Threonine-Based Stimuli-Responsive Nanoparticles with Aggregation-Induced Emission-Type Fixed Cores for Detection of Amines in Aqueous Solutions.

Stimuli-responsive polymeric nanoparticles (NPs) exhibit reversible changes in the dispersion or aggregation state in response to external stimuli. In this context, we designed and synthesized core-shell NPs with threonine-containing weak polyelectrolyte shells and fluorescent cross-linked cores, which are applicable for the detection of pH changes and amine compounds in aqueous solution. Stable and uniform NP(dTh) and NP(Fl), consisting of fluorescent symmetric diphenyl dithiophene (dTh) and diphenyl fluorene (Fl) cross-linked cores, were prepared by site-selective Suzuki coupling reactions in self-assembled block copolymer. NP(Fl) with the Fl unit in the core showed a high fluorescence intensity in different solvents, which is regarded as an aggregation-induced emission-type NP showing strong emission in aggregated states in the cross-linked core. Unimodal NPs were observed in water at different pH values, and the diameter of NP(Fl) changed from 122 (pH = 2) to 220 nm (pH = 11). Furthermore, pH-dependent changes of the fluorescence peak positions and intensities were detected, which may be due to the core aggregation derived from the deprotonation of the threonine-based shell fragment. Specific interactions between the threonine-based shell of NP(Fl) and amine compounds (triethylamine and p-phenylenediamine) resulted in fluorescence quenching, suggesting the feasibility of fluorescent amine detection.

Local atomic structure analysis of GaN surfaces via X-ray absorption spectroscopy by detecting Auger electrons with low energies.

GaN is a promising material for power semiconductor devices used in next-generation vehicles. Its electrical properties such as carrier mobility and threshold voltage are affected by the interface between the oxide and the semiconductor, and identifying the interface states is important to improve these properties. A surface-sensitive measurement of Ga K-edge extended X-ray absorption fine structure (EXAFS) by detecting Ga LMM Auger electrons that originate from Ga K-shell absorption is proposed for GaN. LMM Auger electrons with low energies were detected and the EXAFS oscillation was confirmed, providing information on the Ga atoms at the surface. Investigation of thermally oxidized GaN with an oxide film of defined thickness showed that the analysis depth was less than 10 nm, which is consistent with the inelastic mean free path of 2.3 nm estimated for LMM Auger electrons in GaN.

Distinguishing nitrogen-containing sites in SiO2/4H-SiC(0001) after nitric oxide annealing by X-ray absorption spectroscopy.

The atomic structure of nitrogen at the SiO2/4H-SiC(0001) interface has been investigated using X-ray absorption spectroscopy (XAS) in two nitric oxide annealed samples, one of which was oxidized in dry O2 (NO-POA) prior to the experiment. The peak shapes and energies of the observed and simulated spectra are in agreement and indicate that the N-containing sites could be the substitutional C site at the interface for the NO-annealed sample and the interstitial site in the interior of SiC for the NO-POA-annealed sample. XAS analysis distinguished between the N-containing sites at the SiO2/SiC interface.

Self-Assembled Single-Crystalline GaN Having a Bimodal Meso/Macropore Structure To Enhance Photoabsorption and Photocatalytic Reactions.

This paper describes the self-assembled fabrication of single-crystal GaN with a bimodal pore (meso/macropore) size distribution (BiPS-GaN). A 4.7 µm-thick BiPS-GaN layer was grown spontaneously using halogen-free vapor phase epitaxy in conjunction with boron impurity doping (>1 × 1019 atoms/cm3) on a GaN template fabricated via metalorganic chemical vapor deposition (MOCVD-GaN). The boron impurity acted as a surfactant, and its segregation generated a dense (>1 × 1010 cm-2), homogeneous distribution of mesopores with sizes of 30-40 nm in GaN during growth. In addition, macropores with sizes of 0.1-2 µm were produced by the fusion of mesopores in close proximity to one another. As a result, BiPS-GaN exhibited a high density of both meso- and macropores, all aligned in the vertical direction (that is, along the c axis). BiPS-GaN showed good electroconductivity and almost the same high degree of crystallinity as the MOCVD-GaN template. Furthermore, the hybrid meso/macropore structure of BiPS-GaN imparted excellent photoabsorption properties and allowed this material to work as an efficient support for a nanosized IrO x catalyst. The photocurrent density in BiPS-GaN was enhanced by as much as a factor of 5 compared to planar GaN by effective absorption due to the hybrid meso/macropore structure of BiPS-GaN. Moreover, the oxygen generation efficiency of BiPS-GaN with the IrO x catalyst was approximately doubled, compared to that of BiPS-GaN without IrO x, while maintaining long-term stability. These results demonstrate that BiPS-GaN fabricated in this facile manner has significant potential in applications such as photoelectrochemical reactions and catalysis.

Band bending and dipole effect at interface of metal-nanoparticles and TiO2 directly observed by angular-resolved hard X-ray photoemission spectroscopy.

This paper describes the observation of band bending and band edge shifts at the interfaces between nanoscale metals and TiO2 film over a wide depth range by angular-resolved hard X-ray photoemission spectroscopy (HAXPES). The HAXPES results indicate strong electrostatic interactions between the TiO2 semiconductor and metal nanoparticles, while density functional theory (DFT) calculations suggest that these interactions are primarily associated with charge transfer leading to electric dipole moments at the interface in the ground state. The effects of these dipole moments are not limited to the surface but also occur deep in the bulk of the semiconductor, and are highly dependent on the coverage of the metal nanoparticles on the semiconductor species.

(+)-Pinoresinol is a putative hypoglycemic agent in defatted sesame (Sesamum indicum) seeds though inhibiting α-glucosidase.

Defatted sesame seeds have been reported for hypoglycemic effect in mice and T2DM women. An attempted to identify active components responsible for this effect was conducted using α-glucosidase-guided fractionation, resulting in the isolation of various lignans. Of compounds isolated, only (+)-pinoresinol showed inhibitory activity against rat intestinal maltase with an IC(50) value of 34.3 µM. The kinetic study indicated that enzymatic hydrolysis of maltose is inhibited by (+)-pinoresinol through competitive and noncompetitive manners. However, a lower dissociation constant (k(i) 288 M) of EI complex suggested that competitive inhibition is predominant over noncompetitive mode (k'(i) 1342 M).