Millimeter and submillimeter wave spectroscopic investigations into the rotation-tunneling spectrum of gGg ethylene glycol, HOCH2CH2OH

The rotation-tunneling spectrum of the second most stable gGg^′ conformer of ethylene glycol (1,2-ethanediol) in its ground vibrational state has been studied in selected regions between 77 and 579 GHz. Compared to the study of the more stable aGg^′ conformer, a much larger frequency range was studied, resulting in a much extended frequency list covering similar quantum numbers, J?55 and K_a?19. While the input data were reproduced within experimental uncertainties up to moderately high values of J and K_a larger residuals remain at higher quantum numbers. The severe mixing of the states caused by the Coriolis interaction between the two tunneling substates is suggested to provide a considerable part of the explanation. In addition, a Coriolis interaction of the gGg^′ ground vibrational state with an excited state of the aGg^′ conformer may also contribute. Relative intensities of closely spaced lines have been investigated to determine the signs of the Coriolis constants between the two tunneling substates relative to the dipole moment components and to estimate the magnitudes of the dipole moment components and the energy difference between the gGg^′ and the aGg^′ conformers. Results of ab initio calculations on the total dipole moment and the vibrational spectrum were needed for these estimates. The current analysis is limited to transitions with quantum numbers J?40 and K_a?6 plus those having J?22 and K_a?17 which could be reproduced within experimental uncertainties. The results are aimed at aiding radioastronomers to search for gGg^′ ethylene glycol in comets and in interstellar space.     

Crystallization of Arthrobacter sp. strain 1C N-(1-D-carboxyethyl)-L-norvaline dehydrogenase and its complex with NAD+

The novel NAD+-linked opine dehydrogenase from a soil isolate Arthrobacter sp. strain 1C belongs to an enzyme superfamily whose members exhibit quite diverse substrate specificites. Crystals of this opine dehydrogenase, obtained in the presence or absence of co-factor and substrates, have been shown to diffract to beyond 1.8 ? resolution. X-ray precession photographs have established that the crystals belong to space group P21212, with cell parameters a = 104.9, b = 80.0, c = 45.5 ? and a single subunit in the asymmetric unit. The elucidation of the three-dimensional structure of this enzyme will provide a structural framework for this novel class of dehydrogenases to enable a comparison to be made with other enzyme families and also as the basis for mutagenesis experiments directed towards the production of natural and synthetic opine-type compounds containing two chiral centres.     

Molecular structure of gaseous vanadyl(V) fluoride as studied by electron diffraction,and its modified valence force field

The molecular structure of gaseous OVF₃ has been determined by electron diffraction to be: r_g(V-O) = 1.570(5) Å, r_g(V-F) = 1.729(2) Å and ∠_α(OVF) = 107.5(4)°. A modified force field has been fitted to results from spectroscopic as well as diffractional studies. A similar attempt to determine the force field for OVCl₃ was not as successful as for OVF₃, probably because the Coriolis constants are less accurately determined for that molecule.     

A resonance Raman,surface-enhanced resonance Raman,IR, and ab initio vibrational spectroscopic study of nickel(II) tetraazaannulene complexes

The IR and resonance Raman spectra of the nickel(II) complexes of dibenzo[b,i][1,4,8,11]tetraaza[14]annulene (TAA) and 5,7,12,14-tetramethyldibenzo[b,i][1,4,8,11]tetraaza[14]annulene (TMTAA) have been measured and compared with ab initio calculations of the vibrational wavenumbers at the B3-LYP level using the LanL2DZ basis set. An excellent fit is found between the experimental and calculated data, enabling precise vibrational assignments to be made. Surface-enhanced resonance Raman spectra were obtained following adsorption on Ag electrodes, with potentials in the range -0.1 to -1.1 V vs Ag/AgCl. There is evidence for contributions from both the electromagnetic and charge transfer (CT) surface enhancement mechanisms. The data indicate that variations in band intensities with electrode potential can be interpreted in terms of the CT mechanism.     

