A zero differential overlap study of chemical binding in ammonia-borane and carbony l-borane

A cndo/2D study of the charge distribution obtained through Mulliken population analysis in the ground state of the title compounds shows that the features of charge distribution found by severalab initio calculations are fairly well reproduced by this method. The one-particle density, the interference density at the mid-point of the bond axis and the kinetic part of the interference energy calculated through the deorthogonalized density matrices over a wide range of intermolecular separation between the donor and the acceptor show that the one-particle density and the interference density steadily grow with decreasing internuclear separation, while the kinetic interference energy starts with negative value at large distance, then decreases and passes through a minima near but above the equilibrium distance and then increases rapidly below it conforming to the characteristic general behaviour of the kinetic component of Morse curve. The orbital pairwise interference density and the corresponding kinetic energy components reveal that the orbitals involved in the covalent binding are σ_2p AO of B and 2S and σ_2p AO of N and C atoms in H₃B-NH₃ and H₃B-CO respectively.     

Synthesis of N-substituted piperazinyl carbamoyl and acetyl derivatives of tetrahydropapaverine: potent antispasmodic agents

The synthesis and structure-activity-relationship (SAR) for a series of N-substituted piperazinyl carbamoyl 7-15 and piperazinyl acetyl 18-26 derivatives of tetrahydropapaverine have been carried out. The general synthetic methods of carbamoyl tetrahydropapaverine analogues involve N-substituted piperazines and carbamoyl imidazole tetrahydropapaverine as starting materials. Another route for synthesizing these compounds, involving the formation of carbamoyl imidazole piperazine has also been explored. Acylation of tetrahydropapaverine followed by substitution with various piperazinyl moities afforded the acetyl tetrahydropapaverine derivatives. Variously substituted piperazines have been used to monitor the effect of electron releasing and electron withdrawing substituents upon the antispasmodic activity of the molecules. Effect of varying electron densities on the antispasmodic activity, by altering the position of these groups on the benzene ring has also been monitored. Pharmacological methods involve the in vitro antispasmodic activity studies on a freshly removed guinea pig ileum using a force displacement transducer amplifier connected to a physiograph. Among the analogues synthesized in the present study, a promising compound 7, a potent muscle relaxant as compared to papaverine has been obtained.     

Photopolymerization of methyl methacrylate initiated by sulphur dioxide

In catalytic concentrations (10^?5?10^?4 mol l^?1) sulphur dioxide induces polymerization of MMA, particularly on photoactivation. The effective initiating species appears to be the monomer-SO₂ complex rather than free SO₂. A mechanism involving biradical initiation by decomposition of the initiating species, linear propagation in two directions, and significant termination of growing chains by chain transfer with initiating species has been suggested. The initiator transfer constant is 1.6 at 40°.     

Exact expressions for row correlation functions in the isotropicd=2 ising model

We present exact explicit expressions for the row spin-spin correlation functions _{00 n}0 in the isotropicd= 2 Ising model, in terms of elliptic integrals, forn 5. We also give a general structural formula for _{00 n}0.     

Steric guided change of electron transfer mechanism in benzene

In fluorescence quenching study via electron transfer (ET), the quenching rate constant (k(q)) values generally decrease with lowering of quencher concentration, since smaller concentration of quencher always leads to a red shift in the donor-acceptor (D-A) distance in ET [M. Tachiya, S. Murata, J. Phys. Chem. 96 (1992) 8441; S. Murata, M. Tachiya, J. Phys. Chem. 100 (1996) 4064; L. Burel, M. Mastafavi, S. Murata, M. Tachiya, J. Phys. Chem. A 103 (1999) 5882]. However, while doing a comparative study with different carbazole (CZ) derivatives-1,4-dicyanobenzene (DCB) systems in benzene (BZ), we observed a deviation from that normal behaviour. It was found that for all of them with lower quencher (DCB) concentration, k(q) values actually increase instead of the expected reduction. Exceptionally, for simple CZ (C12H9N) with decrease in concentration of DCB, k(q) values can even reach the order of energy transfer (10(11) s(-1)). Interestingly, it is not observed when toluene (TL) or xylene (XY) is used as solvent. To explain this unique observation, a sandwich type of molecular structure is predicted, where BZ sliding in between CZ and DCB brings them closer enough, imparting more through bond character to CZ-DCB interaction and hence a higher rate of ET (k(q)) is observed [L. Burel, M. Mastafavi, S. Murata, M. Tachiya, J. Phys. Chem. A. 103 (1999) 5882].     

Effect of adsorption of vapours on the electrical conductivity of some polyene semiconductors: adsorption and desorption kinetics

The change in semiconductive properties of β-apo-8′-carotenal, astacene and methyl bixin on adsorption of various vapours on the crystallite surfaces has been studied at a constant sample temperature. The adsorption of vapours enhances the semiconductivity of the polyenes appreciably. This enhancement depends on the chemical nature and also on the pressure of the adsorbed vapour. The adsorption and desorption kinetics follow the modified Roginsky-Zeldovich relation. A two stage desorption process, the first stage of which gives a Lennard-Jones potential energy curve and is followed by a rate-determining transition over a potential energy barrier to the second stage of adsorption forming weakly bound complexes between the vapour molecules and the polyene crystallites, can explain satisfactorily the experimentally observed kinetic data.     

Convenient route to enantiopure aryl cyclopentanes via Diels-Alder reaction of asymmetric dienes. Total synthesis of (+)-herbertene and (+)-cuparene

A general route for the synthesis of highly substituted aryl cyclopentanes has been developed involving Diels-Alder reaction of asymmetric dienes prepared from (+)-camphoric acid followed by aromatization of the resulting cyclohexene derivatives. Employing this protocol enantiospecific synthesis of (+)-herbertene and (+)-cuparene has been accomplished.     

Synthesis,Conformation, and Metabolism of a Selenium Bilirubin

Summary. A symmetrical C(10)-selena-bilirubin analog, 8,12-bis(2-carboxyethyl)-7,13-dimethyl-2,3,17,18-tetraethyl-10-selenabiladiene-ac-1,19(21H,24H)-dione was synthesized from 8-(2-carboxyethyl)-2,3-diethyl-7-methyl-(10H)-dipyrrin-1-one in one step by reaction with diselenyl dichloride. The selena-rubin exhibited UV-vis and NMR spectroscopic properties similar to those of the parent mesobilirubin, and like bilirubin and mesobilirubin, it adopts an intramolecularly hydrogen-bonded conformation, shaped like a ridge-tile but with a steeper pitch. The longer C–Se bond lengths (2.2Å) and smaller bond angles at C–Se–C (88°), as compared to C–CH₂–C (1.5Å, 106°), lead to an interplanar angle between the two dipyrrinones of only 72°, which is considerably less than that of bilirubin (100°) and close to that (74°) of its 10-thia-rubin analog. Despite the conformational distortion, the sensitivity of Se toward oxidation and the typically weak C–Se bond, the selena-rubin is metabolized in normal rats, like bilirubin, to acyl glucuronides, which are secreted into bile. In mutant (Gunn) rats lacking bilirubin glucuronosyl transferase (UGT1A1), glucuronide or other metabolites of the selena-rubin were not detected in bile, demonstrating the importance of hepatic glucuronidation for its biliary excretion.