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.     

Association Behavior of 4-Acylpyrazolone Derivative and Tertiary Amine of High Molecular Weight in Antagonistic Synergistic Extraction of Palladium

To find an effective extraction and removal method for palladium(II), which is one of the main fission products from an acidic nuclear spent fuel solution, the extraction behavior of palladium(II) from a nitric acid medium by an acidic chelating extractant, 1-phenyl-3-methyl-4-trifluoroacetylpyrazolone-5-one (HPMTP) and a tertiary amine of high molecular weight, tri-n-octylamine (TOA), has been studied by spectrophotometry. A noticeable antagonistic extraction effect was observed in the extraction system under the given conditions. To understand this phenomenon, a preliminary investigation was performed to explain the mechanism of this reaction. According to the theory of corresponding solutions (TCS), the association reaction between HPMTP and TOA is proposed in the organic phase. An associated species, HPMTP·TOA, formed through hydrogen bonding in a chloroform medium might be the main reason why an antagonistic extraction effect occurred. The association constant between HPMTP and TOA was calculated to be 2.86±0.05.     

Evaluation of the molecular recognition of peptide-conjugated polymer.

We have recently reported on dodecamer peptides (HPPMDFHKAMTR, CHPQPLKSRNPL) which recognize 52-58th and 197-203rd amino acid sequences of glucose oxidase (GOx) by screening via a phage random peptide library. In this study, a side-chain protected peptide monomer (PPM) was synthesized using two peptides (HPPMDFHKAMTR, SHPQPLKSRNPL) and acryloyl chloride. The peptide-conjugated polymer (PCP) was copolymerized with PPMs and N,N-diethylacrylamide (DEAA). The affinity of PCPs to GOx was estimated using surface plasmon resonance detection. This study suggests that PCP is a valuable molecular recognition biomolecule.     

Acoustic characteristics of Ni–Nb–Zr–H glassy alloys by ultrasonic shear waves

The propagation characteristics of shear horizontally polarized (SH) waves passing through (Ni₄₂Nb₂₈Zr₃₀)_100–x H_x (x = 0–15.2) glassy alloys were investigated as a function of hydrogen content. With an increase in hydrogen content, the propagation time and main frequency of the receiving waves show increase and decrease, respectively, indicating expan‐ sion in average atomic distance which comes from solution of hydrogen. In sharp contrast to crystalline alloys, the decrease in damping ratio and the delay in phase with increasing hydrogen suggest a strong settlement of hydrogen into four‐coordination sites surrounded tetrahedrally by four Zr atoms and the resulting increase in dynamic elasticity, respectively. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis and properties of furo[4,3,2-de][1]benzopyran

A new heterocycle, furo[4,3,2-de][1]benzopyran ( 2 ), was synthesized. A key step in the sequence was the allylic bromination of 3,4-dihydrofuro[4,3,2-de][1]benzopyran ( 8 ) to give 3-bromo-3,4-dihydrofuro[4,3,2-de][1]-benzopyran ( 10 ) using N-bromosuccinimide under irradiation and high dilution conditions. Bromide 10 was dealt with 1,8-diazabicyclo[5.4.0]undec-7-ene to afford compound 2 . Several reactions of 2 were examined. Protonation of 2 in trifluoroacetic acid occurred at the 2-position to form a pyrylium ion 12 . Catalytic hydrogenation of 2 with palladium on charcoal proceeded smoothly to give 8 . Reduction of 2 by sodium and ethanol afforded 3-ethyl-4-hydroxybenzofuran ( 14 ). Electrophilic substitutions of 2 such as formylation, acetylation, and bromination, occurred easily at the 2-position. The above results show that compound 2 has both properties of benzofuran and 4-methylenepyran.     

Short-step synthesis of tamoxifen and its derivatives via the three-component coupling reaction and migration of the double bond

The anti-tumor agent, tamoxifen, is easily synthesized by the successive allylation of benzaldehyde and the Friedel-Crafts alkylation reaction of anisole with the intermediary homoallyl silyl ethers, followed by the migration of the double bond to form the desired tetra-substituted ethylenes. Several derivatives of tamoxifen are also produced according to a similar synthetic strategy.