Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

Experimental study for adsorption and photocatalytic reaction of ethyl methylphosphonate molecule as organophosphorus compound adsorbed at surface of titanium dioxide under UV irradiation in ambient condition

The adsorption and photocatalytic degradation of Ethyl methylphosphonate (EMPA) on powdery TiO₂ film has experimentally investigated using attenuated total reflection-infrared Fourier transform spectroscopy (ATR-FTIR) in ambient condition. Characteristic IR frequency as P-O-C vibration mode as EtO was observed by EMPA adsorbed at the surface of TiO₂. By TiO₂ photocatalysis, the adsorbed EMPA was decomposed to methyl phosphonic acid and phosphoric acid. The increment of IR intensity of which is assigned to Ti–O-P-O-Ti of EMPA was accompanied with increasing the IR peak intensity assigned to MPA. About that, we suggest that the appearance of the Ti–O-P-O-Ti of EMPA by the TiO₂ photocatalysis is regarded as acceleration of the hydrolysis of EMPA by the surface OH groups of TiO₂. The plausible adsorption structure and the photocatalytic reaction mechanism of EMPA at the surface of TiO₂ photocatalyst were elucidated.

     

Intramolecular photocycloaddition of β-stilbazoles tethered by silyl chains

Intramolecular (2+2) photocycloaddition of β-stilbazoles tethered by silyl chains took place with high efficiency. Complexation with dicarboxylic acid or catechol further enhanced both the efficiency and stereoselectivity.     

Ion-transfer voltammetry at a polarized room-temperature molten salt/water interface.

Tetraoctylammonium cation forms a room-temperature molten salt (RTMS) with 2,4,6-trinitrophenolate anion. The RTMS is immiscible with water (W) and forms a stable RTMS/W interface. It has been shown that the RTMS/W interface can be electrochemically polarized. A well-defined voltammetric wave due to the transfer of thiocyanate ion across the RTMS/W interface was observed within the potential window. This is the first example of a polarized RTMS/W interface.     

DNA-conjugated polymers for self-assembled DNA chip fabrication.

We developed two DNA-conjugated polymers, one based on polyallylamine and the other on polyacrylic acid, for use in DNA chips. A 30-mer single-stranded DNA probe and thioctic acid were covalently attached to polyallylamine as sidechains. The same single-stranded DNA and 3-(pyridyldithio)propionyl hydrazide were covalently attached to polyacrylic acid as sidechains. Both DNA-conjugated polymers could be specifically immobilized onto a gold sensor substrate by a self-assembly technique. The interactions between fully matched DNA and each DNA-conjugated polymer were investigated by surface plasmon resonance. A gold surface modified with either DNA-conjugated polymer recognized fully matched DNA much better than unmatched DNA. The hybridization selectivity and efficiency of DNA-conjugated polyallylamine was optimized by adjusting the pH so as to reduce the effects of cationic polymer sidechains. The hybridization selectivity and efficiency of DNA-conjugated polymers were higher than those of a conventional immobilized thiol-based DNA. The coating of DNA-conjugated polymers reduced nonspecific adsorption of DNA by the gold substrate. DNA-conjugated polyacrylic acid was more selective toward fully matched DNA than was DNA-conjugated polyallylamine. Therefore, DNA-conjugated polymers show promise for application in novel DNA chips.     

High-quality InAlN/GaN heterostructures grown by metal–organic vapor phase epitaxy

We fabricated high-quality InAlN/GaN heterostructures by metal–organic vapor phase epitaxy (MOVPE). X-ray diffraction measurements revealed that InAlN/GaN heterostructures grown under optimal conditions have flat surfaces and abrupt heterointerfaces. Electron mobility from 1200 to 2000 cm²/V s was obtained at room temperature. To our knowledge, this mobility is the highest ever reported for InAlN/GaN heterostructures. We also investigated the relationship between the Al composition and sheet electron density (N_s) for the first time. N_s increased from 1.0×10¹² to 2.7×10¹³ cm⁻² when the Al composition increased from 0.78 to 0.89.     

Rapid and sensitive determination of the conversion of UV-cured acrylic ester resins by pyrolysis-gas chromatography in the presence of an organic alkali.

The double-bond conversion of UV-cured resins prepared from pentaerythritol triacrylate (PETA) was determined by pyrolysis-gas chromatography in the presence of an organic alkali, tetramethylammonium hydroxide (TMAH). The pyrogram of the uncured prepolymer compound, consisting of PETA and a photoinitiator, 2,2-dimethoxy-2-phenylacetophenone, contained specific products reflecting the original acrylate structure, such as methyl acrylate (MA) and methyl ethers of pentaerithritol. Meanwhile, in pyrograms of the UV-cured PETA, the yields of MA considerably decreased. The double-bond conversions of the cured resins, irradiated with various UV dosages, were calculated based on the relative yields of MA among specific products in the pyrograms. The conversions determined by this approach were analyzed by comparing them with those estimated by Fourier-transform infrared spectroscopy.