Liquid crystalline gel with refractive index gradient of curdlan

Curdlan dissolved in aqueous sodium hydroxide was dialyzed to aqueous calcium chloride to form a gel. Transparent and turbid concentric layers observed in the gel cross section perpendicular to the long axis of the dialysis tube were identified as liquid crystalline gels with refractive index gradient and amorphous gels, respectively. The thickness of each layer was proportional to the diameter of the dialysis tube, and the gelation proceeded in proportion to the root of time. The unique pattern formation was attributed to the change of curdlan conformation and calcium-induced cross-linking resulting from a diffusion of calcium cations and hydroxide anions through the dialysis tube. It is suggested that the orderedness of the curdlan molecules decreases by the increase of the curvature of the concentric liquid crystal layers as the layer comes toward the center of the dialysis tube.     

Ligand binding properties of myoglobin reconstituted with iron porphycene: unusual O2 binding selectivity against CO binding

Sperm whale myoglobin, an oxygen storage hemoprotein, was successfully reconstituted with the iron porphycene having two propionates, 2,7-diethyl-3,6,12,17-tetramethyl-13,16-bis(carboxyethyl)porphycenatoiron. The physicochemical properties and ligand bindings of the reconstituted myoglobin were investigated. The ferric reconstituted myoglobin shows the remarkable stability against acid denaturation and only a low-spin characteristic in its EPR spectrum. The Fe(III)/Fe(II) redox potential (-190 mV vs NHE) determined by the spectroelectrochemical measurements was much lower than that of the wild-type. These results can be attributed to the strong coordination of His93 to the porphycene iron, which is induced by the nature of the porphycene ring symmetry. The O2 affinity of the ferrous reconstituted myoglobin is 2600-fold higher than that of the wild-type, mainly due to the decrease in the O2 dissociation rate, whereas the CO affinity is not so significantly enhanced. As a result, the O2 affinity of the reconstituted myoglobin exceeds its CO affinity (M' = K(CO)/K(O2) < 1). The ligand binding studies on H64A mutants support the fact that the slow O2 dissociation of the reconstituted myoglobin is primarily caused by the stabilization of the Fe-O2 sigma-bonding. The IR spectra for the carbon monoxide (CO) complex of the reconstituted myoglobin suggest several structural and/or electrostatic conformations of the Fe-C-O bond, but this is not directly correlated with the CO dissociation rate. The high O2 affinity and the unique characteristics of the myoglobin with the iron porphycene indicate that reconstitution with a synthesized heme is a useful method not only to understand the physiological function of myoglobin but also to create a tailor-made function on the protein.     

Fabrication of Rh based solid-solution bimetallic alloy nanoparticles with fully-tunable composition through femtosecond laser irradiation in aqueous solution

Many late transition binary alloy nanoparticles (NPs) have been fabricated through a wide variety of techniques. Various steps are involved in the fabrication of such NPs. Here, we used a simple and green route to fabricate solid-solution Rh–Pd and Rh–Pt bimetallic alloy NPs through femtosecond laser irradiation in a solution without any chemicals like reducing agents. X-ray diffraction (XRD) peaks of NPs obtained in the solutions with different ratios of Rh–Pd and Rh–Pt ions monotonically varied from the position of pure Rh to those of Pd and to Pt which respectively indicated that these NPs were alloy. Composition of fabricated NPs was fully tuned over the entire range of Rh_1?x –Pd _x , and Rh_1?x –Pt _x with varying the mixing ratio of metal ions in the solution. Studies of Rh–Pd and Rh–Pt solid-solution system suggest that the alloy formation occurs through the nucleation of Rh and then followed by the diffusion of Rh, Pd and Rh, Pt to form a homogeneous alloy. The variety of average size of the alloy NPs for different compositions could be attributed to different reduction rate and surface energies of metal ions. Our result implies that femtosecond laser irradiation in aqueous solution is one of the potential methodologies to form multimetallic solid-solution alloy NPs with fully tunable composition.     

Dependences of structural and electrical properties on thickness of polycrystalline Ga-doped ZnO thin films prepared by reactive plasma deposition

Polycrystalline Ga-doped (Ga content: 4 wt%) ZnO (GZO) thin films were deposited on glass substrates at 200 C by a reactive plasma deposition with DC arc discharge technique. The dependences of structural and electrical properties of GZO films on thickness, ranging from 30 to 560 nm, were investigated. Carrier concentration, n, and Hall mobility, μ, increases with increasing film thickness below 100 nm, and then the n remains nearly constant and the μ gradually increases until the thickness reaches 560 nm. The resistivity obtained of the order of 10⁻⁴ Ω cm for these films decreases with increasing film thickness: The highest resistivity achieved is 4.4×10⁻⁴ Ω cm with n of 7.6×10²⁰ cm⁻³ and μ of 18.5 cm²/V s for GZO films with a thickness of 30 nm and the lowest one is 1.8×10⁻⁴ Ω cm with n of 1.1×10²¹ cm⁻³ and μ of 31.7 cm²/V s for the GZO film with a thickness of 560 nm. X-ray diffraction pattern for all the films shows a hexagonal wurtzite structure with its strongly preferred orientation along the c-axis. Full width at half maximum of the (002) preferred orientation diffraction peak of the films decreases with increasing film thickness below 100 nm.     

Compensation of effect of field instability by reference deconvolution with phase reconstruction

A compensation method based on reference deconvolution is developed to obtain high-resolution NMR spectra under an unstable magnetic field. It is shown that the applicability of the original deconvolution method is limited for small fluctuation, and a process what may be called phase reconstruction is proposed to compensate large field fluctuation. We demonstrate the method using a probe with a coil that can generate a fluctuation field artificially. A high-resolution 1H NMR spectrum of ethylbenzene was obtained under the unstable field after compensation with this method.