Reassessment of methyl rotation barriers and conformations by correlated quantum chemistry methods

Internal rotations of the methyl group in ortho‐substituted and 2,6‐disubstituted toluenes in their ground state have been investigated by means of various ab initio quantum chemistry methods. Computed barriers at the Hartree‐Fock (HF) level using medium sized basis sets agreed reasonably with experimental results in the case of the studied ortho‐substituted toluenes. However, this agreement worsens when using very large basis sets. Furthermore, the determination of the conformation and barriers of more weakly hindered methyl groups, that is, for 2,6‐dihalogenotoluenes or toluene itself, necessitates high level correlated computations, because of a possible failure of HF calculations in this case. Density functional theory (DFT) techniques required, in several cases, much more extended basis sets than the post‐HF Møller‐Plesset perturbation (MP2, MP4) ones, to insure the convergence of the computed barriers. Non‐negligible variations of the computed barriers when using different DFT functionals are observed for some systems. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 2093–2100, 2003     

Mixed-Ligand Complexes of 2-(Aminomethyl)benzimidazole Palladium(II) with Various Biologically Relevant Ligands

cis-Dichloro(2-(aminomethyl)benzimidazole)palladium(II), [Pd(AMBI)Cl₂], was synthesized and characterized. The stoichiometry and stability constants of the complexes formed between [Pd(AMBI)(H₂O)₂]²⁺ with various biologically relevant ligands containing different functional groups are investigated. The ligands used are dicarboxylic acids, amino acids, peptides and DNA constitutents. The results show the formation of 1:1 complexes with amino acids and dicarboxylic acids. The effect of the chelate ring size of the dicarboxylic acid complexes on their stability constants is examined. Peptides form both 1:1 complexes and the corresponding deprotonated amide species. Structural effects of the peptide on the amide deprotonation are investigated. DNA pyrimidinic constituents such as uracil, uridine, thymidine and thymine form 1:1 and 1:2 complexes, whereas purinic constituents such as inosine 5′-monophosphate (5′-IMP) and guanosine 5′-monophosphate (5′-GMP) form only 1:1 complexes. The concentration distribution of the complexes in solution was evaluated. The effect of increasing chloride ion concentration on the formation constant of CBDCA with Pd(AMBI)²⁺ was reported.     

Crystallization kinetics of PHB/PVAc blends using time resolved dielectric spectroscopy

Crystallization kinetics of poly(hydroxy butyrate), PHB, and its blends with poly(vinyl acetate), PVAc, have been thoroughly investigated using broadband dielectric technique over a wide range of frequencies (10⁻²-10⁵ Hz) as functions of crystallization temperature and blend composition. The dielectric strength of the amorphous segments, Δε, which is directly proportional to the volume fraction of the mobile amorphous phase in the blend decreases exponentially with increasing the crystallization time. However, on the other hand, the dielectric strength of the rigid amorphous segments, Δε_α′, which is related to the percentage of crystallinity in the blend increases dramatically with increasing crystallization time. A great variation in the dynamical constraints of relaxation segments with increasing crystallization time has been observed as a result of different environments, which would lead to a variation in the consistency of the cooperative regions. The value of the dielectric constant, ε′, decreases dramatically with increasing crystallization time, after that it reaches an equilibrium value at the end of the crystallization process. This dramatic decrease in the value of ε′ as a result of crystallization at a given crystallization temperature, was taken as an accurate evaluation for the amount of the amorphous phase that has undergone crystallization considering the theoretical approach of Avrami. The Avrami exponent, n, was found to be crystallization temperature, T_c, independent (n ∼ 3) indicating a three-dimensional crystal growth for pure PHB. The crystallization rate constant, k, increases greatly with increasing T_c due to the high crystallization rate. In the blend the value of n was found to be concentration dependent (n ∼ 1.8-3.2). The different values of n indicate that the shapes of the growing crystals are affected by blend concentration. For n ∼ 1.8, the crystals can either grow sporadically as rods or instantaneously as disks, while for n ∼ 3 a three-dimensional crystal growth takes place.     

Reactions of hydrazonoyl halides 43 : Synthesis of some new 2,3‐dihydro‐1,3,4‐thiadiazoles,pyrazoles, pyrazolo[3,4‐d]‐pyridazines,thieno[2,3‐b]pyridines,pyrimidino[4′,5′:4,5]thieno[2,3‐b]‐pyridines and pyrrolo[3,4‐d]pyrazoles

2,3‐Dihydro‐1,3,4‐thiadiazoles, pyrazoles, pyrazolo[3,4‐d]pyridazines, thieno[2,3‐b]pyridines, pyrim‐idino[4′,5′:4,5]thieno[2,3‐b]pyridines and pyrrolo[3,4‐d]pyrazoles were obtained in a good yields by treatment of hydrazonoyl halides with each of alkyl carbodithioates, 3‐(dimethylamino)‐1‐naphtho[1,2‐d]furan‐2‐ylprop‐2‐en‐1‐one and N‐arylmalemides.     

New periodic solutions for nonlinear evolution equations using Exp-function method

The Exp-function method is used to obtain generalized solitonary solutions and periodic solutions for nonlinear evolution equations arising in mathematical physics using symbolic computation. The method is straightforward and concise, and its applications are promising.     

Numerical solutions of nonlinear evolution equations using variational iteration method

The variational iteration method is used to solve three kinds of nonlinear partial differential equations, coupled nonlinear reaction diffusion equations, Hirota–Satsuma coupled KdV system and Drinefel’d–Sokolov–Wilson equations. Numerical solutions obtained by the variational iteration method are compared with the exact solutions, revealing that the obtained solutions are of high accuracy. He's variational iteration method is introduced to overcome the difficulty arising in calculating Adomian polynomial in Adomian method. The method is straightforward and concise, and it can also be applied to other nonlinear evolution equations in mathematical physics.     

Convenient and Efficient Method for Synthesis of Bis‐Hetaryl Ketones and Evaluation of Their Antimicrobial Activity

Sodium 1‐aryl‐3‐(3‐(ethoxycarbonyl)‐5‐methyl‐1H‐pyrazol‐4‐yl)‐3‐oxoprop‐1‐en‐1‐olate was used as precursor for the preparation of some novel derivatives of various fused azolotriazine ring systems via coupling reactions with hetaryldiazonium salts. Hydrazinolysis of the latter products yielded the corresponding pyrazolopyridazine derivatives. The structures of the products were established by their spectral data and elemental analyses. The antibacterial and antifungal activities of some of the new products were also evaluated.     

On asymptotic method in contact problems of Fredholm integral equation of the second kind

Besides asymptotic methods, the method of orthogonal polynomials has been used to obtain the solution of the Fredholm integral equation. The principal (singular) part of the kernel which corresponds to the selected domain of parameter variation is isolated. The unknown and known functions are expanded in a Chebyshev polynomial and an infinite algebraic system is obtained.     

A molecular orbital treatment of the electronic spectra of some tryptamines

The electronic absorption spectra of tryptamine, 5-methoxytryptamine, 6-fluorotryptamine, N-acetyl-5-hydroxytryptamine, gramine, and melatonin were investigated. The observed transitions were π–π*, and the values of band maxima and intensity reflected an extent of interaction between the indole ring and the alkylamine side chain. Molecular orbital calculations at the level of INDO /S –CI were performed on all the studied molecules. State functions and transition energies were calculated. The correspondence between the experimental and theoretical results was satisfactory. © 1992 John Wiley & Sons, Inc.