Molecular structure and vibrational spectra of Bis(melaminium) terephthalate dihydrate: a DFT computational study.

The experimental and theoretical vibrational spectra of Bis(melaminium) terephthalate dihydrate were studied. The Fourier transform infrared (FT-IR) spectra of the Bis(melaminium) terephthalate dihydrate and its deuterated analogue were recorded in the solid phase. The molecular geometry and vibrational frequencies of Bis(melaminium) terephthalate dihydrate in the ground state have been calculated by using the density functional method (B3LYP) with 6-31++G(d,p) basis set. The results of the optimized molecular structure are presented and compared with the experimental X-ray diffraction. The molecule contains the weak hydrogen bonds of N-H···O, N-H···N and O-H···O types, and those bonds are calculated with DFT method. In addition, molecular electrostatic potential, frontier molecular orbitals and natural bond orbital analysis of the title compound were investigated by theoretical calculations. The lack of the second harmonic generation (SHG) confirms the presence of macroscopic center of inversion.

X-ray diffraction, vibrational and quantum chemical investigations of 2-methyl-4-nitroanilinium trichloroacetate trichloroacetic acid.

The structural investigations of the molecular complex of 2-methyl-4-nitroaniline with trichloroacetic acid, namely 2-methyl-4-nitroanilinium trichloroacetate trichloroacetic acid (C(11)H(10)Cl(6)N(2)O(6)) have been performed by means of single crystal and powder X-ray diffraction method. The complex was formed with accompanying proton transfer from trichloroacetic acid molecule to 2-methyl-4-nitroaniline. The studied crystal is built up of singly protonated 2-methyl-4-nitroanilinium cations, trichloroacetate anions and neutral trichloroacetic acid molecules. The crystals are monoclinic, space group P2(1)/c, with a=14.947Å, b=6.432Å, c=19.609Å and Z=4. The vibrational assignments and analysis of 2-methyl-4-nitroanilinium trichloroacetate trichloroacetic acid have also been performed by FTIR, FT-Raman and far-infrared spectral studies. More support on the experimental findings were added from the quantum chemical studies performed with DFT (B3LYP) method using 6-31G, cc-pVDZ, 6-31G and 6-31++G basis sets. The structural parameters, energies, thermodynamic parameters and the NBO charges of 2M4NATCA were also determined by the DFT methods.

Synthesis, vibrational and quantum chemical investigations of hydrogen bonded complex betaine dihydrogen selenite.

The molecular complex of betaine with selenious acid namely, betaine dihydrogen selenite (C(5)H(13)NO(5)Se, BDHSe) was synthesised by the reaction of betaine and SeO(2) in a 1:1:1 solution of isopropanol, methanol and water. Crystals were grown from this solution by cooling to 253 K for few days. The complex was formed without accompanying proton transfer from selenious acid molecule to betaine. The complete vibrational assignments and analysis of BDHSe have been performed by FTIR, FT-Raman and far-infrared spectral studies. More support on the experimental findings was added from the quantum chemical studies performed with DFT (B3LYP) method using 6-311++G(**), 6-31G(**), cc-pVDZ and 3-21G basis sets. The structural parameters, energies, thermodynamic parameters and the NBO charges of BDHSe were determined by the DFT method. The (1)H and (13)C isotropic chemical shifts (δ ppm) of BDHSe with respect to TMS were also calculated using the gauge independent atomic orbital (GIAO) method and compared with the experimental data. SHG experiment was carried out using Kurtz-Perry powder technique. The efficiency of second harmonic generation for BDHSe was estimated relatively to KDP: d(eff)=0.97 d(eff) (KDP).

3-Amino-1,2,4-triazolium ion in [24(3at)]Cl and [24(3at)]2SnCl6·H2O. Comparative X-ray, vibrational and theoretical studies.

Crystal structures of 3-amino-1,2,4-triazolium chloride and bis(3-amino-1,2,4-triazolium) hexachloridostannate monohydrate were determined by means of X-ray single crystal diffraction. The route of protonation of organic molecule and tautomer equilibrium constants for the cationic forms were calculated using B3LYP/6-31G* method. The most stable protonated species is 2,4-H(2)-3-amino-1,2,4-triazolium ion, 24(3at)(+). Very good agreement between theoretical and experimental frequencies was achieved due to very weak interactions existing in studied compounds. Significantly weaker intermolecular interactions are found in [24(3at)](2)SnCl(6)·H(2)O than in [24(3at)]Cl. The differences in strength of interactions are manifested in red and blue shifts for stretching and bending motions, respectively. PED calculations show that for 24(3at)(+) ion the stretching type of motion of two N(ring)H bonds is independent, whereas bending is coupled.

A comparative study on vibrational, conformational and electronic structure of 2-chloro-4-methyl-3-nitropyridine and 2-chloro-6-methylpyridine.

Experimental FTIR and FT-Raman spectroscopic analysis of 2-chloro-4-methyl-3-nitropyridine (2C4M3NP) and 2-chloro-6-methylpyridine (2C6MP) have been performed. A detailed quantum chemical calculations have been carried out using B3LYP and B3PW91 methods with 6-311++G** and cc-pVTZ basis sets. Conformation analysis was carried for 2C4M3NP and 2C6MP. The temperature dependence of thermodynamic properties has been analysed. The atomic charges, electronic exchange interaction and charge delocalisation of the molecule have been performed by natural bond orbital (NBO) analysis. Molecular electrostatic surface potential (MESP), total electron density distribution and frontier molecular orbitals (FMOs) are constructed at B3LYP/6-311++G** level to understand the electronic properties. The charge density distribution and site of chemical reactivity of the molecules have been obtained by mapping electron density isosurface with electrostatic potential surfaces (ESP). The electronic properties, HOMO and LUMO energies were measured by time-dependent TD-DFT approach.

Chronic liver and renal diseases differently affect structure of human serum albumin.

Human serum albumin (HSA) binding with endogenous metabolites and drugs is substantially decreased in chronic renal and liver diseases. To test the hypothesis that the decreased binding ability is caused by conformational changes of the protein, we analyzed infrared and Raman spectra of HSA isolated from healthy donors and patients with chronic uremia and liver cirrhosis. Uremia did not affect the secondary structure of HSA but modified the environment of its Asp/Glu residues. Liver cirrhosis increased the amount of extended and beta-structures, modified the environment of Asp/Glu and Tyr side chains, and changed the configuration of disulfide bridges in albumin molecules. The conformational changes of "cirrhotic" albumin were not caused by reversibly bound ligands and resembled a partial unfolding of the protein induced by adsorption on the charcoal surface. The dramatic structural alterations of HSA in liver cirrhosis may be caused by its oxidative modification and might underlie the decreased binding ability and changed body distribution of albumin.