Conformational Landscape and Polymorphism in 5-Acetic Acid Hydantoin.

The conformational space of 5-acetic acid hydantoin {5AAH; [2-(2,5-dioxoimidazolidin-4-yl)acetic acid]} was investigated by quantum chemical calculations performed at the DFT(B3LYP)/6-311++G(d,p) level of theory. A total of 13 conformers were located in the potential energy surface of the molecule, six of them bearing the carboxylic group in the cis arrangement (O═C-O-H dihedral equal to ∼0°) and the other seven possessing this group in the trans configuration (O═C-O-H dihedral equal to ∼180°). The most stable conformer (cis-I) was trapped from the gas phase into a low temperature argon matrix (10 K), and its infrared spectrum was fully assigned, also with help of results of normal coordinates' analysis based on the DFT computed vibrational data. The electronic structure of this conformer was analyzed by using the natural bond orbital (NBO) method. The investigation of the thermal properties of 5AAH was undertaken by differential scanning calorimetry (DSC), polarized light thermal microscopy (PLTM) and Raman spectroscopy, allowing identification of five different polymorphs. Very interestingly, in the room temperature stable polymorph the molecular units of 5AAH assume the geometry of the highest-energy conformer predicted by the calculations for the isolated molecule.

5-Methylhydantoin: From Isolated Molecules in a Low-Temperature Argon Matrix to Solid State Polymorphs Characterization.

The molecular structure, vibrational spectra and photochemistry of 5-methylhydantoin (C4H6N2O2; 5-MH) were studied by matrix isolation infrared spectroscopy and theoretical calculations at the DFT(B3LYP)/6-311++G(d,p) theory level. The natural bond orbital (NBO) analysis approach was used to study in detail the electronic structure of the minimum energy structure of 5-MH, namely the specific characteristics of the σ and π electronic systems of the molecule and the stabilizing orbital interactions. UV irradiation of 5-MH isolated in argon matrix resulted in its photofragmentation through a single photochemical pathway, yielding isocyanic acid, ethanimine, and carbon monoxide, thus following a pattern already observed before for the parent hydantoin and 1-methylhydantoin molecules. The investigation of the thermal properties of 5-MH was undertaken by differential scanning calorimetry (DSC), polarized light thermal microscopy (PLTM) and Raman spectroscopy. Four different polymorphs of 5-MH were identified. The crystal structure of one of the polymorphs, for which it was possible to grow up suitable crystals, was determined by X-ray diffraction (XRD). Two of the additional polymorphs were characterized by powder XRD, which confirmed the molecules pack in different crystallographic arrangements.

Micro-Raman, FTIR, SEM-EDX and structural analysis of the Çanakkale meteorite.

This study demonstrates for the first time, the spectroscopic characterization of Çanakkale Meteorite that fell at Çanakkale, Republic of Turkey (40°8'44″N; 26°24'23″E). The olivine group [(Mg, Fe)(2)SiO(4)], enstatite [Mg(2)Si(2)O(6)] (one of the orthopyroxene minerals) and plagioclase were identified by the micro-Raman and FTIR spectroscopies and EDX-SEM analyses. This meteorite has not yet been classified in the World's Database of Meteorites. The aim of this study is to investigate this meteorite by vibrational spectroscopic techniques and open the possibility to classify it and list in the World's Database of Meteorites.