Gas phase ion/molecule reactions in laser desorption mass spectrometry

The desorption of neutrals, alkali ions and quasimolecular ions of sucrose was studied as function of substrate temperature in laser desorption mass spectrometry. These phenomena were also investigated in thermal desorption experiments. It was concluded that in these experiments gas phase cationization is the major ionization process.     

Lattice dynamics of tetracyanoethylene

Lattice dynamics calculations for both crystalline forms of tetracyanoethylene are presented. The comparison of the calculated static and dynamical properties with the experimental data, leads us to suggest an improved parameter set for the “6-exp” potential function for crystals with cyano groups.     

Stereoelectronic control of exo/endo rate ratios in the solvolysis of 2-norbornyl p-toluenesulfonates

The variable exo/endo rate ratios observed in the solvolysis of 6-exo-substituted exo- and endo-2-norbornyl p-toluenesulfonates are due to differential transmission of polar effects in the transition state for ionization.     

Spirophostins: conformationally restricted analogues of adenophostin A

The synthesis, biological evaluation, and molecular modeling of two conformationally restricted analogues of adenophostinA (1), denominated as spirophostin (3R)-10 and (3S)-11, as novel ligands for the D-myo-inositol 1,4,5-trisphosphate receptor (IP3R), is presented. These diastereoisomeric spiroketals are synthesized by spiroketalization of D-glucose derivatives (2S)-15 and (2R)-16, separation of the protected isomers (3R)-19 and (3S)-20, followed by phosphorylation and deprotection. The spirophostins (3R)-10 and (3S)-11 display comparable biological activity, with a 3H-IP3-displacing and Ca2+-releasing potency less than IP3 and adenophostin A.     

Internally coordinated organozinc-transition metal compounds. Crystal structure of (CH3)2N(CH2)3ZnW(ν-C5H5)(CO)3

The stabilities of simple and internally coordinated organozinc-transition metal compounds towards disproportionation have been investigated by the microwave titration technique. Simple alkyl- and aryl-derivatives disproportionate to such an extent as to preclude isolation. Internal coordination was found to stabilize the asymmetric compounds, and several derivatives containing the dimethylaminopropyl group were isolated. The crystal structure of one of them, Me₂N(CH₂)₃-ZnW(Cp)(CO)₃, was determined by a single-crystal X-ray study. The crystals are orthorhombic, space group P2₁2₁2₁, with four molecular units in a cell with parameters a 8.406(1), b 12.179(2) and c 16.642(2) Å. The structure was solved by standard Patterson and Fourier techniques. The refinement, with anisotropic temperature factors for the two heavy atoms, converged at R_F = 0.092 (R_wF = 0.089) for 1536 observed reflections with I>2.5σ(I). The molecule consists of a central tungsten atom, surrounded in a tetragonal pyramidal fashion by a cyclopentadienyl group in the apical position and three carbon monoxyde molecules and a zinc atom occupying the basal positions. The zinc atom is three-coordinate, being surrounded by the tungsten atom and the chelating dimethylaminopropyl group; there is, however, a short intermolecular contact between zinc and a carbonyl oxygen atom at 2.61(3) Å.     

Systematic computer-aided interpretation of infrared and raman vibrational spectra based on the crise program

The CRISE computer program is used to correlate wavenumber regions and 6 structural elements containing carbon, hydrogen and oxygen on the basis of 2 standard files with 549 infrared and Raman spectra. The degree of correlation, including score percentages and interfering percentages, is established for different types of intervals in relation to various intensity thresholds. Specific regions (score 100%, interference 0%) proved to be rare, whereas pseudo-specific regions (score < 100%, interference 0%) are normally present. The usefulness of selective regions (score 100%, interference > 0%) is doubtful. The infrared and Raman results for a structural element can differ appreciably, yet neither technique is clearly superior for interpretative purposes.     

Dynamic imaging of single DNA-protein interactions using atomic force microscopy

Atomic force microscopy (AFM) imaging of static DNA-protein complexes, in air and in liquid, can be used to directly obtain quantitative and qualitative information on the structure of different complexes. For example, DNA length, the location of preferential binding sites for proteins and bending of DNA as a result of the complexation can all be measured. Recording consecutive AFM images of DNA and protein molecules under conditions that they are still able to move and interact, or dynamic AFM imaging, however, can reveal information on the dynamic aspects of the interactions between these molecules. Here, an overview is given of the technical challenges that need to be considered for successful dynamic AFM imaging studies of individual DNA-protein interactions. Necessary technical improvements to the AFM set-up and the development of new sample preparation methods are described in this paper.     

Synthesis of (E)- and (Z)-fluoro-olefin analogues of potent dipeptidyl peptidase IV inhibitors

(E)- and (Z)-fluoro-olefin analogues of potent dipeptidyl peptidase IV inhibitors were synthesized. A Wadsworth-Horner-Emmons reaction, followed by amide formation and reduction of the amide were used for the construction of the α-fluoro-α,β-unsaturated amine functionality.