Ordered arrays of copper nanostructures were fabricated and modified with porphyrin molecules in order to evaluate fluorescence enhancement due to the localized surface plasmon resonance. The nanostructures were prepared by thermally depositing copper on the upper hemispheres of two-dimensional silica colloidal crystals. The wavelength at which the surface plasmon resonance of the nanostructures was generated was tuned to a longer wavelength than the interband transition region of copper (>590 nm) by controlling the diameter of the underlying silica particles. Immobilization of porphyrin monolayers onto the nanostructures was achieved via self-assembly of 16-mercaptohexadecanoic acid, which also suppressed the oxidation of the copper surface. The maximum fluorescence enhancement of porphyrin by a factor of 89.2 was achieved as compared with that on a planar Cu plate (CuP) due to the generation of the surface plasmon resonance. Furthermore, it was found that while the fluorescence from the porphyrin was quenched within the interband transition region, it was efficiently enhanced at longer wavelengths. It was demonstrated that the enhancement induced by the proximity of the fluorophore to the nanostructures was enough to overcome the highly efficient quenching effects of the metal. From these results, it is speculated that the surface plasmon resonance of copper has tremendous potential for practical use as high functional plasmonic sensor and devices.

We demonstrate that Pd nanospheres exhibit much higher susceptibility of the localized surface plasmon resonance (LSPR) peak to medium refractive index changes than commonly used plasmonic sensing materials such as Au and Ag. The susceptibility of spherical Au nanoparticle-core/Pd-shell nanospheres (Au/PdNSs, ca. 73 nm in diameter) was found to be 4.9 and 2.5 times higher, respectively, than those of Au (AuNSs) and Ag nanospheres (AgNSs) having similar diameters. The experimental finding was theoretically substantiated using the Mie exact solution. We also showed from a quasi-static (QS) approximation framework that the high susceptibility of Pd LSPR originates from the smaller dispersion of the real part of its dielectric function than those of Au and Ag LSPR around the resonant wavelength. We conclude that the Pd nanoparticle is a promising candidate of "the third plasmonic sensing material" following Au and Ag to be used in ultrahigh-sensitive LSPR sensors.

We characterize the two-site marginals of exchangeable states of a system of quantum spins in terms of a simple positivity condition. This result is used in two applications. We first show that the distance between two-site marginals of permutation invariant states on N spins and exchangeable states is of order 1/N . The second application relates the mean ground state energy of a mean-field model of composite spins interacting through a product pair interaction with the mean ground state energies of the components.PACS numbers: 05.30.−d, 03.67.−a, 02.50.Cw * This paper is dedicated to A Verbeure on the occasion of his 65th anniversary.

Redox-active ionic liquids (RAILs) require no other additional reagents such as solvent and supporting electrolyte for electrochemical reactions under undiluted condition. Viologen-based RAILs are one of the electrochromic (EC) ionic liquids with sharp color contrast and high chemical stability. An operation of an EC cell requires two electroactive elements, an EC material and a charge compensating material. In this study, an equimolar composite of a viologen-based RAIL as the EC material and a ferrocene-based RAIL as the charge compensation material, was synthesized and applied to an EC cell. The EC cell with the composite RAIL of as high concentration as 0.92 M each redox species showed good coloration efficiency (91.4 cm2 C–1 at 540 nm on 1.0 V). The coloration process of the EC cell was diffusion-limited process. The current and absorbance of the EC cell reached constant values at large enough bias voltage because of the charge recombination between reduced viologens and oxidized ferrocenes. The recombination affected rapid color erasing process. Almost no deterioration of the composite RAIL was found by 1H NMR after 13 000 potential cycle durability experiment.

We demonstrated the usefulness of Cu light-harvesting plasmonic nanoantennae for the development of inexpensive and efficient artificial organic photoelectric conversion systems. The systems consisted of the stacked structures of layers of porphyrin as a dye molecule, oxidation-suppressing layers, and plasmonic Cu arrayed electrodes. To accurately evaluate the effect of Cu nanoantenna on the porphyrin photocurrent, the production of CuO by the spontaneous oxidation of the electrode surfaces, which can act as a photoexcited species under visible light irradiation, was effectively suppressed by inserting the ultrathin linking layers consisting of 16-mercaptohexadecanoic acid, titanium oxide, and poly(vinyl alcohol) between the electrode surface and porphyrin molecules. The reflection spectra in an aqueous environment of the arrayed electrodes, which were prepared by thermally depositing Cu on two-dimensional colloidal crystals of silica with diameters of 160, 260, and 330 nm, showed clear reflection dips at 596, 703, and 762 nm, respectively, which are attributed to the excitation of localized surface plasmon resonance (LSPR). While the first dip lies within the wavelengths where the imaginary part of the Cu dielectric function is moderately large, the latter two dips lie within a region of a quite small imaginary part. Consequently, the LSPR excited at the red region provided a particularly large enhancement of porphyrin photocurrent at the Q-band (ca. 59-fold), compared to that on a Cu planar electrode. These results strongly suggest that the plasmonic Cu nanoantennae contribute to the substantial improvement of photoelectric conversion efficiency at the wavelengths, where the imaginary part of the dielectric function is small.