The synthesis of bicyclo[6.2.0]decapentaene

The parent bicyclo[6.2.0]decapentaene is synthesized for the first time by thermal ring opening of its valence isomer. Thermal dimerization of the compound is also described.     

Lasing conditions in recombining helium plasmas

Lasing conditions for He have been evaluated numerically. We have used a collisional radiative model to calculate overpopulation densities Δn_ij, which are defined as differences between population densities per unit statistical weight of the upper and lower excited levels i and j, respectively. Laser oscillations for the level pairs 2¹P-3¹S, 2¹P-4¹S, 2¹P-3¹D, 2¹P-4¹D, 3¹D-4¹F, 3¹P-4¹S, 3¹P-4¹D, and 3³P-4³S are possible when the electron densities are within well defined limits at low electron temperature (T_e = 0.1 eV). For level pairs of the singlet state, the inversion mechanism for He is the same as for H. Only collisional processes produce population inversion in the triplet level pair 3³P-4³S.     

Doping dependence of the vortex glass and sublimation transitions in the high-T<Subscript>c</Subscript> superconductor La<Subscript>2-x</Subscript>Sr<Subscript>x</Subscript>CuO<Subscript>4</Subscript> as determined from macroscopic measurements

Magnetization and ac-susceptibility measurements are used to characterize the mixed phase of the high-temperature cuprate superconductor La_2-xSr_xCuO₄ over a large range of doping (0.075 0.20). The first order vortex lattice phase transition line H_FOT(T), the upper critical field H_c2(T) and the second peak H_sp(T) have been investigated up to high magnetic fields (8 Tesla applied perpendicular to the CuO₂ planes). Our results reveal a strong doping dependence of the magnetic phase diagram, which can mainly be explained by the increasing anisotropy with underdoping. Within our interpretation, the first order vortex lattice phase transition is due to the sublimation (rather than melting) of the vortex lattice into a gas of pancake vortices, whereas the second peak is related to the transition to a more disordered vortex glass state.     

Lipid-bound apolipoproteins in tyrosyl radical-oxidized HDL stabilize ABCA1 like lipid-free apolipoprotein A-I

Background  

ATP-binding cassette transporter A1 (ABCA1) mediates the lipidation of exchangeable apolipoproteins, the rate-limiting step in the formation of high density lipoproteins (HDL). We previously demonstrated that HDL oxidized ex vivo by peroxidase-generated tyrosyl radical (tyrosylated HDL, tyrHDL) increases the availability of cellular cholesterol for efflux and reduces the development of atherosclerosis when administered to apolipoprotein E-deficient mice as compared to treatment with control HDL.     

Vinyl Polymerization. 269. Polymerization of Methyl Methacrylate Initiated by p,p'-Dimethoxydiphenyldiazomethane

Using p,p'-dimethoxydiphenyldiazomethane (DMDM) as initiator, the polymerization of methyl methacrylate (MMA) in benzene or in bulk was carried out. The initial rate of polymerization, R_p, was found to be expressed by the following equation:

R_p = k[DMDM]^0.53 [MMA]^0.84

The polymerization was confirmed to proceed by a radical mechanism. The over-all activation energy for the polymerization in benzene was calculated as 19.3 kcal/mole. The rate of thermal decomposition of DMDM was also measured in benzene and the rate equation was obtained as follows:

k_d (sec^?1) = 1.0 × 10¹⁵ exp (^?29.1 kcal/RT) (for 50-80°C)

Explanations of these observations are discussed in connection with those of the preceding papers.     

Liquid crystalline polyurethane. Polyurethanes containing bis-(p-oxymethylphenyl) terephthalate

Several polyurethanes based on bis-(p-oxymethylphenyl) terephthalate (BOPT) were synthesized and studied with respect to some of their thermal properties. BOPT exhibits a mesomorphic phase at 252–264°C. Polymerization was carried out by equimolar reaction with hexamethyl-ene diisocyanate (HDI), 4,4-dicyclohexylmethane diisocyanate (H₁₂MDI) α,α'-diisocyanate-1,3-dimethylcyclohexane (H6 XDI), 4,4′-diphenylmeth-ane diisocyanate (MDI), 2,4-tolylene diisocyanate (TDI), and phenylene diisocyanate (PDI). It became clear that polyurethanes obtained from BOPT with HDI, H₁₂MDI, H₆XDI, and TDI have mesomorphic phases at 243–291, 214–250, 172–229, and 180–234°C, respectively, as determined by DSC and polarized microscopy, and that all polyurethanes are crystalline as evidenced by x-ray diffraction.     

Synthesis of Substituted Phenyl Esters of Amino Acids and Polycondensation in Langmuirblodgett Films

Long-alkyl-chain phenyl esters of β-alanine, glycine, and L-valine were prepared, and their monolayer properties were correlated with their molecular structures. These compounds formed stable monolayers on acidic subphases. In particular, the p-hexadecylphenyl esters of β-alanine and glycine were remarkably stable, and their monolayers could be deposited on calcium fluoride plates as Y-type film by Blodgett's technique. The polycondensation of multilayers under an atmosphere saturated with triethylamine was investigated by changes in the IR spectra. It was determined that the polycondensation proceeded by a first-order reaction mechanism in the initial stage and that the rate in multilayers was faster than that in the bulk crystalline powder. These results suggest that the polycondensation is accelerated by a regular arrangement of the monomer in the multilayers, where the active sites are concentrated and located better for the polycondensation. In the case of the polycondensation in multilayers of the glycine ester, two kinds of condensation proceeded to afford poly(glycine) and 2,5-piperazinedione.