Conformational study of monomeric 2,3-butanediols by matrix-isolation infrared spectroscopy and DFT calculations

The FT-IR spectra of two diastereomers of 2,3-butanediol, (R,S) and (S,S), isolated in low-temperature argon and xenon matrixes were studied, allowing the identification of two different conformers for each compound. These conformers were characterized by a +/-gauche arrangement around the O-C-C-O dihedral angle, thus enabling the establishment of a very weak intramolecular hydrogen bond of the O...H-O type. No other forms of these compounds were identified in matrixes, despite the fact that these four conformers had calculated relative energies from 0 to 5.1 kJ mol(-1) and were expected to be thermally populated from 50 to 6% in the gaseous phase of each compound. The nonobservation of additional conformers was explained in terms of low barriers to intramolecular rotation, resulting in the conformational relaxation of the compounds during deposition of the matrixes. The barriers to internal rotation of the OH groups were computed to be less than 4 kJ mol(-1) and are easily overcome in matrixes within the family of conformers with the same heavy atom backbone. The barriers for intramolecular rearrangement of the O-C-C-O dihedral angle in both diastereomers were calculated to range from 20 to 30 kJ mol(-1). Interconversions between the latter conformers were not observed in matrixes, even after annealing up to 65 K. Energy calculations, barriers, and calculated infrared spectra were carried out at the DFT(B3LYP)/6-311++G theory. Additional MP2/6-311++G calculations of energies and vibrational frequencies were performed on the most relevant conformers. Finally, independent estimations of the hydrogen-bond enthalpy in the studied molecules were also obtained based on theoretical structural data and from vibrational frequencies (using well-established empirical correlations). The obtained values for -DeltaH for both diastereomers of 2,3-butanediol amount to ca. 6-8 kJ mol(-1).     

Photoisomerization and photochemistry of matrix-isolated 3-furaldehyde

3-Furaldehyde (3FA) was isolated in an argon matrix at 12 K and studied using FTIR spectroscopy and quantum chemistry. The molecule has two conformers, with trans and cis orientation of the O=C-C=C dihedral angle. At the B3LYP/6-311++G(d,p) level of theory, the trans form was computed to be ca. 4 kJ mol(-1) more stable than the cis form. The relative stability of the two conformers was explained using the natural bond orbital (NBO) method. In fair agreement with their calculated relative energies and the high barrier of rotamerization (ca. 34 kJ mol(-1) from trans to cis), the trans and cis conformers were trapped in an argon matrix from the compound room temperature gas phase in proportion ~7:1. The experimentally observed vibrational signatures of the two forms are in a good agreement with the theoretically calculated spectra. Broad-band UV-irradiation (λ > 234 nm) of the matrix-isolated compound resulted in partial trans → cis isomerization, which ended at a photostationary state with the trans/cis ratio being ca. 1.85:1. This result was interpreted based on results of time-dependent DFT calculations. Irradiation at higher energies (λ > 200 nm) led to decarbonylation of the compound, yielding furan, cyclopropene-3-carbaldehyde, and two C(3)H(4) isomers: cyclopropene and propadiene.     

EPMA and Microstructural Characterization of Yttrium Doped BaTiO3 Ceramics

 Yttrium-doped BaTiO₃ ceramics have been studied as a potential material for positive temperature coefficient resistors (PTCR). The mechanism of Y incorporation into BaTiO₃ plays an important role for displaying good electrical properties. Determination of the amount of yttrium in the BaTiO₃ as well as microstructure characterization of the samples were performed using SEM, EDS and WDS analysis. An optimized trace element WDS quantitative analysis was applied to determine elemental concentrations for Ba, Ti and Y in the samples as accurately as possible. BaTiO₃ and Y₂O₃ were used as standards. Analysis was undertaken using a JEOL JXA 840A electron probe microanalyzer. WDS X-ray intensity measurements were performed under 20 kV, 50 nA beam current and 0.2% preset standard counting deviation (σ_c) using a PET crystal. Measured k-ratios were quantified by ZAF matrix correction. Average results of WDS quantitative analysis showed 20.17 ± 0.08 at % Ti, 19.95 ± 0.09 at % Ba, 0.22 ± 0.03 at % Y, and 59.66 at % O. The results suggest incorporation of yttrium in the BaTiO₃ preferentially at the Ba-sites, however partial incorporation of Y at Ti-sites could not be excluded.     

Lattice modeling: Accuracy of energy calculations

Energy calculations based on lattice models of protein chains are always approximate, because any such a model distorts distances between chain links and, consequently, the energies of interaction between them. The energetic errors of lattice models are examined here for 15 proteins of different sizes and types of secondary structure, for lattice spacings ranging from 0.25 to 2.5 Å. The lattice models are derived using previously described algorithms which insure a minimal root mean square (rms) deviation from the off-lattice structure for any given lattice-protein orientation. For each protein structure we computed a set of different lattice models with virtually equal rms deviations, and then compared their energies. Energy calculations were based on the pairwise potentials. We found that the energies of lattice models follows a normal distribution with a nonnegligible dispersion, even at a fine lattice spacing of 0.25 Å. For any lattice model of a protein, the lattice spacing must be 1.0 Å or less in order to be able to distinguish energetically between the folded and extended states. However, when an ensemble of lattice models is considered, this distinction can be made for lattice spacing up to 2.0 Å. We conclude that to attain a better approximation of the protein lattice model energies, one must adjust potentials to the lattice spacing. © 1996 by John Wiley & Sons, Inc.     

On the pyrolysis mechanism of 2-pyranones and 2-pyranthiones: thermally induced ground electronic state chemistry of pyran-2-thione

[reaction: see text] This work reports studies of thermochemistry of pyran-2-thione (PT), a sulfur derivative of alpha-pyrone (AP). Moderate heating of PT results in scrambling of sulfur and oxygen atoms in the molecule and formation of isomeric thiapyran-2-one (TP). The products of pyrolysis of PT were studied experimentally by a combined use low temperature matrix isolation and Fourier transform infrared spectroscopy. The infrared spectrum of the TP monomer isolated in solid argon at 10 K was completely assigned based on comparison with theoretical calculations undertaken at the DFT(B3LYP)/6-311++G(d,p) level. The upper limit of thermal stability of PT was investigated using the differential scanning calorimetry technique. It was found that pyrolysis of PT is already initiated at temperatures below 130 degrees C. The mechanism of the observed pyrolytical conversion has been studied theoretically at the MP2/6-311++G(d,p) level, in the ground electronic state. The primary step of the pyrolytical reaction in PT is the alpha-cleavage of the C-O single bond. It proceeds via an open-ring thioketene-aldehyde structure, TK1. According to the calculations, the ring-opening reaction from PT to TK1 requires an activation energy less than 80 kJ mol(-1), at 130 degrees C, being the rate-determining step. Further steps of the pyrolytical reaction involve internal rotations around single bonds and [1,5] sigmatropic shift of the aldehydic hydrogen. Pyrolytical ring-opening reactions were studied theoretically also for AP and TP and compared to the pyrolysis of PT. It is suggested that the relative ease of the pyrolytical transformation in PT can be explained in terms of existence of the additional minimum TK1 in the reaction path. No counterparts for this structure could be theoretically located for AP and TP.