Biosensor for peptide determination constructed by immobilizing proteolytic enzymes on coated-wire electrodes

A biosensor for peptide determination was constructed with trypsin or α-chymotrypsin immobilized on hydrogen ion-selective coated-wire electrode and its fundamental properties were investigated with two artificial peptides. The substrates could be determined in the range 0.1–40 mM with response times of 5–10 min. The effects of pH and concentration of buffer solution on the determination were investigated.     

Enantioselective preparation of C-ring fragment of cotylenin A via catalytic asymmetric intramolecular cyclopropanation of α-diazo β-keto ester

A synthetic pathway to the C-ring fragment of cotylenin A which emerged from our retrosynthetic analysis of cotylenin A is described. The catalytic asymmetric intramolecular cyclopropanation (CAIMCP) of the α-diazo-β-keto ester bearing 2,4,6-trimethylphenyl group as the ester part has been found to afford the crystalline product with high ee, which allowed to establish the approach to the C-ring fragment which required ten-pot operations. The developed approach would be beneficial to a large scale synthesis of the C-ring fragment for the total synthesis of cotylenin A.     

An experimental study on effects of solid concentration and ζ-potential on pseudoplastic flow of suspensions

The pseudoplastic flow of suspensions, alumina or styrene-acrylamide copolymer particles in water or an aqueous solution of glycerin has been studied by the step-shear-rate method. The relation between the shear rate,D, and the shear stress,, in the step-shear-rate measurements, where the state of dispersion was considered to be constant, was expressed as = AD ^1/2 +CD. The effective solid volume fraction,ø _F, andA were dependent on the shear rate and expressed byø _F =aD ^b andA = D . Combining the above relations, the steady flow curve was expressed by = D ^{1/2 +} + ₀ (1 – a D ^b/0.74)^–1.85 D, where ₀ is the viscosity of the medium.With an increase in solid volume fraction and a decreases in the absolute value of the-potential, the flow behavior of the suspensions changed from Newtonian ( = = b = 0), slightly pseudoplastic ( = b = 0), pseudoplastic ( = 0) to a Bingham-like behavior.The change in viscosity of the medium had an effect on the change in the effective volume fraction.     

Catalytic enantioselective 1,3-dipolar cycloadditions of nitrones with propioloylpyrazoles and acryloylpyrazoles induced by chiral π-cation catalysts

A chiral copper(II) complex of 3-(2-naphthyl)-l-alanine amide successfully catalyzes the enantioselective 1,3-dipolar cycloaddition reaction of nitrones with propioloylpyrazole and acryloylpyrazole derivatives. The asymmetric environment created by intramolecular π-cation interaction gives the corresponding adducts in high yields with excellent enantioselectivity. This is the first successful method for the catalytic enantioselective 1,3-dipolar cycloaddition of nitrones with acetylene derivatives. The 1,3-dipolar cycloadducts can be stereoselectively converted to β-lactams via reductive cleavage of the N-O bond using SmI(2).     

An 8-sulfonamidoquinoline derivative with imidazolium unit as an extraction reagent for use in ionic liquid chelate extraction systems

To evaluate the superiority of using a task-specific onium salt (TSOS), a novel TSOS reagent 1-methyl-3-[2-(8-quinolinylaminosulfonyl)ethyl]imidazolium chloride (HmimesqCl) was synthesized, and its performance in extraction of different divalent metal cations was investigated. This TSOS reagent has both a cationic imidazolium unit and an anionic (proton-dissociable) complexation unit for the extraction of metal cations into an ionic liquid. In the use of HmimesqCl, relatively high extraction of metals resulted in comparison with the use of its non-imidazolium analogs, without changing the extraction selectivity.     

Photoinduced change in the spin state of itinerant correlated electron systems

A photoinduced spin-state change in the itinerant correlated electron system is studied. A photon introduced in the low-spin band insulator induces a bound state of the high-spin state and a photoexcited hole. This bound state brings a characteristic peak in the pump-probe optical absorption spectra which are completely different from the spectra in thermal-excited states. The present results well explain the recent experiments of the ultrafast optical spectroscopy in perovskite cobaltites.     

Octave-spanning carrier-envelope phase stabilized visible pulse with sub-3-fs pulse duration

The visible second harmonic of the idler output from a noncollinear optical parametric amplifier was compressed using adaptive dispersion control with a deformable mirror. The amplifier was pumped by and seeded in the signal path by a common 400 nm second-harmonic pulse from a Ti:sapphire regenerative amplifier. Thus, both the idler output and the second harmonic of the idler were passively carrier-envelope phase stabilized. The shortest pulse duration achieved was below 3 fs.     

Synthesis of chiral 3,3′-disubstituted 1,1′-binaphthyl-2,2′-disulfonic acids

A convenient synthesis of chiral 3,3′-disubstituted 1,1′-binaphthyl-2,2′-disulfonic acids (BINSA, 1) was developed. The key was directed ortho-lithiation of BINSA methyl ester 2 with n-BuLi and subsequent reaction with an electrophile. Electrophiles such as Br₂, I₂, Me₃SiOTf, and i-PrOB(Pin) reacted smoothly with 3,3′-dilithiated BINSA methyl ester, and the corresponding 3,3′-dihalo-, 3,3′-bis(trimethylsilyl)-, and 3,3′-diboryl-BINSA derivatives were obtained in yields of 21–78%. This simple synthetic method is highly attractive since the ability to prepare 3,3′-disubstituted BINOLs in advance can be useful.     

Electrocatalysts for methanol oxidation with ultra low content of Pt and Ru

We have developed efficient electrocatalysts for methanol oxidation using new synthetic method facilitating deposition of Pt–Ru very thin nanoplatelets on carbon nanoparticles The method involves oxidation of carbon support, adsorption of Pb²⁺, its reduction and galvanic displacement of Pb⁰ by Pt and/or Ru. The Pt mass activity of this catalyst is about 10 times higher than that of the commercial Pt–Ru/C. The catalyst with the 1:1 Pt/Ru ratio displayed the highest methanol oxidation activity per surface Pt atom. Our results demonstrate the new synthetic method that yields the catalyst with potential for solving the problem of high Pt loading in direct methanol fuel cell anodes.