant to the electrode as well as of time-dependent changes in the adsorption layer. A decrease of the radius of the hanging mercury drop electrode from 220 μm to 80 μm at a constant accumulation time of t_ac = 70 s resulted in an about 4-fold increase of the evaluated signal (i-E pre-wave) of monensin. A 7-fold increase of the voltammetric desorption peak of monensin at conc. 5 · 10^–7 mol/L was observed as result of a compressive accumulation of the surfactant due to a contraction of the mercury drop electrode. A scheme of an apparatus for voltammetric/polarographic measurements by means of the contractible (compressible) mercury drop electrode is described. The controlled contraction of the electrode surface is presented together with preliminary results covering a new way of accumulation of surfactants, new accumulation effects, effective in adsorptive voltammetry, and other electroanalytical techniques.     

REVIEW: metal complexes as urease inhibitors

Urease plays a significant role in the pathogenesis of several diseases and also has practical implications in other fields, such as agriculture or chemical analysis. Among the multitude of chemical species known to inhibit urease, metal complexes stand out as a special category due to their specific mechanism of action, distinct from purely organic substances. Their inhibitory activity seems to depend on the type of metal and its oxidation state as well as on the coordination environment of the central atom. Furthermore, the study of the interaction between metal ions and their complexes with urease renders valuable insights into detailed catalytic mechanisms of this enzyme. This brief survey attempts to provide an overview of the published research on urease inhibition by metal complexes.     

Electrochemical processes during plating Fe powder particles by Ni and Ni/Cu coating in the fluidized bed

Ni electrodeposition on Fe powder was studied with respect to an inhibiting adsorbed hydroxycomplex layer. Its elimination was done in three possible ways: by increasing the rotation speed of the circular stirring of the suspension, by chemical dissolution of the adsorbed layer during interrupted electrolysis, and by addition of a complexing agent – sodium citrate into the electrolyte. The simultaneous deposition of a Cu/Ni coating was enabled by proper electrolyte composition as to the ratio of both metallic compounds and by the addition of a suitable complexing agent. The Cu/Ni ratio was influenced, beside electrochemical parameters, also by the particle size of the Fe powder and by the suspension density. Increasing the suspension density supports the deposition of Ni, and increasing the particle size supportsthe deposition of Cu. Electronic Publication