Forces between surfaces in electrolyte solutions

Density functional theories of solvation forces in charged fluids are extended to treat electrolytes consisting of finitesized ions and neutral solvent particles. The resulting forces display pronounced oscillations whose magnitude is a strong function of the bulk density of the neutral species.     

Kinetic and thermodynamic characterization of the cobalt and manganese oxyhydroxide cores formed in horse spleen ferritin

Horse spleen ferritin (HoSF) containing 800-1500 cobalt or 250-1200 manganese atoms as Co(O)OH and Mn(O)OH mineral cores within the HoSF interior (Co-HoSF and Mn-HoSF) was synthesized, and the chemical reactivity, kinetics of reduction, and the reduction potentials were measured. Microcoulometric and chemical reduction of HoSF containing the M(O)OH mineral core (M = Co or Mn) was rapid and quantitative with a reduction stoichiometry of 1.05 +/- 0.10 e/M forming a stable M(OH)(2) mineral core. At pH 9.0, ascorbic acid (AH(2)), a two-electron reductant, effectively reduced the mineral cores; however, the reaction was incomplete and rapidly reached equilibrium. The addition of excess AH(2) shifted the reaction to completion with a M(3+)/AH(2) stoichiometry of 1.9-2.1, consistent with a single electron per metal atom reduction. The rate of reaction between M(O)OH and excess AH(2) was measured by monitoring the decrease in mineral core absorbance with time. The reaction was first order in each reactant with second-order rate constants of 0.53 and 4.74 M(-1) min(-1), respectively, for Co- and Mn-HoSF at pH 9.0. From the variation of absorbance with increasing AH(2) concentration, equilibrium constants at pH 9.0 of 5.0 +/- 1.9 for Co-HoSF and 2.9 +/- 0.9 for Mn-HoSF were calculated for 2M(O)OH + AH(2) = 2M(OH)(2) + D, where AH(2) and D are ascorbic acid and dehydroascorbic acid, respectively. Consistent with these equilibrium constants, the standard potential for the reduction of Co(III)-HoSF is 42 mV more positive than that of the ascorbic acid reaction, while the standard potential of Mn(III)-HoSF is 27 mV positive relative to AH(2). Fe(2+) in solution with Co- and Mn-HoSF under anaerobic conditions was oxidized to form Fe(O)OH within the HoSF interior, resulting in partial displacement of the Co or Mn by iron.     

Air sampling of aromatic hydrocarbons in the presence of ozone by solid-phase microextraction

Effects of ozone on air sampling of standard gas mixtures of aromatic hydrocarbons were tested using solid-phase microextraction (SPME). Standard concentrations of ozone ranging from 10 ppb (v/v) to 6400 ppm (v/v) were generated using an in-house built ozone generator based on corona discharge. Effects of temperature, discharge voltage, and oxygen flow on the ozone generation were tested. The working dc voltage had the greatest effect on generated ozone concentration and was proportional to the ozone concentration. Generation temperature and oxygen flow rate were inversely proportional to ozone concentrations. Produced ozone was mixed with standard benzene, toluene, ethylbenzene, and xylenes (BTEX) gas at less than 100 ppb (v/v). Air samples were collected with poly(dimethylsiloxane) (PDMS) 100 microm SPME fibers and analyzed by gas chromatography (GC)-flame ionization detection (FID) and GC-MS. Significant reductions of BTEX concentrations were observed. In addition, some products of BTEX-ozone-oxygen reactions were identified. SPME worked well as a rapid sampler for BTEX and BTEX-ozone-oxygen reaction products. No significant deterioration of the PDMS coating and no significant reduction of absorption capacity were observed after repeated exposure to ozone.     

Reversible energy transfer

Analysis of the transient and steady-state kinetics of reversible energy transfer shows that while the interpretation of lifetime measurements is difficult unless the donor and acceptor lifetimes are appreciably different, quantum yield measurements are relatively easy to interpret.

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Zusammenfassung Die Analyse der Kinetik der Übergangszustände und der stationären Zustände der reversiblen Energieübertragung zeigt, daß im Gegensatz zu einer schwierigen Interpretation der Messungen der Lebensdauer — es sei denn die Lebensdauer von Donor und Acceptor sind wesentlich voneinander verschieden — die Messungen der Quantumausbeute verhältnismäßig einfach zu interpretieren sind.

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Résumé L'analyse de la cinétique de l'état transitoire et de l'état stationnaire du transfert réversible d'énergie montre que, si l'interprétation des mesures de durée de vie est difficile, à moins queles durées de vie du donneur et de l'accepteur soient très différentes, il est par contre relativement facile d'interpréter les mesures de rendement quantique.

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Dedicated to the memory of Professor K. H. Hansen.     

