Internal energy content of n-butylbenzene, bromobenzene, iodobenzene and aniline molecular ions generated by two-photon ionization at 266 nm. A photodissociation study

A technique to investigate photodissociation kinetics on a nanosecond time scale has been devised for molecular ions generated by multiphoton ionization (MPI) using mass-analyzed ion kinetic energy spectrometry. The branching ratio or rate constant has been determined for the photodissociation of the n-butylbenzene, bromobenzene, iodobenzene, and aniline molecular ions generated by MPI at 266 nm. The ion internal energies have been estimated by comparing the measured kinetic data with the previous energy dependence data. The analysis has shown that only those molecular ions generated by two-photon ionization contribute to the photodissociation signals. Around half of the available energy has been found to remain as molecular ion internal energy in the two-photon ionization process. Copyright 1999 John Wiley & Sons, Ltd.     

Characterization of the copper-sulfur chromophores in nitrous oxide reductase by resonance raman spectroscopy: evidence for sulfur coordination in the catalytic cluster.

Nitrous oxide reductase (N(2)OR) from Pseudomonas stutzeri, a dimeric enzyme with a canonical metal ion content of at least six Cu ions per subunit, contains two types of multinuclear copper sites: Cu(A) and Cu(Z). An electron-transfer role for the dinuclear Cu(A) site is indicated based on its similarity to the Cu(A) site in cytochrome c oxidase (CcO), a dicysteinate-bridged, mixed-valence cluster. The Cu(Z) site is the catalytic site, which had long been thought to have novel spectroscopic properties. However, the low-energy electronic transitions and resonance Raman features attributable to Cu(Z) have been difficult to reconcile with a lack of conserved cysteine residues in standard alignments of N(2)OR sequences, other than those associated with the Cu(A) site. Recent evidence indicates that nitrous oxide reductase contains acid-labile sulfide and that this sulfide is a constituent of the Cu(Z) site (Rasmussen, T.; Berks, B. C.; Sanders-Loehr, J.; Dooley, D. M.; Zumft, W. G.; Thomson, A. J. Biochemistry 2000, 39, 12753-12756). We have used resonance Raman (RR) spectroscopy to selectively probe the Cu(A) and Cu(Z) sites of N(2)OR in three oxidation states (oxidized, semireduced, and reduced) as well as Cu(A)-only and Cu(Z)-only variants. The Cu(A) (mixed-valence, also designated as A(mv)) RR spectrum exhibits 10 vibrational modes between 220 and 410 cm(-1), with >1-cm(-1) (34)S isotope shifts that sum to -16.6 cm(-1). Many of these modes are also sensitive to (65)Cu and (15)N(His) and, thus, can be assigned to coupling of the Cu-S stretch, nu(Cu-S), with cysteine and histidine vibrations of the Cu(2)Cys(2)His(2) core. The RR spectrum of the Cu(Z) site (Z(ox)) reveals a novel Cu-sulfur chromophore with four S isotope-sensitive modes at 293, 347, 352, and 408 cm(-1), with a total (34)S shift of -19.9 cm(-)(1). The magnitude of the S isotope shifts and wide spread of perturbed frequencies are similar to those observed in Cu(A) and therefore suggest a sulfur-bridged cluster in Z(ox). The Z(ox) site has its nu(Cu-S)-containing modes at higher energy and exhibits less mixing with ligand deformations, compared to Cu(A). Reduction by dithionite produces a mixed-valence Cu(Z) site (Z(mv)) with six S isotope-sensitive RR modes between 282 and 382 cm(-1) and a total (34)S-shift of -16.9 cm(-1). The observation of a nearly identical RR spectrum in the C622D variant of N(2)OR, which lacks one of the conserved Cu(A) Cys residues, establishes that Cu-S vibrations observed in this variant arise from the Z(mv) site. Furthermore, none of the features assigned to Cu(Z) are detected in a second variant that contains only Cu(A). Therefore the resonance Raman spectra reported here provide compelling evidence for a unique Cu-S cluster in the catalytic site of nitrous oxide reductase.     

Gas-phase kinetic and mechanistic studies of some interconverting alkylcyclopropene pairs: involvement of dialkylvinylidene intermediates and their quantitative behaviour

The pyrolyses of two isomeric pairs of alkylcyclopropenes, namely 1,3-dimethyl-(15) and 1-ethyl-cyclopropene (16), and 1,3,3-trimethyl-(5) and 1-isopropyl-cyclopropene (17), have been studied in the gas phase. Complete product analyses at various conversions up to 95% were obtained for the decomposition of each compound at five temperatures over a 40 degrees C range. The time-evolution data showed that the isomerisation reactions 15<==>16 and 5<==>17 were occurring. Kinetic modelling of each system allowed the determination of rate constants for these and all other decomposition processes. Tests confirmed that all reactions were unimolecular and homogeneous. Arrhenius parameters are reported for overall reactions and individual product pathways. Further kinetic analysis allowed us to extract the propensities (at 500 K) for 1,3-C-H insertion of the dialkylvinylidene intermediates involved in the rearrangements as follows: k(prim):k(sec): k(tert)= 1:16.5:46.4. Additional experiments with 13C-labelled cyclopropenes yielded alkyl group migration aptitudes for the dialkylvinylidenes (from the pattern of 13C in the alkyne products) as follows: Me:Et:iPr=1:3.1:1.5. Explanations for these trends are given. Another important finding is that of the dramatic rate enhancements for 1,3-diene product formation from the 1-alkylcyclopropenes; this can be explained by either hyperconjugative stabilisation of the vinylcarbene intermediates involved in this pathway, or their differing propensities to 1,2 H-shift. The observed large variations in product distribution amongst these four cyclopropenes is interpreted in terms of these specific effects on individual pathways.     

