Crosslinking of poly(-caprolactone) by radiation technique and its biodegradability

Poly(-caprolactone), PCL, (melting temperature, 60°C) was gamma-irradiated in the solid state at 30–55°C, the molten state, and the supercooled state (irradiation at 45–55°C after melting, 80°C) under vacuum to improve its heat resistance. Irradiation of PCL in the supercooled state led to the highest gel content and this polymer has high heat resistance. On the other hand, relatively smaller doses such as 15 and 30 kGy were effective to improve processability of PCL by formation of branch structure during irradiation.     

Ferromagnetic exchange couplings showing a chemical trend in Cu-Ln-Cu complexes (Ln = Gd, Tb, Dy, Ho, Er)

Exchange couplings in isomorphous [LnCu(2)] were evaluated by high-frequency electron paramagnetic resonance and magnetization studies. The exchange parameter J(Ln-Cu) was decreased with an increase in the atomic number; J(Ln-Cu)/k(B) = 4.45(11), 2.27(6), 0.902(10), 0.334(3), and 0.136(8) K for Ln = Gd, Tb, Dy, Ho, and Er, respectively.     

The structure of a new cardenolide diglycoside and the biological activities of eleven cardenolide diglycosides from Nerium oleander

A new cardenolide diglycoside (1) was isolated from Nerium oleander together with ten known cardenolide diglycosides 2-11. The structure of compound 1 was established on the basis of their spectroscopic data. The in vitro anti-inflammatory activity of compounds 1-11 was examined on the basis of inhibitory activity against the induction of the intercellular adhesion molecule-1 (ICAM-1). Compounds 2-5 were active at an IC(50) value of less than 0.8 μM. The cytotoxicity of compounds 1-11 was evaluated against three human cell lines normal human fibroblast cells (WI-38), malignant tumor cells induced from WI-38 (VA-13), and human liver tumor cells (HepG2). Compound 3 was active toward VA-13 cells, and compounds 2-5 were active toward HepG2 cells at IC(50) values of less than 1.3 μM. The multidrug resistance (MDR)-reversal activity of compounds 1-11 was evaluated on the basis of the amount of calcein in MDR human ovarian cancer 2780AD cells in the presence of each compound. Compounds 1 and 8 showed moderate effects on calcein accumulation.     

Directed assembly of nanoscale Co(ii)-substituted {Co(9)[P(2)W(15)](3)} and {Co(14)[P(2)W(15)](4)} polyoxometalates

Herein we report two structurally intriguing Co(ii)-substituted polyoxometalates, a {Co(9)[P(2)W(15)](3)} and {Co(14)[P(2)W(15)](4)} (compounds 1 and 2) that are formed from the same building blocks under subtly different conditions. Compound 1 displays a structure previously predicted but never before realised, whilst compound 2 is the first Co-containing Dawson-based single-molecule magnet and has a unique cruciform structure.     

New synthesis of (+/-)-isonucleosides

[Structure: see text] A novel method for synthesizing isonucleosides, a new class of anti-HIV nucleosides, is described. 2,2-Dimethyl-1,3-dioxan-5-one was converted into a dioxabicyclohexane derivative in six steps. After cleaving the epoxide group with thiophenol, the resulting product was subjected to the Mitsunobu reaction in the presence of a nucleobase to give the desired isonucleoside derivative via migration of the thiophenyl group. Removal of the thiophenyl group under radical conditions followed by deprotection led to the 4'-substituted 2',3'-dideoxyisonucleosides as a racemic mixture.     

Free energy profiles for penetration of methane and water molecules into spherical sodium dodecyl sulfate micelles obtained using the thermodynamic integration method combined with molecular dynamics calculations

The free energy profiles, ΔG(r), for penetration of methane and water molecules into sodium dodecyl sulfate (SDS) micelles have been calculated as a function of distance r from the SDS micelle to the methane and water molecules, using the thermodynamic integration method combined with molecular dynamics calculations. The calculations showed that methane is about 6-12 kJ mol(-1) more stable in the SDS micelle than in the water phase, and no ΔG(r) barrier is observed in the vicinity of the sulfate ions of the SDS micelle, implying that methane is easily drawn into the SDS micelle. Based on analysis of the contributions from hydrophobic groups, sulfate ions, sodium ions, and solvent water to ΔG(r), it is clear that methane in the SDS micelle is about 25 kJ mol(-1) more stable than it is in the water phase because of the contribution from the solvent water itself. This can be understood by the hydrophobic effect. In contrast, methane is destabilized by 5-15 kJ mol(-1) by the contribution from the hydrophobic groups of the SDS micelle because of the repulsive interactions between the methane and the crowded hydrophobic groups of the SDS. The large stabilizing effect of the solvent water is higher than the repulsion by the hydrophobic groups, driving methane to become solubilized into the SDS micelle. A good correlation was found between the distribution of cavities and the distribution of methane molecules in the micelle. The methane may move about in the SDS micelle by diffusing between cavities. In contrast, with respect to the water, ΔG(r) has a large positive value of 24-35 kJ mol(-1), so water is not stabilized in the micelle. Analysis showed that the contributions change in complex ways as a function of r and cancel each other out. Reference calculations of the mean forces on a penetrating water molecule into a dodecane droplet clearly showed the same free energy behavior. The common feature is that water is less stable in the hydrophobic core than in the water phase because of the energetic disadvantage of breaking hydrogen bonds formed in the water phase. The difference between the behaviors of the SDS micelles and the dodecane droplets is found just at the interface; this is caused by the strong surface dipole moment formed by sulfate ions and sodium ions in the SDS micelles.     

Fermionic solutions of chiral Gross–Neveu and Bogoliubov–de Gennes systems in nonlinear Schrödinger hierarchy

The chiral Gross–Neveu model or equivalently the linearized Bogoliubov–de Gennes equation has been mapped to the nonlinear Schrödinger (NLS) hierarchy in the Ablowitz–Kaup–Newell–Segur formalism by Correa, Dunne and Plyushchay. We derive the general expression for exact fermionic solutions for all gap functions in the arbitrary order of the NLS hierarchy. We also find that the energy spectrum of the n  -th NLS hierarchy generally has n+1$n+1$ gaps. As an illustration, we present the self-consistent two-complex-kink solution with four real parameters and two fermion bound states. The two kinks can be placed at any position and have phase shifts. When the two kinks are well separated, the fermion bound states are localized around each kink in most parameter region. When two kinks with phase shifts close to each other are placed at distance as short as possible, the both fermion bound states have two peaks at the two kinks, i.e., the delocalization of the bound states occurs.     

Stereochemistry of the base-catalyzed methanolysis of 2-phenyl-tetrahydropyrrolo-1,3,2-oxazaphospholes

Diastereomerically pure bicyclic oxazaphospholes were prepared from L-prolinol and phenylphosphonic or thiophosphonic dichloride and their absolute configurations were determined based on the interpretation of NMR spectra. The base-catalyzed methanolysis of those compounds was found to proceed by exclusive PO bond cleavage with complete inversion of configuration.