The reaction of iodine monochloride and monobromide with tetraorganotins

The reactions of iodine monochloride and iodine monobromide with a tetraalkyltin (butyl) and a tetraaryltin (phenyl) have been studied with a view to establishing their utility as routes to organotin chlorides and bromides respectively. Rapid high yield syntheses of the triorganotin bromides, diorganotin dichlorides and trialkyltin chloride were achieved. Some further suggestions are made on the mechanism of interhalogen fission of tincarbon bonds.     

Optimal double-configuration study of the lowest excited Π states of H2

Various levels of approximation (Hartree-Fock, configuration interaction and double-configuration Hartree-Fock method) are compared for extensive and limited exponent optimization of the atomic orbitals of the wavefunctions. The potential energy curves for the lowest-lying ¹ _u, ³ _u, ¹ _g, ³ _g states of the hydrogen molecule are presented. The shapes of the curves on the highest level of approximation, i.e. with the optimal double-configuration wavefunction, are basically in agreement with previous, more sophisticated and time-consuming work. The influence of the various approximations is also studied for several one-electron properties: charge distribution of the wavefunction along and perpendicular to the molecular axis, quadrupole moment and core attraction energy distribution. Differences arise to the work of Zemke et al. [1], who used a limited exponent optimization with a larger basis set, in the _g states where the orbitals are very diffuse. The differences concern magnitude and location of minima and maxima of potential curves, as well as considerable changes in one-electron properties which depend strongly on the spatial distribution of the orbitals.

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Zusammenfassung Verschiedene Approximationsstufen (Hartree-Fock, Konfigurationenwechselwirkung und Doppelkonfigurationen-Hartree-Fock-Methode) werden für ausgedehnte und begrenzte Exponentenoptimisierung von Atomorbitalen der Wellenfunktionen verglichen. Die Potentialkurven für die niedrigsten ¹ _u, ³ _u, ¹ _g, ³ _g Zustände des Wasserstoffmoleküls werden angegeben. Die Form der Kurven im Rahmen der besten Näherung, d. h. mit Doppelkonfiguration, stimmen im wesentlichen mit früheren aufwendigeren Rechnungen überein. Der Einfluß der verschiedenen Approximationen wird auch an einigen Einelektroneneigenschaften studiert: Ladungsverteilung der Wellenfunktion längs und senkrecht zur Molekülachse, Quadrupolmoment und Verteilung der Rumpfenergie. Unterschiede erscheinen zur Arbeit von Zemke et al. [1], die einen größeren Basissatz mit begrenzter Optimisierung verwandten, bei den _g Zuständen, wo die -Orbitale sehr diffus sind. Die Unterschiede betreffen Größe und Lage der Minima und Maxima der Potentialkurven sowie beträchtliche Änderungen in solchen Einelektroneneigenschaften, die stark von der räumlichen Verteilung der Orbitale abhängen.

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Résumé Comparaison de différents niveaux d'approximation (Hartree-Fock, interaction de configuration et Hartree-Fock à deux configurations) pour des optimisations étendues et limitées des orbitales atomiques de base. Calcul des courbes d'énergie potentielle pour les plus bas états ¹ _u, ³ _u, ¹ _g, ³ _g de la molécule d'hydrogène. Pour la fonction d'onde la plus raffinée: H.F. à deux configurations, la forme des courbes est en accord avec les résultats obtenus dans des travaux précédents plus complexes et plus coûteux. On étudie aussi l'influence des diverses approximations sur plusieurs propriétés monoélectroniques: distribution de charge le long de l'axe moléculaire et perpendiculairement à celui-ci, moment quadrupolaire et distribution de l'énergie d'attraction de coeur. On trouve des différences avec le travail de Zemke et al. (1), qui utilisent une plus grande base partiellement optimisée, pour les états _g où les orbitales sont très diffuses. Les différences concernent la grandeur et la position des extrema des courbes de potentiel, ainsi que des variations importantes des propriétés monoélectroniques qui dépendent fortement de la distribution spatiale des orbitales.

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On leave to: Institut für Theoretische Chemie, Universität Stuttgart.

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On leave to: Office of Computing Activities, National Science Foundation, Washington, D.C.     

Ion mobility–mass spectrometry: a new paradigm for proteomics

Matrix-assisted laser desorption/ionization (MALDI) coupled with ion mobility–mass spectrometry (IM–MS) provides a rapid (μs–ms) means for the two-dimensional (2D) separation of complex biological samples (e.g., peptides, oligonucleotides, glycoconjugates, lipids, etc.), elucidation of solvent-free secondary structural elements (e.g., helices, β-hairpins, random coils, etc.), rapid identification of post-translational modifications (e.g., phosphorylation, glycosylation, etc.) or ligation of small molecules, and simultaneous and comprehensive sequencing information of biopolymers. In IM–MS, protein-identification information is complemented by structural characterization data, which is difficult to obtain using conventional proteomic techniques. New avenues for enhancing the figures of merit (e.g., sensitivity, limits of detection, dynamic range, and analyte selectivity) and optimizing IM–MS experimental parameters are described in the context of deriving new information at the forefront of proteomics research.     

