Physics in plasmonic and Mie scattered near-field for efficient surface-enhanced Raman scattering template

We describe the physics of the SERS based on the optical near-field intensity enhancement on the metallic (plasmonic) and the nonmetallic (Mie scattering) nanostructured substrates with two-dimensional (2D) periodic nanohole arrays. The calculation by the Finite-Difference Time-Domain (FDTD) method revealed that the optical intensity enhancement increases with the increase of the thickness of a gold film coating on the nonmetallic (dielectric) nanostructured Si, GaAs, and SiC substrates. The resonance spectrum shifts with the changes in the geometrical structure of the void diameter and inter-void distance. It was clarified that the optical intensity enhancement obtained with the gold-coated substrate is equivalent to that with a gold substrate at 70-nm thick gold coating on the dielectric substrates in this structure. The resonance spectral bandwidth for Mie scattering and plasmonic near-fields is different. Therefore, if the Stokes line of the Raman scattering is located within the resonance bandwidth, the SERS signal is enhanced proportionally to the fourth power of the electric near-field. However, if the Stokes shift is located out of the resonance bandwidth, the SERS signal enhancement is only proportional to the square of the scattered near-field.     

NDMAP: the best material to study the Haldane's prediction

As predicted by Haldane, spin, S=1 one-dimensional (1D) Heisenberg antiferromagnet (HAF) has an energy gap between the singlet ground state and first excited triplet. On application of magnetic field, the triplet state Zeeman splits and the energy of one of the triplet state becomes zero at a critical field, H_c. Above H_c the system recovers magnetism. Then, we expect that a quasi-1D HAF will show a magnetic long-range ordering (LRO) at low temperatures due to the inter-chain coupling. This field-induced LRO has not been observed before due to complication of the crystal structure in the materials studied so far and/or technical difficulty.From a heat capacity measurement on a single crystal of an S=1 quasi-Q1D HAF, Ni(C₅H₁₄N₂)₂N₃(PF₆), we found an anomaly at a temperature in finite fields indicating a field-induced phase transition. A magnetic LRO is confirmed by a neutron diffraction measurement on the same sample. The temperature versus magnetic field phase diagram of this compound is constructed and discussed.     

Superconductivity in heavy fermion systems

The heavy fermion state in the f-electron systems is due to competition between the RKKY interaction and the Kondo effect. The typical compound is CeCu₆. To understand the electronic state, we studied the Fermi surface properties via the de Haas–van Alphen (dHvA) experiment and energy band calculation for CeSn₃,CeRu₂Si₂,UPt₃, and nowadays, transuranium compounds. Pressure is also an important technique to control the electronic state. The Néel temperature T_N decreases with increasing pressure P and becomes zero at the critical pressure for . The typical compound is an antiferromagnet CeRhIn₅, which we studied from the dHvA experiment under pressure. A change of the 4f-electronic state from localized to itinerant is realized at , revealing the first-order phase transition, together with a divergent tendency of the cyclotron mass at P_c. It is stressed that appearance of superconductivity in CeRhIn₅ is closely related to the heavy fermion state. It is also noted that the parity-mixed novel superconducting state might be realized in a pressure-induced superconductor CeIrSi₃ without inversion symmetry in the crystal structure.     

Spin Excitations in the Field-Induced Phase of the Quasi-One-Dimensional S = 1 Heisenberg Antiferromagnet NDMAP

The S = 1 quasi-one-dimensional Heisenberg antiferromagnet [Ni(C₅H₁₄N₂)₂N₃](PF₆), abbreviated as NDMAP, has been studied by electron spin resonance in a magnetic field above the critical field (H _c). We studied angular and frequency dependences of spin excitations. The angular dependence of the spin excitations in the vicinity of H _c is explained well by a phenomenological field theory, but the agreement between the experiment and the calculation is not satisfactory above 10 T. In high magnetic fields above 15 T, we obtained some characteristic spin excitations which are well explained by conventional antiferromagnetic resonance modes. These results suggest that the spin excitations change from a quantum state to a classical one due to the suppression of quantum fluctuations by high magnetic fields.     

Contribution of conformational change of polymer structure to electrochemomechanical deformation based on polyaniline

The pH dependencies of electrochemomechanical deformation (ECMD) including the cyclic voltammetry and the expansion ratio in conducting polymers, polyaniline (PANI), and poly(o-methoxyaniline) film were studied to elucidate the mechanisms. It was found that the ECMD is governed by the conformational change of polymer structure as well as the insertion of bulky ions in the manner of comparable magnitude. Expansion ratios >20% in the ECMD were demonstrated for the thickness direction of PANI film. The results suggest that the magnitude of ECMD can be improved by choosing the preparation method of films.     

