Studies in sesquiterpenes—LVI: Isolongifolene (part 7): mechanism of rearrangement of longifolene to isolongifolene—II

The question of possible neutral intermediates which may lie on the reaction pathway in going from longifolene to isolongifolene has been investigated using BF₃·Et₂O-AcOD and D₃PO₄-dioxane, as reagents. It has been found that longicyclene is not an obligatory intermediate. The mode of cleavage of cyclopropane ring in longicyclene has been investigated.     

Inner shell structure of heavy atoms

The inner-shell structure of some heavy atoms is examined using a self-consistent relativistic local density method. Ar(K), Kr(K) and Xe (K,L ₁,L ₂ andL ₃) binding energies and {ie863-1} (hyper-satellite) energies of Tl, Hg and Tm are calculated. The results are compared with available experimental data. A part of this work was presented byMPD at the Trieste International Symposium on “Core level excitations in atoms, molecules and solids,” 22–26 June 1981, Extended Abstracts (ed.) E Tosatti, ICTP Report No. 89/81 p. 11.     

Polymerization of acrylonitrile. Kinetics of the reaction initiated by the Ce(IV)/thioacetamide redox system

Vinyl polymerization of acrylonitrile initiated by the Ce(IV)/thioacetamide redox system has been investigated in aqueous sulfuric acid in the temperature range of 10–20°C. The rate of polymerization (R_p) and the rate of Ce(IV) disappearance (?R_Ce) were measured. The effect of certain water-soluble organic solvents, added electrolytes, and aromatic and heterocyclic organic nitrogen compounds on the rate of polymerization has been investigated. Depending on the experimental results, we have suggested a suitable reaction scheme for the system which involves the production of initiating radicals from the oxidation of thioacetamide (TAm) by ceric ion and the termination of the polymer chain by metal ions.     

A classical description of deep inelastic collisions with surface friction and deformation

The friction model for heavy ion induced fusion and deep inelastic nuclear reaction is extended to include deformation. Spheroidal deformation and relative motion of the mass centres of the two interacting nuclei are treated as dynamical variables. The radial frictional force has been assumed to be proportional to the rate of change of the separation between the two surfaces instead of the two centres of mass. The friction coefficients remain unaltered. The potential as a function of deformation and separation distance are generated by a single folding procedure. The model is applied to⁴⁰Ar+²³²Th at 379 MeV (Lab) and¹³⁶Xe+²⁰⁹Bi at 1,130 MeV (Lab). In case of the former, the energy loss, which has not been properly accounted for before, is now satisfactorily explained and in the case of the latter the model predicts the absence of fusion in agreement with experiment.     

A characterization based on the equidistribution of the first two spacings of record values

Summary For a sequence {X _n:n=0, 1, 2,...} of i.i.d. discrete random variables let X ₀ denote the zeroeth record value and X _L(1), the first record value. It is shown that X ₀ and X _L(1) –X ₀ are identically distributed if and only if X ₀ has the geometric distribution over the lattice k :k=1, 2,... for some >0.     

Aqueous polymerization of acrylonitrile initiated by the bromate–thiourea redox system

The aqueous polymerization of acrylonitrile initiated by an acidified bromate–thiourea redox system has been studied under nitrogen atmosphere. The rate of polymerization is independent of thiourea concentration over the range 2–9 × 10^?3M and reaches maximum at 9 × 10^?3M. The rate varies linearly with [monomer]. The initial rate of polymerization as well as the maximum conversion increases within the range of 4–22.5 × 10^?3M KBrO₃, but beyond 22.5 × 10^?3M the rate of polymerization decreases. The initial rate and the limiting conversion increases with increasing polymerization temperature in the range 30–45°C; and beyond 45°C they decrease. The effect of certain neutral salts, water-soluble solvents, and micelles of cationic, anionic, and nonionic surfactants on the rate of polymerization has been investigated.     

Hexavalent Chromium-Thioacetamide Redox System Initiated Polymerization of Acrylonitrile

Polymerization of acrylonitrile initiated by the Cr⁶⁺/thioacetamide redox system was studied in nitrogen atmosphere in the temperature range 35–45°C. The rate of polymerization and the rate of Cr⁶⁺ ion disappearance were measured. The effect of certain water-miscible organic solvents, neutral electrolytes, and complexing agents on the rate of polymerization was investigated. Chromic acid alone did not initiate the polymerization under deaerated and undeaerated conditions. Depending on the results obtained, a suitable kinetic scheme was proposed and various rate parameters were evaluated.     

Thermal properties and cold crystallization kinetics of surface-treated banana fiber (BF)-reinforced poly(lactic acid) (PLA) nanocomposites

Nucleation capacity of organically modified natural montmorillonite within the surface-treated banana fiber (BF)-reinforced PLA biocomposites has been studied using DSC analysis in the present investigation. Both the surface treatments and nanoclays play vital roles in the variation in nucleation process of PLA during cold crystallization process. Biocomposite made up of silane-treated BF and its bionanocomposite prepared using cloisite 30B (C30B) were showed superior nucleation parameters, n and K values, in the Avrami plots. Enhanced equilibrium melting point and lower E _a suggests the reinforcing effect imparted by the BF surface treatments and C30B within the PLA matrix. Even though, Louritzen–Hoffmann theory was revealed that no change in crystallization regimes of PLA even after the biocomposite and bionanocomposite preparation. TG analysis revealed better heat barrier capacity for all the biocomposites and bionanocomposites in comparison with virgin PLA (V-PLA). Increased storage modulus values for biocomposites and bionanocomposites also confirm the reinforcing effects of the fillers. Heat deflection temperature and the flammability studies concluded better application window for newly developed materials than that V-PLA.