Enhanced near-neighbour aggregation of dichloro- and trichloromethane in liquid methane solution from molecular dynamics simulation of radial site–site distribution functions: a simple predictor of solute–solvent compatibility

Molecular dynamics simulations have been performed for a range of equi-site and site–site radial distribution functions for the five-atom halomethane species dichloro-, trichloro-, and tetrachloromethane dissolved in the low-molecular weight hydrocarbons liquefied methane and cyclopropane, with the general aim of using this approach to predict good or bad solvent characteristics. It was found that methane solutions of dichloro- and trichloromethane showed an enhancement of near-neighbour occupancy, the methane solvent seemingly exhibiting a phobic, structure-promoting solvation behaviour towards the two solutes by increasing the number of nearest neighbours above the values that would result from a pure dilution effect caused by the solvent. It was verified that there were no significant regions of solid-like conformations nor remnants of imperfect average homogeneity within the system at the necessarily low temperature (183?K). On the other hand, simulated site–site radial functions with solvents tetrachloromethane and cyclopropane indicate normal solution characteristics towards solutes dichloro- and trichloromethane. The cause of the phobic solvation behaviour of solvent liquid methane towards di- and trichloromethane is not obvious, except that it seemingly involves the presence of hydrogen atoms on the solute species because the site–site centre-of-mass radial distribution functions of tetrachloromethane in liquid methane implied normal solution behaviour.     

Direct coulomb and exchange interaction in artificial atoms

We determine contributions from the direct Coulomb and exchange interactions to the total interaction in artificial semiconductor atoms. We tune the relative strengths of the two interactions and measure them as a function of the number of confined electrons. The electrons tend to have parallel spins when they occupy nearly degenerate single-particle states. We use a magnetic field to adjust the single-particle-state degeneracy, and find that the spin configurations in an arbitrary magnetic field are well explained in terms of two-electron singlet and triplet states.     

Electron-mediating Cu(A) centers in proteins: a comparative high field (1)H ENDOR study

High field (W-band, 95 GHz) pulsed electron-nuclear double resonance (ENDOR) measurements were carried out on a number of proteins that contain the mixed-valence, binuclear electron-mediating Cu(A) center. These include nitrous oxide reductase (N(2)OR), the recombinant water-soluble fragment of subunit II of Thermus thermophilus cytochrome c oxidase (COX) ba(3) (M160T9), its M160QT0 mutant, where the weak axial methionine ligand has been replaced by a glutamine, and the engineered "purple" azurin (purpAz). The three-dimensional (3-D) structures of these proteins, apart from the mutant, are known. The EPR spectra of all samples showed the presence of a mononuclear Cu(II) impurity with EPR characteristics of a type II copper. At W-band, the g( perpendicular) features of this center and of Cu(A) are well resolved, thus allowing us to obtain a clean Cu(A) ENDOR spectrum. The latter consists of two types of ENDOR signals. The first includes the signals of the four strongly coupled cysteine beta-protons, with isotropic hyperfine couplings, A(iso), in the 7-15 MHz range. The second group consists of weakly coupled protons with a primarily anisotropic character with A(zz) < 3 MHz. Orientation selective ENDOR spectra were collected for N(2)OR, M160QT0, and purpAz, and simulations of the cysteine beta-protons signals provided their isotropic and anisotropic hyperfine interactions. A linear correlation with a negative slope was found between the maximum A(iso) value of the beta-protons and the copper hyperfine interaction. Comparison of the best-fit anisotropic hyperfine parameters with those calculated from dipolar interactions extracted from the available 3-D structures sets limit to the sulfur spin densities. Similarly, the small coupling spectral region was simulated on the basis of the 3-D structures and compared with the experimental spectra. It was found that the width of the powder patterns of the weakly coupled protons recorded at g(perpendicular) is mainly determined by the histidine H(epsilon)(1) protons. Furthermore, the splitting in the outer wings of these powder patterns indicates differences in the positions of the imidazole rings relative to the Cu(2)S(2) core. Comparison of the spectral features of the weakly coupled protons of M160QT0 with those of the other investigated proteins shows that they are very similar to those of purpAz, where the Cu(A) center is the most symmetric, but the copper spin density and the H(epsilon)(1)-Cu distances are somewhat smaller. All proteins show the presence of a proton with a significantly negative A(iso) value which is assigned to an amide proton of one of the cysteines. The simulations of both strongly and weakly coupled protons, along with the known copper hyperfine couplings, were used to estimate and compare the spin density distribution in the various Cu(A) centers. The largest sulfur spin density was found in M160T9, and the lowest was found in purpAz. In addition, using the relation between the A(iso) values of the four cysteine beta-protons and the H-C-S-S dihedral angles, the relative contribution of the hyperconjugation mechanism to A(iso) was determined. The largest contribution was found for M160T9, and the lowest was found for purpAz. Possible correlations between the spin density distribution, structural features, and electron-transfer functionality are finally suggested.