On the chemical states of nitrogen on iron surfaces reacted with ammonia and sodium cyanide,studied by X-ray photoelectron spectroscopy

The reaction products of iron reacted with ammonia gas and molten sodium cyanide are studied using X-ray photoelectron spectroscopy. Ammonia gas dissociates on iron surfaces to form a nitride and a loosely bound NH₃-like species with N 1sB.E.'s at 397.2 and 399.8 eV, respectively. On iron specimens dipped into molten NaCN three species are found at 398.6, 397.8 and 397.2 eV. The 398.6-eV peak is ascribed to adsorbed ?CN, and the 397.8-eV peak to carbonitride formed by the reaction of the cyanide with iron. Decreasing binding energies are found for adsorbed ?CN ligand, carbonitride compound and nitride, which seem to correspond to an apparent order of stronger interaction of nitrogen with iron. An iron sample was scratched with a file and the surface species of nitrogen were observed below 400°C. The nitrogen atoms in the sample diffuse and concentrate on the surface, depending on the nitrogen content in the bulk. Desorption patterns of nitrogen from a heated iron surface are examined with a view to the determination of gaseous constituents in metal samples.     

Thermodynamic properties in the approach to the quantum critical point of the spin-ladder material Na2Co2(C2O4)3(H2O)2

Magnetic susceptibility and heat capacity measurements as a function of temperature on a single-crystal sample of a spin-ladder material, Na2Co2(C2O4)3(H2O)2, are reported. Principal susceptibilities, parallel and perpendicular to the ladder direction, respectively, show broad maxima around 22 and 17 K. Both susceptibilities decay exponentially down to about 5 K and thereafter they are essentially independent of temperature. These findings amount to a signature of a quantum phase transition from a spin-liquid to Néel ordered state previously predicted theoretically. No anomaly is found in the heat capacity around the transition temperature.     

Improving the spectral resolution of wedged etalons and linear variable filters with incidence angle

Compact spectrometers fabricated by placing a wedged etalon or a linear variable filter in front of a linear photodiode array typically do not exhibit the spectral resolution of a parallel filter of the same finesse. A theoretical analysis of the beam emerging from a wedged etalon is shown to predict a comalike aberration, explaining the loss in resolution. This analysis also predicts a focused beam waist whose axial position depends on the incidence angle, indicating that resolution can be improved by placing this waist on the detector. These results are experimentally confirmed in a multicavity linear variable filter to achieve 0.09 nm spectral resolution at 1550 nm.     

Synthesis and evaluation of 6-nitro-7-(1-piperazino)quinazolines: dual-acting compounds with inhibitory activities toward both tumor necrosis factor-alpha (TNF-alpha) production and T cell proliferation

We investigated the chemical modifications of the nitroquinazoline derivative (1) through the replacement of the NH group at the C(4)-position with several N-alkyl groups to increase the lipophilicity at the C(4)-position. Among them, we found that the N-methyl analogue (5a) showed a 2-fold loss in the inhibitory activity toward tumor necrosis factor-alpha (TNF-alpha) production in vitro as compared with the NH analogue (1); however, 5a exhibited an oral inhibitory activity on TNF-alpha production with an ED50 value of 26 mg/kg, whereas 1 did not. Moreover, the oral bioavailability of 5a was higher than that of 1 (1, F=1%; 5a, F=21%), and the calculated ClogP value for 5a was higher than that for 1. These results suggest that the improved lipophilicity of 5a compared with that of 1 reflects its greater inhibitory activity on TNF-alpha production in vivo as well as oral bioavailability.     

Analysis of sialo-N-glycans in glycoproteins as 1-phenyl-3-methyl-5-pyrazolone derivatives by capillary electrophoresis

A method for the analysis of the sialo-N-glycans in glycoproteins was established by the electrokinetic chromatography mode of capillary electrophoresis (CE) in sodium dodecyl sulfate (SDS) micelles as 1-phenyl-3-methyl-5-pyrazolone (PMP) derivatives, using sialo-N-glycans in fetuin as a model. Six major and some minor peaks were observed for the N-glycans in fetuin, which were well separated from each other using 50 mM phosphate buffer, pH 6.0, containing SDS to a concentration of 30 mM in an uncoated fused-silica capillary, and these peaks were assigned to sialo-N-glycans having either of the biantennary or β1-3/β1-4 linked galactose-containing complex type triantennary N-glycans as the basic structures, by an indirect method based on the assignment of the peaks in high-performance liquid chromatography separated in parallel with CE and peak collation between these two separation methods. The attaching position of the sialic acid residue was determined using the linkage preference of neuraminidase isozymes. The established system is considered to be useful for routine analysis of microheterogeneity of the carbohydrate moiety of this model glycoprotein from the following reasons: (1) the derivatization with PMP proceeds quantitatively under mild conditions without causing release of the sialic acid residue, (2) the derivatives can be sensitively detected by UV absorption, (3) the procedure is simple, rapid and reproducible. Preliminary results of N-glycan analysis for several other glycoproteins under these conditions are also presented.