Photopolymerization of methyl methacrylate with the use of bromine as photoinitiator

Low concentrations of bromine (0.008–0.06M) were used to initiate photopolymerization of MMA in bulk and in diluted (near bulk) systems, the diluents or solvents used being benzene, toluene, dioxane, tetrahydrofuran, carbon tetrachloride, chloroform, methylene chloride, and methanol. Polymerization in bulk follows usual free-radical kinetics. Inert solvents (benzene, toluene) as well as the other solvents used enhance the rate of polymerization MMA even when used in the range of catalytic concentrations (0.04–0.4M). An initiation mechanism involving solvent molecules appears to be predominant in diluted systems.     

Crotocaudin; a rearranged labdane type norditerpene from Croton caudatus geisel

The structure and stereochemistry of crotocaudin, a new norditerpene occurring as a minor constituent in Crotoncaudatus Geisel (Euphorbiaceae) have been established as ent-8S,10S-15,16-epoxy-19-norcleroda-4,11,13(16), 14-tetraene 18,6S: 20,12-diolactone 7 from the detailed studies of ¹H NMR spectra using lanthanide shift reagents, decoupling experiments and chemical reactions. The congener, teucvidin, ent-10S-15,16-epoxy-19-norcleroda-4,13(16), 14-triene-18,6S: 20,12R-diolactone 1 was obtained as a major component besides several triterpenoids viz taraxerone 2, taraxerol 3 and taraxeryl acetate 4. ¹³C NMR and ¹H NMR spectra and a few novel reactions of teucvidin and its conversion to teucvin, ent-(6R,12R)-15,16-epoxy-19-nor-9,4-friedolabda-4,13(16),14-triene-18,6:20, 12-diolactone 6 are also reported.     

The coupled-cluster method with a multiconfiguration reference state

The coupled-cluster approach to obtaining the bond-state wave functions of many-electron systems is extended, with a set of physically reasonable approximations, to admit a multiconfiguration reference state. This extension permits electronic structure calculations to be performed on correlated closed- or open-shell systems with potentially uniform precision for all molecular geometries. Explicit coupled cluster working equations are derived using a multiconfiguration reference state for the case in which the so-called cluster operator is approximated by its one- and two-particle components. The evaluation of the requisite matrix elements is facilitated by use of the unitary group generators which have recently received wide attention and use in the quantum chemistry community.     

Studies of vulcanization with tetramethylthiuram disulfide and sulfur vulcanization accelerated by tetramethylthiuram disulfide of styrene–butadiene rubber in presence and absence of dicumyl peroxide

The salient features of nonelemental sulfur vulcanization by tetramethylthiuram disulfide (TMTD) and elemental sulfur vulcanization promoted by TMTD both in presence and absence of ZnO and stearic acid have been studied. In stock containing TMTD, a higher rate constant value for dicumyl peroxide (DCP) decomposition was observed. TMTD decreases the crosslinking density due to DCP depending on its concentration. An entirely radical mechanism has been advanced in the absence of ZnO. ZnO or ZnO–stearic acid seems to alter the entire course of reaction. The rate of crosslinking increases in the presence of ZnO or ZnO–stearic acid. Moreover, crosslinks are formed additively (further supported from the activation energy data), and mixed crosslink formation has been confirmed by the methyl iodide test of the vulcanizates. Stearic acid has no effect on crosslink formation. An ionic chain mechanism has been postulated in the presence of ZnO, as suggested by British authors.     

An algebraic approach to q-partial fractions and Sylvester denumerants

The Ramanujan Journal - In 1857, Sylvester established an elegant theory that certain counting functions (which he termed denumerants) are quasi-polynomials by decomposing them into periodic and...