Chemical interactions in the surface-enhanced resonance Raman scattering of ruthenium polypyridyl complexes

Surface-enhanced resonance Raman scattering (SERRS) from the alpha-diimine complexes [Ru(bpm)(3)](2+) and [Ru(bpz)(3)](2+) is reported for the first time at a roughened silver electrode. In both cases, a possible adsorbate orientation has been proposed involving binding through nitrogen lone pair electrons to the silver surface, based on changes in band positions upon adsorption. The SERRS spectra of [Ru(bpm)(3)](2+) were found to change slightly with a change in applied potential. The relative intensity of the nu(C6C6') band was found to be dependent on both excitation wavelength and applied potential. This was ascribed to an active charge transfer (CT) mechanism operating synergistically with the electromagnetic mechanism. No such CT activity was observed in [Ru(bpz)(3)](2+). It is tentatively suggested that this behavior may arise from the different modes of adsorption of the two complexes.     

Synthesis and characterization of layered tetravalent metal terphenyl mono- and bis-phosphonates

The syntheses of p-terphenylphosphonic acid and p,p″-terphenyl-bis-phosphonic acid have been developed, and the resulting products were used to prepare layered Th(IV) and Zr(IV) phosphonates. The monoacidic terphenyl species formed a bilayered structure while the diacid created a pillared geometry. Mixed component phases were also produced. Synthesis, characterization, X-ray and thermal properties of these materials are discussed.     

X-Ray Crystallographic Structure of the Cyclic Di-amino Acid Peptide: <Emphasis Type="Italic">N,N</Emphasis>′-Diacetyl-cyclo(Gly-Gly)

Abstract  

The cyclic di-amino acid peptide N,N′-diacetyl-cyclo(Gly-Gly), C₈H₁₀N₂O₄, crystallizes in the triclinic space group P[`1] P\bar{1} with unit cell parameters a = 9.4855(4) ?, b = 10.0250(3) ?, c = 10.0763(4) ?, α = 73.682(2)°, β = 82.816(2)°, γ = 81.733(2)°, V = 906.40(6) ?<sup>3</sup>, Z = 4 (2 molecules, A and B, per asymmetric unit), D<sub>c</sub> = 1.452 g cm<sup>−3</sup> and linear absorption coefficient 0.118 mm<sup>−1</sup>. The crystal structure determination was carried out with MoKα X-ray data measured at 120(2) K. In the final refinement cycle the data/restraints/parameter ratios were 4124/0/258 and goodness-of-fit on F<sup>2</sup> = 1.0008. Final R indices for [I > 2σ(I)] were R<sub>1</sub> = 0.0501, wR<sub>2</sub> = 0.1007 and R indices (all data) R<sub>1</sub> = 0.0864, wR<sub>2</sub> = 0.11180. The largest electron density difference peak and hole were 0.241 and −0.232 e ?<sup>−3</sup>, respectively. The DKP rings in both molecules A and B have boat conformations with pseudo mm2 (C<sub>2v</sub>) symmetry if the N atoms and CH<sub>2</sub> groups are considered identical. In each case, the prow and stern of the boat are the α-carbons C(3) and C(6). The overall molecular symmetry of molecules A and B is approximately C<sub>2</sub> with the twofold symmetry axis of the DKP boat being maintained through the centre of the DKP ring. Details of the molecular geometry are compared with that of the parent compound cyclo(Gly-Gly) in which the DKP ring is planar with exact symmetry [`1] \bar{1} (C_i).     

Vibrational spectra and crystal structure of the di‐amino acid peptide cyclo(L‐Met‐L‐Met): comparison of experimental data and DFT calculations

Experimental Raman and FT‐IR spectra of solid‐state non‐deuterated and N‐deuterated samples of cyclo(L ‐Met‐L ‐Met) are reported and discussed. The Raman and FT‐IR results show characteristic amide I vibrations (Raman: 1649 cm⁻¹, infrared: 1675 cm⁻¹) for molecules exhibiting a cis amide conformation. A Raman band, assigned to the cis amide II vibrational mode, is observed at ∼1493 cm⁻¹ but no IR band is observed in this region. Cyclo(L ‐Met‐L ‐Met) crystallises in the triclinic space group P1 with one molecule per unit cell. The overall shape of the diketopiperazine (DKP) ring displays a (slightly distorted) boat conformation. The crystal packing employs two strong hydrogen bonds, which traverse the entire crystal via translational repeats. B3‐LYP/cc‐pVDZ calculations of the structure of the molecule predict a boat conformation for the DKP ring, in agreement with the experimentally determined X‐ray structure. Copyright © 2009 John Wiley & Sons, Ltd.