L-leucinium perchlorate: new molecular complex with nonlinear optical properties. Vibrational, calorimetric and theoretical studies

On the basis of prior X-ray crystallographic results published by J. Janczak and G. Perpetuo, detailed vibrational studies were performed. The FT-IR and Raman spectra at ambient temperature were measured. The NLO properties were determined with the Kurtz-Perry experiment. Theoretical vibrational spectra were calculated. A detailed potential energy distribution (PED) analysis was performed. Assignments of observed bands were made. On the basis of these results, the behaviour of hydrogen bonds in the investigated compound was analysed and discussed. The equilibrium geometry of L-leucinium perchlorate was obtained. The results were compared with experimental X-ray data. The DFT formalism was used in theoretical studies. Detailed TDDFT study of hyperpolarizbility of first and second order for the investigated molecule was performed. Results were compared with experiments. Theoretical population analysis was used to determine the local electron density and local charges in investigated molecule. Differential scanning calorimetric study (DSC) was performed.      

Application of NRTL activity coefficient model to describe the kinetics of gas adsorption

The Non-Random Two-Liquid activity coefficient model is applied to describe the kinetics of pure gas adsorption on energetically heterogeneous solid surfaces. The surface energetic heterogeneity has been represented by the Gaussian-like function of the adsorption energy distribution. Two different kinetic isotherms have been presented. One of them, determined by using the statistical rate theory, has been critically discussed. The applicability of the presented approach has been demonstrated by a quantitative analysis of two sets of experimental data previously reported in the literature.      

Preparation of selectively protected protoescigenin derivatives for synthesis of escin analogs and neoglycoconjugates

Protoescigenin, the main aglycone of horse chestnut saponin mixture known as escin, was selected as substrate for exploratory chemistry towards selective protection, followed by propargyl ether formation and subsequent condensation with azido-monosaccharides, to obtain novel triazole linked conjugates of the triterpene.      

Reaction of barbituric acid with organic azides and phosphonium ylides

Amination by organic azides has been carried out to provide aminobarbiturates by fusion of a triazole ring to the 5,6-positions of barbituric acid followed by cleavage and thermal elimination of nitrogen, whereas aza-Wittig reaction gave phosphoranylidene barbituric acid salts.      

Metals content of soil,leaves and wild fruit from Serbia

The concentrations of Zn, Mn, Fe, Pb, Ni, Cu and Cd in soil, leaves and edible wild fruit (Crataegus laevigata L., Cornus mas L. and Prunus spinosa L.) from southeast Serbia were determined by atomic absorption spectroscopy. Metal translocations from soil to fruit were calculated as well as their oral intake and health risk indices. Positive correlations were found among metal concentrations in soil, leaves and fruit.      

The first synthesis of 3-deoxyoripavine and its utilization in the preparation of 10-deoxyaporphines and cyprodime

The synthesis of 3-deoxyoripavine (7) was realized as a novel and promising intermediate towards the synthesis of the important class of dopaminergic and/or serotonergic 10-deoxyaporphines and the special pharmacological tool µ opioid antagonist cyprodime. Generally, the preparation of these valuable biologically active compounds was achieved in remarkable yields.      

Excess interfacial energy change of solid/aqueous salt solution system with increasing salt concentration at a constant charge-determining ion activity based on the Gibbs equation and ionic components of charge

A thermodynamic equation relating the change of interfacial excess (Gibbs) energy in the solid/aqueous salt solution system, caused by a variation of concentration of inorganic salt at a constant charge-determining ion activity, temperature and pressure, is derived. The equation is based on the Gibbs equation and ionic components of charge parameters. On the basis of literature experimental data for the AgI/aqueous KNO₃ and TiO₂/aqueous NaCl systems it was shown that the interfacial excess energy decreases with increasing salt concentration due to variation of the ionic components of charge of the interface.      

Synthesis and biological screening of octasubstituted-triphenodioxazines and its sulphur analogues with some novel intermediates

Attempts have been made to prepare for the first time the octasubstituted-triphenodioxazines and triphenodithiazines heterocycles by cyclisation of 3,6-dichloro-2,5-bis(2′,4′,5′-trichloroanilino)-1,4-benzoquinone and condensation. This wasfollowed by cyclisation of substituted 2-aminobenzenethiol respectively with chloranil and bromanil in ethanolic solution of fused sodium acetate in the presence of benzoyl chloride in nitrobenzene. Their structures were confirmed on the basis of their chemical and spectral analyses. Moreover, the biological activity of these compounds was evaluated against the test organisms viz — E.coli, S. aureus, B. subtilis, M.luteus and C. albicans. These compounds synthesized from 2,4,5-trichloroaniline appeared to possess significant antimicrobial activities and an explicit correlation between structure and biological activity was also observed.      

Spectral properties of coumarin derivatives in various environments

The structural and spectral properties of coumarin derivatives in complex environments were investigated within the time-dependent density functional theory (TD DFT). Absorption spectra calculations were obtained at TD PBE0/6-31+G(d,p) level of theory for coumarin47 in the gas-phase and in various polar and non-polar organic solvents. The geometries of coumarins 6, 30, 47 and 522 in the gas phase and in inclusion complexes with the β-cyclodextrin (βCD) were determined by PM3 and DFT (HCTH/6-31G) calculations. Encapsulation of coumarin in βCD and associated changes in electronic structure produced either a red or blue shift in the absorption spectra of coumarins. A proposed cavity model for βCD-coumarin complex in water solution allowed identification of various contributions to the overall shift in the absorption spectra of coumarin upon complex formation in a solvent environment      

Polymer conjugates with potential biological activity based on new derivatives of 2-mercaptobenzoxazole-synthesis and characterization

New potentially biologically active compounds derived from 2-mercapto-benzoxazole were synthesized and coupled on polymeric support of poly (maleic anhydride-alt-vinyl acetate) for the preparation of polymer-drug conjugates with controlled drug release. All compounds were characterized by elemental and spectroscopy (FT-IR, ¹H-NMR) analysis. The toxicological tests recommend the products for further laboratory screening.      