Interaction with glycine increases stability of a mutagenic tautomer of uracil. A density functional theory study

The most stable structures for the gas-phase complexes of minor tautomers of uracil (U) with glycine (G) were characterized at the density functional B3LYP/6-31++G level of theory. These are cyclic structures stabilized by two hydrogen bonds. The relative stability of isolated tautomers of uracil was rationalized by using thermodynamic and structural arguments. The stabilization energies for complexes between the tautomers of U and G result from interplay between the stabilizing two-body interaction energies and destabilizing one-body terms. The latter are related to the energies of (i) tautomerization of the unperturbed moieties and (ii) distortions of the resulting rare tautomers in the complex. The two-body term describes the interaction energy between distorted tautomers. The two-body interaction energy term correlates with perturbations of length of the proton-donor bonds as well as with deprotonation enthalpies and proton affinities of the appropriate monomer sites. It was demonstrated that the relative instability of rare tautomers of uracil is diminished due to their interactions with glycine. In particular, the instability of the third most stable tautomer (U(III)) is decreased from 11.9 kcal/mol for non-interacting uracil to 6.7 kcal/mol for uracil in a complex with the zwitterionic tautomer of glycine. A decrease of instability by 5.2 kcal/mol could result in an increase of concentration of U(III) by almost 5 orders of magnitude. This is the tautomer with proton donor and acceptor sites matching guanine rather than adenine. Moreover, kinetic characteristics obtained for the glycine-assisted conversion of the most stable tautomer of uracil (U(I)) to U(III) indicate that the U(I)<-->U(III) thermodynamic equilibrium could be easily attained at room temperature. The resulting concentration of this tautomer falls in a mutationally significant range.     

Studies of amine-induced ring opening of some mesoionic xanthines

The ring-opening reactions of seven mesoionic thiazolo[3,2-a]pyrimidine-5,7-diones by a series of primary and secondary amines have been investigated. The rates of the ring fission of five N(8)-substituted mesoionic xanthines with benzylamine were measured and found to follow second order kinetics. The Hammett relationship is followed with ? value of + 0.48 in p-dioxane as solvent. The dependence of rates on temperatures has been studied for the N(8)-ethyl derivative; the energy of activation (Δ E* ) is 25.3 kcals mol^?1, the enthalpy of activation (Δ H* ) is 24.7 kcals mol^?1 and the entropy of activation (Δ S* ) is — 4.9 e.u. A slight increase in rate of reaction was observed when the solvent was changed from p-dioxane to dimethyl sulfoxide. In p-dioxane at constant mesoionic xanthine concentration, the rate constant for ring opening decreased with increasing benzylamine concentration. These results are consistent with a bimolecular nucleophilic mechanism proceeding by the rate-determining formation of a charged tetrahedral transition state.     

Divergent coordination mode of magnesium and zinc alkyls supported by the bifunctional pyrrolylaldiminato ligand

The first magnesium and zinc alkyls derived from N-(iso-propyl)-pyrrolylaldimine have been synthesised and structurally characterised: both tBuM(N,N')-type compounds exist as three-coordinate monomers in benzene solution, but in the solid state the magnesium complex is a centrosymmetric dimer with Mg2(mu-N)2 bridges, whereas the zinc complex is a Zn...pi bonded dimer with a pi-coordinated pyrrole unit.     

The mass spectra of some silver salts

Fifteen of twenty-four silver(I) carboxylates examined give useful electron impact mass spectra. The compounds vaporize at moderate temperatures, apparently mainly as dimer with traces of higher oligomer in only a few cases. The molecular ion for the dimer is generally weak or absent, with the most abundant silver containing ion being [Ag₂(O₂CR)]⁺ in most cases. Metastable defocusing and deuterium labeling experiments on silver acetate have established some of the fragmentation pathways. The reported loss of carbon dioxide from perfluorocarboxylates to give intense peaks for organosilver ions was not observed in this study. Attempts to obtain spectra on the silver salts of organic materials other than carboxylic acids were successful in several cases. Silver trifluoromethanesulfonate, although much less volatile, gives a spectrum and fragmentation very much like the carboxylates, whereas silver trifluoromethanethiolate gives a complex spectrum which suggests tetramer as a major gas phase species. Of three compounds examined which have silver to nitrogen bonding only silver(II) phthalocyanine is sufficiently volatile to give a spectrum without decomposition. The field desorption spectra of the four compounds examined all show the ions Ag_nX_{n ? 1} for X=acetate (n=1 ? 6), X=p-chlorobenzoate (n=1 ? 4), X=methanesulfonate (n=1 ? 7) and X=p-toluenesulfonate (n=1 ? 5).     

Cobalt π-cations in carbocyclic ring constructions

In a combination of cobalt-mediated cationic and free radical chemistry, treatment of the allyl silane substituted β-hydroxycobaloxime 13 with pTSA led predominantly to the trans-disubstituted cyclopentane 14, which on irradiation with TEMPO produced 15. In a similar manner, the cobaloxime 18 was cyclised to 19 in the presence of pTSA which, on irradiation with a sunlamp then underwent radical mediated cyclisation to the substituted indane 20.     

Spectrophotometric methods for the determination of osmium-III Reaction of osmium tetroxide with 1:5-diphenylcarbo- hydrazide in aqueous solutions followed by extraction of the complex

-A spectrophotometric method has been developed which is applicable to the determination of extremely small quantities of osmium. Osmium is oxidised to the octovalent state, then added to an acidic aqueous solution containing 1:5-diphenylcarbohydrazide (DPC). After heating the aqueous solution to 65°, the osmium-DPC complex is extracted with chloroform. A molar absorbancy index of about 150,000 is obtained. From 7 to 25 μg of osmium can be determined with a coefficient of variation of 6%. It was established that Fe^III, Cu^II, Ru^III and Au^III seriously interfere in the determination of osmium by this method, while Cr^VI, Ni^II, Mo^VI, Ir^III and chloride interfere only when present in relatively high concentrations.