We have fabricated a molecular recognition ion gating membrane. This synthetic membrane spontaneously opens and closes its pores in response to specific solvated ions. In addition to this switching function, we found that this membrane could control its pore size in response to a known concentration of a specific ion. The membrane was prepared by plasma graft copolymerization, which filled the pores of porous polyethylene film with a copolymer of NIPAM (N-isopropylacrylamide) and BCAm (benzo[18]crown-6-acrylamide). NIPAM is well-known to have an LCST (lower critical solution temperature), at which its volume changes dramatically in water. The crown receptor of the BCAm traps a specific ion, and causes a shift in the LCST. Therefore, selectively responding to either K(+) or Ba(2+), the grafted copolymer swelled and shrank in the pores at a constant temperature between two LCSTs. The solution flux in the absence of Ba(2+) decreased by about 2 orders of magnitude over a solution flux containing Ba(2+). The pore size was estimated by the filtration of aqueous dextran solutions with various solute sizes. This revealed that the membrane changed its pore size between 5 and 27 nm in response to the Ba(2+) concentration changes. No such change was observed for Ca(2+) solutions. Furthermore, this pore size change occurred uniformly in all pores, as a clear cut-off value for a solute size that could pass through pores was always present. This membrane may be useful not only as a molecular recognition ion gate, but also as a device for spontaneously controlling the permeation flux and solute size.

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Unique molecular‐recognition microcapsules for environmental stimuli‐responsive controlled release have been developed. The microcapsules consist of a core–shell porous membrane. The pores contain linear‐grafted poly(NIPAM‐co‐BCAm) chains, which act as the molecular‐recognition gates. The Figure shows the mechanism of the opening of the pores to release the molecules inside.

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We have investigated electronic band structure of a transparent conducting oxide, Nb-doped anatase TiO2 (TNO), by means of first-principles band calculations and photoemission measurements. The band calculations revealed that Nb 4d orbitals are strongly hybridized with Ti 3d ones to form a d-nature conduction band, without impurity states in the in-gap region, resulting in high carrier density exceeding 1021 cm-3 and excellent optical transparency in the visible region. Furthermore, we confirmed that the results of valence band and core-level photoemission measurements are consistent with prediction by the present band calculations.

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Nb-doped anatase TiO2 [Ti0.94Nb0.06O2 (TNO)] films with high electrical conductivity and transparency were fabricated on nonalkali glass using pulsed laser deposition and subsequent annealing in a H2 atmosphere. The amorphous films as deposited on unheated substrates were found to crystallize, forming polycrystalline films at around 350°C. The films annealed at 500°C showed resistivity down to 4.6×10−4Ωcm at room temperature and optical transmittance of 60%–80% in the visible region, which are comparable to those of epitaxial films. These results indicate that TNO films have the potential to be practical transparent conducting oxides that could replace indium tin oxide.