Fullerenes patched by flowers

Stability measures, such as the total energy and the HOMO-LUMO gap, calculated at the Hartree-Fock and DFT levels of theory, and the aromatic character of five circulenes/flowers with a hexagonal core and petals consisting of 5-, 6- and 7-membered rings are investigated. Geometric (HOMA) and magnetic (NICS) criteria are used to estimate the local aromatic character of every ring of the investigated circulenes. The local aromaticity of the coronene and sumanene patches in two tetrahedrally spanned fullerenes were calculated and compared with the HOMA and NICS values of the corresponding isolated circulenes.      

Molecular structures of metalmacrocyclic chelates of 3d-elements formed at template synthesis in the ion M(II)- thiooxamide-guanidine-formaldehyde quaternary systems

Using density functional theory (DFT) at the OPBE/TZP level, the calculation of the geometric parameters of the molecular structures of M(II) (5456)macrotetracyclic complexes with a tetradentate macrocyclic ligand with (NNNN)-coordination of donor centers, resulting from template reactions in M(II)- thiooxamide- guanidine-formaldehyde quaternary systems, where M= Mn, Fe, Co, Ni, Cu, Zn was performed. The calculation of the molecular structure of this “template” ligand itself was also carried out. The values of the bond lengths, bond and torsion angles in the resulting complexes are presented. The values of the standard enthalpy, entropy and Gibbs free energy of formation of these compounds were also calculated.      

Regio- and stereoselectivity of polar [2+3] cycloaddition reactions between (Z)-C-(3,4,5-trimethoxyphenyl)-N-methylnitrone and selected (E)-2-substituted nitroethenes

[2+3] Cycloaddition reactions of the highly reactive (Z)-C-(3,4,5-trimethoxyphenyl)-N-methylnitrone with (E)-2-R-nitroethenes proceed under mild conditions and yield mixtures of stereoisomeric 2-methyl-3-(3,4,5-trimethoxyphenyl)-4-nitro-5-R-isoxazolidines. The effect of regiospecificity of the cycloadditions may be accounted for by the theory of electrophilicity indexes. Stereoselectivity, however, is determined by a compilation of steric and secondary orbital effects.      

Enantioselective Michael additions of aldehydes to nitroalkenes catalyzed with ionically tagged organocatalyst

Enantioselective organocatalytic Michael additions affords useful building blocks for many biologically and medicinally relevant compounds. Ionically-tagged diphenylprolinol silyl ether efficiently catalyzes several Michael additions of aldehydes to nitroalkenes in ionic liquids. The Michael additions work well in ionic liquids; yields up to 95% and enantioselectivities up to 95% ee were achieved. Furthermore, in some cases, the catalytic system was reusable.      

Salutaridine and its derivatives as thebaine-equivalents in the synthesis of aporphines

Here we report the transformation of tetracyclic morphinan salutaridine (1) into 2,3,10,11-tetrasubstituted (R)-aporphines. This method serves as another chemical proof of the previously verified biosynthetic connection with pentacyclic morphinan-6,8-diene-type thebaine. In the presence of nucleophiles, this procedure could lead to pharmacologically interesting new tetrasubstituted aporphinoids. The enantioselective synthesis of 7S-salutaridinol (2) has been also achieved in order to investigate the acid-catalyzed reactions of this natural morphinan.      

Hydroconversion of parafine LTP56-H over nickel/Na-mordenite catalysts

Nickel catalysts supported on Na-mordenite were used for paraffin LTP56-H hydroconversion into liquid material as a possible component for engine fuels. The effects of none-catalytic thermal treatment and catalytic conditions-zeolite type and reaction conditions (solvent) on the process of liquefaction of LTP56-H paraffin and physicochemical properties of catalysts were studied. The physicochemical properties of catalytic systems were investigated using XRD, TPR, TPD-NH3 and SEM-EDS methods.      

Oxygen decorating at the one ring and at the N-mouth of (10, 0) aluminum nitride nanotube: A DFT investigation

We have investigated oxygen decorating in the (10, 0) aluminum nitride nanotube (AlNNT) by density functional theory. Band gaps, total (TDOS) and partial (PDOS) densities of state and chemical-shielding isotropic (CSI) and chemical-shielding anisotropic (CSA) have been calculated or determined in three models of the investigated (10, 0) AlNNT: pristine (model.0), O-decorating at the one ring in the middle of AlNNT (Model.1) and O-decorating at the nitrogen mouth of AlNNT (Model.2). The results indicated that the dipole moment does not detect the significant effects of dopant whereas TDOS, PDOS and band gap energies detect notable effects. The CSI and CSA values for the Al and N atoms-contributed to the Al-O bonds or those atoms close to the decorated region, in both models of O-decorated AlNNTs are changed.      

QSAR of caffeines by similarity cluster prediction

A novel QSAR approach based on correlation weighting and alignment over a hypermolecule that mimics the investigated correlational space was performed on a set of 40 caffeines downloaded from the PubChem database. The best models describing log P and LD50 values of this set of caffeine derivatives were validated against the external test set and in a new predictive model by using clusters of similarity.