Sorption and diffusion of gases in a polyimide

Sorption and diffusion of gases (CO₂, N₂, and He) in a polyimide (PI2080) film were measured by using an apparatus which gives the sorption rate curves from the initial state to the equilibrium state. Nonlinear isotherms observed for CO₂ sorption were interpreted successfully in terms of the dual-mode model for sorption in glassy polymers. Linear isotherms observed for N₂ and He seemed to obey Henry's law. Two diffusion coefficients (D_I and D_E) were obtained using the short-time method and the long-time method for a Fickian diffusion model, together with the equilibrium solubility (C_e) from each experiment. The initial sorption rate curves agreed with the calculated curves using D_I, however near sorption equilibrium the curves are in accord with the calculated curves using D_E. These observations suggest that some relaxation process is superimposed on the diffusion process. The non-Fickian transport data were correlated successfully with a model that combines time-dependent diffusion and the Fickian model.     

Asymmetric transport due to spin injection into a Kondo alloy

Spin injection is found to have a significant effect on the transport properties of the Kondo alloy Cu(Fe). When a spin-polarized electron current flows from Co into Cu(Fe) wires through the Co/Cu(Fe) interface, the resistivity of the Cu(Fe) wire is suppressed near the interface, as distinct from the ordinary logarithmic increase in the resistivity at low temperatures. For the opposite current direction, no significant changes are observed. The asymmetry of the resistivity with respect to the current direction decays with a characteristic length of 1.5+/-0.4 microm at 2.5 K as the distance from the interface is increased. Possible mechanisms for the asymmetry are discussed.     

An alternative formulation of the theory of superconductivity

The cluster variation method of the cooperative phenomena has been applied to the study of the theory of superconductivity. The results obtained in this formulation are equivalent to the BCS results and follow in a straight forward and natural way both at zero and finite temperatures.     

Short total synthesis of (+)-madindolines A and B

[reaction: see text] A short and efficient total synthesis of (+)-madindolines A (1) and B (2), potent and selective inhibitors of interleukin 6, has been achieved. The synthesis features a key chelation-controlled 1,4-diastereoselective acylation to generate the quaternary carbon and an intramolecular acylation of allylsilane to build up the cyclopentene unit.     

Durability of oxygen evolution of photosystem II incorporated into lipid bilayers

Photosystem II (PSII) has attracted a lot of attention for use in the construction of artificial photosynthetic materials due to its high activity of oxidation of water molecules. However, the robustness of PSII needs to be improved for in vitro application. In this study, we incorporated PSII (Thermosynechococcus vulcanus) into various phospholipid membranes to examine the activity and durability of oxygen evolution. PSII was incorporated into anionic 1,2-dioleoyl-sn-glycero-3-phospho-(1′-rac-glycerol) (PSII-DOPG), zwitterionic 1,2-dioleoyl-sn-glycero-3-phosphocholine (PSII-DOPC), and cationic 1,2-dioleoyl-sn-glycero-3-ethylphosphocholine (PSII-EDOPC). Structural integrity of PSII was examined by absorption and fluorescence spectroscopy. Compared with PSII dissolved in a micellar solution of n-dodecyl-β-d-maltoside (PSII-micelle), durability of PSII-DOPC and PSII-DOPG were enhanced by 1.3- and 1.5-fold, respectively. The activity and durability of PSII-EDOPC was significantly low. Lipid-dependent activity and durability were discussed in terms of kinetic parameters of V _max and K _m, and inhibition of the electron acceptor, phenyl-p-benzoquinone.     

The first total synthesis and reassignment of the relative stereochemistry of 16-hydroxy-16,22-dihydroapparicine

We report the first total synthesis and reassignment of the relative stereochemistry of naturally occurring 16-hydroxy-16,22-dihydroapparicine. Our novel route proceeds by a cascade reaction to efficiently construct a 1-azabicyclo[4.2.2]decane core, along with two stereocenters (C-15 and C-16). The C-16 quaternary carbon was constructed through stereospecific 1,2-addition using an indole nucleophile to an aldehyde or a methylketone. The stereospecific synthesis of two diastereomers of the target product has revealed the true relative stereochemistry of the natural compound.     

Asymmetric Total Synthesis of Indole Alkaloids Containing an Indoline Spiroaminal Framework

The total synthesis of the indole alkaloids, neoxaline, oxaline and meleagrin A, all containing a unique indoline spiroaminal framework, was accomplished through the stereoselective introduction of a reverse prenyl group to the congested benzylic carbon of furoindoline, a two‐pot transformation of indoline (containing three nitrogen atoms at appropriate positions) to the featured indoline spiroaminal framework, and elimination of carbonate assisted by the adjacent imidazole moiety to construct the (E)‐dehydrohistidine. The absolute stereochemistry of neoxaline was elucidated through our total synthesis. In addition, we evaluated the bioactivity, especially the anti‐infectious properties, of neoxaline and oxaline, and of some synthetic intermediates.     

A second-generation total synthesis of (+)-phorboxazole A.

A highly convergent second-generation synthesis of (+)-phorboxazole A has been achieved. Highlights of the synthetic approach include improved Petasis-Ferrier union/rearrangement conditions on a scale to assemble multigram quantities of the C(11-15) and C(22-26) cis-tetrahydropyrans inscribed with the phorboxazole architecture, a convenient method to prepare E- and Z-vinyl bromides from TMS-protected alkynes utilizing radical isomerization of Z-vinylsilanes, and a convergent late-stage Stille union to couple a fully elaborated C(1-28) macrocyclic iodide with a C(29-46) oxazole stannane side chain to establish the complete phorboxazole skeleton. The synthesis, achieved with a longest linear sequence of 24 steps, proceeded in 4.6% overall yield.     

Light-induced hydrogen production by photosystem I–Pt nanoparticle conjugates immobilized in porous glass plate nanopores

In recent years, a number of light-induced hydrogen production systems composed of photosystem I (PSI) and hydrogen production catalysts (e.g. hydrogenases and Pt nanoparticles) have been reported. However, the utility of these systems under aerobic conditions is limited due to their poor stability in the presence of oxygen. The development of light-induced hydrogen production systems that work under aerobic conditions is, therefore, of great importance to establish artificial photosynthetic devices. Ideally, these systems should utilise water as an electron source, via water splitting by photosystem II (PSII). We report the construction of a novel light-induced hydrogen production system composed of PSI-platinum nanoparticle conjugates and cytochrome c ₆ (cyt c ₆) immobilised in nanoporous glass plates (PGP50, 50-nm pore diameter). PSI trimer (PSI_t) from Thermosynechococcus elongatus and Pt nanoparticles (PtNPs) were conjugated via electrostatic interactions (PSI_t-PtNP). PSI_t-PtNP and cyt c ₆ were spontaneously absorbed in nanopores of PGP50 without denaturation. Upon irradiation in the presence of ascorbate as a sacrificial electron donor, catalytic H₂ evolution was observed for PSI_t-PtNP immobilised in the pores of PGP50 (PSI_t-PtNP/PGP50) under both anaerobic and aerobic conditions, indicating that an effective photoinduced electron transfer system had been established. PSI_t-PtNP/PGP50 was found to exhibit improved oxygen resistivity over the homogeneous solution system consisting of PSI_t-PtNP, cyt c ₆, and ascorbate, suggesting that the PSI_t-PtNP/PGP50 system could be a potential candidate for artificial photosynthetic systems. The distribution of the components, PSI_t-PtNP and cyt c ₆, in PGP50 was characterised to discuss the efficiency of light-induced hydrogen production.