Product distribution of peroxynitrite decay as a function of pH, temperature, and concentration.

The decay of peroxynitrite [O=NOO(-), oxoperoxonitrate(1-)] was examined as a function of concentration (0.050-2.5 mM), temperature (5-45 degrees C), and pH (2.2-10.0). Below 5 degrees C and pH 7, little amounts of the decomposition products nitrite and dioxygen are formed, even when the peroxynitrite concentration is high (2.5 mM). Instead, approximately > or =90% isomerizes to nitrate. At higher pH, decomposition increases at the expense of isomerization, up to nearly 80% at pH 10.0 at 5 degrees C and 90% at 45 degrees C. Much less nitrite and dioxygen per peroxynitrite are formed when the peroxynitrite concentration is lower; at 50 microM and pH 10.2, < or =40% decomposes. In contrast to two other reports (Pfeiffer, S.; Gorren, A. C. F.; Schmidt, K.; Werner, E. R.; Hansert, B.; Bohle, D. S.; Mayer, B. J. Biol. Chem. 1997, 272, 3465-3470, and Coddington, J. W.; Hurst, J. K.; Lymar, S. V. J. Am. Chem. Soc. 1999, 121, 2438-2443), we find that the extent of decomposition is dependent on the peroxynitrite concentration.     

Carbene Complexes of Pnictogen Pentafluorides and Boron Trifluoride

Summary.  Synthesis, characterization, and solid state X-ray crystallographic structures for 12-Pn-6 complexes derived from carbene 4,5-dichloro-1,3-dimesitylimidazol-2-ylidene and phosphorus, arsenic, or antimony pentafluoride are reported. The adducts show octahedral geometries at the pnictogen centers with C-Pn bond distances of 189.8 (P), 199.9 (As), and 217.5 (Sb) pm. The structures are those of internal zwitterions with imidazolium ion character in the heterocyclic ring and a pentafluoropnictanide anion bonded to C². Adducts of BF₃ with 1,3-dimesitylimidazol-2-ylidene and 4,5-dichloro-1,3-dimesitylimidazol-2-ylidene are also reported for comparison. Although the reactivity of chlorinated and non-chlorinated carbenes varies considerably, the spectroscopic and structural properties of analogous adducts are remarkably similar. Received September 6, 1999. Accepted (revised) October 20, 1999     

Effect of surfactants on the stability of thin liquid film flow on a rotating disk

The effect of surfactants on surface instabilities of thin liquid film flow on a rotating disk was studied at different flow rates Q (0.5相似文献   

Structural insights into aluminum chlorofluoride (ACF)

The structure of the very strong solid Lewis acid aluminum chlorofluoride (ACF, AlCl(x)F(3-x), x = 0.05-0.3) was studied by IR, ESR, Cl K XANES, (19)F MAS NMR, and (27)Al SATRAS NMR spectroscopic methods and compared with amorphous aluminum fluoride conventionally prepared by dehydration of alpha-AlF(3) x 3H(2)O. The thermal behavior of both compounds was investigated by DTA and XRD. In comparison to ACF, amorphous AlF(3) prepared in a conventional way is not catalytically active for the isomerization reaction of 1,2-dibromohexafluoropropane, which requires a very strong Lewis acid. Both compounds are mainly built up of corner-sharing AlF(6) octahedra forming a random network. The degree of disorder in ACF is higher than in amorphous AlF(3). Terminal fluorine atoms were detected in ACF by (19)F NMR. The chlorine in ACF does not exist as a separate, crystalline AlCl(3) phase. Additionally, chlorine-containing radicals, remaining from the synthesis, are trapped in cavities of ACF. These radicals are stable at room temperature but do not take part in the catalytic reaction.     

