Creation of high-refractive-index amorphous titanium oxide thin films from low-fractal-dimension polymeric precursors synthesized by a sol-gel technique with a hydrazine monohydrochloride catalyst

Amorphous titanium dioxide (TiO(2)) thin films exhibiting high refractive indices (n ≈ 2.1) and high transparency were fabricated by spin-coating titanium oxide liquid precursors having a weakly branched polymeric structure. The precursor solution was prepared from titanium tetra-n-butoxide (TTBO) via the catalytic sol-gel process with hydrazine monohydrochloride used as a salt catalyst, which serves as a conjugate acid-base pair catalyst. Our unique catalytic sol-gel technique accelerated the overall polycondensation reaction of partially hydrolyzed alkoxides, which facilitated the formation of liner polymer-like titanium oxide aggregates having a low fractal dimension of ca. (5)/(3), known as a characteristic of the so-called "expanded polymer chain". Such linear polymeric features are essential to the production of highly dense amorphous TiO(2) thin films; mutual interpenetration of the linear polymeric aggregates avoided the creation of void space that is often generated by the densification of high-fractal-dimension (particle-like) aggregates produced in a conventional sol-gel process. The mesh size of the titanium oxide polymers can be tuned either by water concentration or the reaction time, and the smaller mesh size in the liquid precursor led to a higher n value of the solid thin film, thanks to its higher local electron density. The reaction that required no addition of organic ligand to stabilize titanium alkoxides was advantageous to overcoming issues from organic residues such as coloration. The dense amorphous film structure suppressed light scattering loss owing to its extremely smooth surface and the absence of inhomogeneous grains or particles. Furthermore, the fabrication can be accomplished at a low heating temperature of <80 °C. Indeed, we successfully obtained a transparent film with a high refractive index of n = 2.064 (at λ = 633 nm) on a low-heat-resistance plastic, poly(methyl methacrylate), at 60 °C. The result offers an efficient route to high-refractive-index amorphous TiO(2) films as well as base materials for a wider range of applications.     

Phase behavior of aqueous solutions of copolymers of N,N'-diisopropylfumaramide and N-isopropylacrylamide: effect of the density of side chains

This letter describes the phase behavior of aqueous solutions of an N-isopropylacrylamide (NIPAM) homopolymer and copolymers of N,N'-diisopropylfumaramide (DIPFAM) and NIPAM as studied by transmittance measurements, infrared spectroscopy, and differential scanning calorimetry to reveal the effect of the density of N-isopropylamide side chain upon the phase behavior. The clouding-point and clearing-point temperatures decreased with increasing the mole fraction of DIPFAM (x(D)). It was noteworthy that only an extra side chain per ca. 7 NIPAM units had a remarkable effect on the phase behavior; the interactions between side chains were stronger, the intrapolymer contraction was less favorable, and the cooperativity of phase transition was lower at x(D) = 0.15 presumably because of the steric hindrance of dense side chains.     

Rational design of smart supramolecular assemblies for gene delivery: chemical challenges in the creation of artificial viruses

Polymeric materials have been extensively developed as a delivery vehicle for nucleic acids over the past two decades. Many previous studies have demonstrated that synthetic delivery vehicles can be highly functionalized by chemical approaches to overcome biological barriers in nucleic acid delivery, similar to viruses. Based on our current knowledge, this tutorial review describes rational strategies in the design of polymeric materials to achieve construction of the versatile vehicles, that is "artificial viruses", for successful gene therapy, especially focusing on the chemical structures with the minimal adverse effects.     

Survey meter combining CVD diamond and silicon detectors for wide range of dose rates and high accumulated doses

We have developed a prototype of a survey meter combining a CVD diamond detector and silicon detectors to appropriately take temporal measurements of γ-ray radiations over a wide range of the dose rates and to measure high accumulated doses of γ-ray radiations. In order to carry out this, at first, we have studied the radiation hardness of diamond detectors suitably fabricated with high-quality single-crystalline CVD diamond films to confirm that such CVD diamond detectors have greatly superior radiation hardness, compared with commercially available silicon detectors. It is evidenced that the performance of the CVD diamond detector did not significantly change even after heavy γ-ray irradiation of 0.7 MGy while the silicon detectors have a remarkable increase in the dark current, a detection peak shift to the low energy side, and a decrease in detection counts for 5.486-MeV α particles. Due to a size limitation of the CVD diamond detector, such a CVD diamond detector was combined with six commercially available silicon detectors to fabricate a survey meter which can appropriately work under severe irradiation conditions, or, at accumulated doses larger than at least 0.5 MGy and which can cover a wide range of the dose rates from 1 μGy/h to at least 1 kGy/h. The prototype survey meter had a practically useful linearity in this dose rate range. Thus, we have confirmed that such a diamond-Si combined survey meter can be put into practical use.     

Application of mixture analysis to crude materials from natural resources (III): NMR spectral studies to analyze chalcones from Angelica keiskei

This study presents the application of the NMR-based analyses, DOSY and ROSY, to the chalcones, xanthoangelol (1) and 4-hydroxyderricin (2) from Angelica keiskei. We investigated whether virtual separation and structural information from each compound can be obtained. DOSY displays spectra of (1) and (2) in one dimension and diffusion spectra in the other. And the 1H slice spectra were analyzed in detail by comparison with authentic samples previously isolated from the same material. The resulting ROSY spectrum clearly showed two distinct peaks in the 1H T1 dimension. Each slice of the ROSY spectrum along the 13C dimension contains over-lapped signals, which are difficult to assign at this time.     

A catalytic version of hypervalent aryl-λ3-iodane-induced Hofmann rearrangement of primary carboxamides: iodobenzene as an organocatalyst and m-chloroperbenzoic acid as a terminal oxidant

The first catalytic version of hypervalent aryl-λ(3)-iodane-induced Hofmann rearrangement of primary carboxamides, which probably involves in situ generation of a tetracoordinated bis(aqua)(hydroxy)phenyl-λ(3)-iodane complex as an active oxidant from a catalytic amount of iodobenzene by the reaction with m-chloroperbenzoic acid in the presence of HBF(4) in dichloromethane-water under mild conditions, was developed.     

A vapoluminescent Eu-based metallo-supramolecular polymer

An Eu-based metallo-supramolecular polymer (polyEu) was prepared by self-assembly coordination polymerization. Unique vapoluminescence property of polyEu triggered by acid-base vapor was found and a photoluminescence display in switchable imaging by acid-base vapor was fabricated.     

Fluorescence imaging of potassium ions in living cells using a fluorescent probe based on a thrombin binding aptamer-peptide conjugate

When a biotinylated FRET probe based on a peptide-thrombin binding aptamer conjugate was introduced together with streptavidin and biotinylated nuclear export signal peptide into HeLa cells, the resulting ternary complex enabled visualization of K(+) concentration changes in the cell.     

NanoPARCEL: a method for controlling cellular behavior with external light

We developed a simple preparation procedure for the protein encapsulated nanoparticle and used the nanoparticle for spatiotemporal activity control of various proteins. We succeeded in the local protein activation within cells by light using the nanoparticle.     

Silica-porphyrin hybrid nanotubes for in vivo cell tracking by near-infrared fluorescence imaging

Near-infrared fluorescent silica-porphyrin hybrid nanotubes (HNTs) were successfully synthesized by π-π stacking, electrostatic interaction and a sol-gel reaction. The HNTs-labeled macrophages were detected in vivo, and the minimum detectable number of cells was 200. Furthermore, the biodistribution of HNTs-labeled macrophages was tracked by fluorescence imaging.