Size-selected (2-10 nm) gold nanoparticles for matrix assisted laser desorption ionization of peptides

In this report, first use of size-selected gold nanoparticles (AuNPs) as matrixes for matrix assisted laser desorption/ionization (MALDI) is described for peptides and proteins. In comparison with conventional organic acid MALDI matrixes, the optimum matrix-to-analyte ratio with AuNP matrixes is reduced by 10-14 orders of magnitude. Significant differences in the relative abundances of the ions observed in positive and negative mode MALDI-time-of-flight mass spectrometry (TOFMS) are revealed as the AuNP size distribution is decreased from 10 to 2 nm, whereby 2-nm AuNPs exhibit quantum confinement effects prevalent in quantum dots. AuNP matrixes allow for selective analyte ionization, as demonstrated in the selective MALDI-TOFMS of phosphotyrosine in a background of phosphoserine and phosphothreonine peptides.     

Structural isomers of C2N+: a selected-ion flow tube study

Reactivities of the structural isomers CCN+ and CNC+ were examined in a selected-ion flow tube at 300 +/- 5 K. The less reactive CNC+ isomer was identified as the product of the reactions of C(+) + HCN and C(+) + C2N2; in these reactions only CNC+ can be produced because of energy constraints. Rate coefficients and branching ratios are reported for the reactions of each isomer with H2, CH4, NH3, H2O, C2H2, HCN, N2, O2, N2O, and CO2. Ab initio calculations are presented for CCN+ and CNC+; a saddle point for the reaction CCN+ --> CNC+ is calculated to be 195 kJ mol-1 above the CNC+. The results provide evidence that the more reactive CCN+ isomer is unlikely to be present in measurable densities in interstellar clouds.     

Cyclopropane chemistry. Part 5 [1,2]. Hexafluorocyclopropane as a source of difluorocarbene

Thermolysis of hexafluorocyclopropane in the presence of ethylene, propene, vinyl chloride, and vinyl bromide gives good yields of the corresponding 1,1-difluorocyclopropanes, formed by addition of difluorocarbene to the olefin. The tetrafluoroethylene formed dimerises to octafluorocyclobutane, co-dimerises with the olefin, or survives, depending on the reaction conditions. With allene, hexafluorocyclopropane gives 1-(difluoromethylene)cyclopropane, 2,2,3,3-tetrafluorospiropentane, and products derived from tetrafluoroethylene and allene.     

Calculations on the competition between association and reaction for C3H(+) + H2

A potential energy surface has been calculated for the competing associative and reactive ion-molecule processes involving the reactants C3H(+) + H2. Our ab initio results show that the linear ion C3H+ and H2 can directly access the deep potential well of the propargyl ion H2CCCH+, which is calculated to lie 390 kJ mol-1 below the zero-point energy of the reactants. Isomerization between the propargyl ion and the lower energy, cyclic C3H3+ ion, calculated to lie 501 kJ mol-1 below the zero-point energy of reactants, can subsequently occur via two pathways. One of these pathways involves a transition state lying 22 kJ mol-1 below the energy of the reactants while the other, which occurs at much lower energies, involves two transition states and an intermediate. The dissociation of c-C3H3+ into c-C3H2(+) + H is calculated to occur directly, without any intermediate potential energy maximum, but the energy of the products lies 7.3 kJ mol-1 above the energy of the reactants. Using the minimum energy potential pathway and properties of the stationary point structures determined via ab initio methods, we have calculated both the association rate coefficient to produce C3H3+ as a function of density and the branching ratio between the propargyl and cyclic structures of the ion. Our results are in good agreement with some experimental results and in conflict with others. Specifically, we agree with the 1:1 branching ratio measured for the propargyl and cyclic isomers of C3H3+ at 80 and 300 K and we agree with the rate coefficient for radiative association measured at 80 K. We cannot reproduce reported measurements that the reactive channel (C3H2(+) + H) is the dominant channel at 80 K and at low gas densities, or that the association channel at high densities saturates at an effective rate coefficient well below the Langevin value -2x10(-11) cm3 s-1 at 300K and 1x10(-10) cm3 s-1 at 80K.     

Magnetic Field Effects on the Behavior of Radicals in Protein and DNA Environments

We have examined the behavior of radical pairs derived by hydrogen abstraction of triplet benzophenone and some of its derivatives from bovine serum albumin, human serum albumin and calf thymus DNA. They have been investigated by means of nanosecond laser flash photolysis techniques. The dynamics of radical pair behavior are shown to be sensitive to external magnetic fields; these effects are interpreted using the established model for the influence of magnetic fields on radical pairs in micellar aggregates, in which intersystem crossing of the radical pair is slowed by the external magnetic field. Our results indicate that proteins and DNA can confine the radicals for a sufficiently long period of time for spin evolution to be affected by external fields. In proteins the radical pair retains its geminate character ( i.e . remains confined) for about 0.5–1 μs. Interestingly, the magnetic field effects observed in proteins and in DNA seem to occur in distinct timescales; for example, for 2,3,4,5,6-pentafluorobenzophenone bound to DNA, the magnetic field alters the radical reactivity only over times ≤50 ns, suggesting poor confinement. The timescale for these effects can be increased by promoting Coulombic attraction between DNA and the radical precursor. Electron transfer interactions play a role in the case of DNA.