Identification and characterization of individual airborne volcanic ash particles by Raman microspectroscopy

We present for the first time the Raman microspectroscopic identification and characterization of individual airborne volcanic ash (VA) particles. The particles were collected in April/May 2010 during research aircraft flights, which were performed by Deutsches Zentrum für Luft- und Raumfahrt in the airspace near the Eyjafjallajökull volcano eruption and over Europe (between Iceland and Southern Germany). In addition, aerosol particles were sampled by an Electrical Low Pressure Impactor in Munich, Germany. As references for the Raman analysis, we used the spectra of VA collected at the ground near the place of eruption, of mineral basaltic rock, and of different minerals from a database. We found significant differences in the spectra of VA and other aerosol particles (e.g., soot, nitrates, sulfates, and clay minerals), which allowed us to identify VA among other atmospheric particulate matter. Furthermore, while the airborne VA shows a characteristic Raman pattern (with broad band from ca. 200 to ca. 700 cm^?1 typical for SiO₂ glasses and additional bands of ferric minerals), the differences between the spectra of aged and fresh particles were observed, suggesting differences in their chemical composition and/or structure. We also analyzed similarities between Eyjafjallajökull VA particles collected at different sampling sites and compared the particles with a large variety of glassy and crystalline minerals. This was done by applying cluster analysis, in order to get information on the composition and structure of volcanic ash.

Study of Interactions Between Sugammadex and Penicillins Using Affinity Capillary Electrophoresis

Sugammadex, a new modified gamma cyclodextrin, reverses the neuromuscular blockage induced by rocuronium by forming a strong complex with this muscle relaxant. To evaluate possible interactions with potentially co-administered drugs, interactions between sugammadex and penicillins were investigated using the affinity capillary electrophoresis method for the first time. Capillary electrophoresis coupled to an ultra violet detector was used as an analytical device for the analysis and detection of cyclodextrin inclusion complexes. Changes in the effective mobility of guest drugs (amoxicillin, ampicillin, oxacillin, dicloxacillin and azlocillin) were correlated with the increasing concentration of host molecules in background electrolyte, and successfully fitted into a non-linear curve equation; assuming 1:1 stoichiometric interaction. The calculated association constants (K _a) were: 383.44, 184.54, 265.34 and 95.06 M⁻¹ for amoxicillin, ampicillin, oxacillin and dicloxacillin, respectively. No complex formation with sugammadex could be detected for both penicillin G and piperacillin. The difference in the chemical structure of the penicillins, especially in the (R) side chains, is suggested to be responsible for the variety of binding strength between penicillins and sugammadex. The displacement study demonstrated that interactions between sugammadex and co-administered penicillins could reduce the pharmacological effects of both.

     

Water increases rates of epoxidation by Mn(III)porphyrins/imidazole/IO4(-) in CH2Cl2. Analogy with peroxidase and chlorite dismutase

Manganese(III)-meso-tetraphenylporphyrin [Mn(TPP)] and manganese(III)-meso-tetrakis(pentafluorophenyl)porphyrin [Mn(TPFPP)] catalyse the epoxidation of cyclooctene by IO(4)(-) in the presence of excess imidazoles, in both dry CH(2)Cl(2) and CH(2)Cl(2) saturated with H(2)O. The reaction rates of the electron deficient Mn(TPFPP) are a factor 24 less than those of Mn(TPP); however, the former increases 15-30 times in the presence of water, while those of Mn(TPP) do so by a factor of 2-3. The most striking catalytic enhancement caused by the addition of water was observed with 2-methylimidazole and Mn(TPFPP). As deprotonation of imidazoles may play a significant role in the presence of water, we found that manganese(III)-meso-tetrakis(phenyl-4-sulfonato)porphyrin [Mn(TPPS)] decreases the NH proton pK(a) of axially coordinated imidazole from 14.2 to 9.5. We conclude that the imidazole ligand is partially deprotonated in the presence of water. The latter enables the solvation of imidazolium ions that are formed simultaneously. The imidazolate form of the co-catalyst is a much stronger donor than the imidazole itself, providing electron density to Mn(III) and thus promoting oxygen transfer. The failure of N-methylimidazole to increase the reaction rates upon addition of water supports this hypothesis. A functionally related deprotonation has been shown to occur in horseradish peroxidase (J. S. de Ropp, V. Thanabal, G. N. La Mar, J. Am. Chem. Soc. 1985, 107, 8270-8272) and in chlorite dismutase (B. R. Goblirsch, B. R. Streit, J. L. Dubois, C. M. Wilmot, J. Biol. Inorg. Chem. 2010, 15, 879-888). Mn(III)porphyrins in combination with imidazoles and water constitute a functional biomimetic model of peroxidases.