Role of Arg123 in Light‐driven Anion Pump Mechanisms of pharaonis Halorhodopsin†

Halorhodopsin (HR) acts as a light‐driven chloride pump which transports a chloride ion from the extracellular (EC) to the cytoplasmic space during a photocycle reaction that includes some photointermediates initiated by illumination. To understand the chloride uptake mechanisms, we focused on a basic residue Arg123 of HR from Natronomonas pharaonis (NpHR), which is the only basic residue located in the EC half ion channel. By the measurements of the visible absorption spectra in the dark and the light‐induced inward current through the membrane, it was shown that the chloride binding and transport ability of NpHR completely disappeared by the change of arginine to glutamine. From flashphotolysis analysis, the photocycle of R123Q differed from that of wildtype NpHR completely. The response of the R123H mutant depended on pH. These facts imply that the positive charge at position 123 is essential for chloride binding in the ground state and for the chloride uptake under illumination. On the basis of the molecular structures of HR and the anion‐transportable mutants of bacteriorhodopsin, the effects of the positive charge and the conformational change of the Arg123 side chain as well as the chloride‐pumping mechanism are discussed.     

Stepwise phosphine sulfide formation and metal-bridging reaction of tetradentate and tridentate phosphine ligands on palladium(II)

Kinetic studies on the stepwise phosphine sulfide formation reaction of the five-coordinate trigonal-bipyramidal Pd(II) complexes with the tripodal tetradentate phosphine ligand, [PdCl(pp₃)]Cl and [Pd(4-Cltp)(pp₃)](BF₄) (pp₃ = tris[2-(diphenylphosphino)ethyl]phosphine; 4-Cltp = 4-chlorothiophenolate), were carried out, and it was revealed that the reactions proceeded via the intermediate with a pendant dissociated phosphino group. Formation of the intermediate was utilized for the bridging reaction onto Pt(II) to form the phosphine-bridged linear trinuclear and cyclic tetranuclear mixed-metal complexes. Difference in the steric conversion mechanism in the phosphine-bridging reaction between the linear tridentate phosphine (bis[2-(diphenylphosphino)ethyl]phenylphosphine) and pp₃ is also reported.     

Rapid enantioseparation of 1-aminoindan by microchip electrophoresis with linear-imaging UV detection.

Chiral separations of 1-aminoindan (AI) by cyclodextrin electrokinetic chromatography (CDEKC) were investigated on microfluidic quartz chips. By using a microchip electrophoresis (MCE) instrument equipped with a linear-imaging UV detector, the separation process of the enantiomeric compounds was observed. When sulfated beta-cyclodextrin was employed as a chiral selector, the baseline separation of AI could be achieved within 1 min with a high repeatability. The relative standard deviation of the migration time was less than 6%. The fastest separation was achieved in 14 s, utilizing a separation length of only 6.1 mm. These results show that the MCE analysis employing a linear imaging UV detector has a significant potential for fast chiral analysis.     

Analysis of the3 He(K−,K +)n reaction by the potential quark model

We analyze the production of H dihyperson (J ^π=0⁺,S=?2) via the (K ^?, K⁺) reaction by means of the non-relativistic quark model. First, the H mass and mass spectrum of single baryons are calculated. When the single baryon spectrum is well reproduced, the H dihyperson has the binding energies about 20 MeV or 60 MeV corresponding to the choice of the strength of the confinement potential. Using this model and parameters, cross sections for H production are estimated. A new effect, contributions from color-octetQ ³?Q ³ components of H dihyperson, is taken into account. The cross sections for H production are enhanced about ten times by these contributions. TheK ⁺-neutron coincidence cross section for H production is found to be 99–115 nb/sr² at theK ⁺ forward direction forM _H=2212 MeV and theK ^? beam momentum 1.8 GeV/c.     

Sensitized luminescence properties of dinuclear lanthanide macrocyclic complexes bearing a benzophenone antenna

Dinuclear lanthanide (Ln=Tb³⁺ or Eu³⁺) complexes (Ln₂L2) of two octadentate macrocyclic polyaminopolycarboxylic ligands connected through a benzophenone (BP) moiety (L2) have been synthesized. Sensitized luminescence properties of Ln₂L2 in water have been studied in comparison to those of BP-conjugated mononuclear Ln complexes (LnL1). The luminescence intensity of Tb₂L2 is lower than that of TbL1 because of lower triplet quantum yield of the BP moiety. In contrast, Eu₂L2 shows higher intensity than EuL1. For both Eu complexes, energy level of triplet excited-state BP (³BP*) is only 3 kJ mol⁻¹ higher than that of ⁵D₂ excited-state of Eu³⁺. The ⁵D₂ state formed by a triplet-energy transfer (TET) from ³BP* is therefore deactivated by a back energy transfer (BET) to the ground-state BP, resulting in low luminescence intensity of EuL1. In contrast, within Eu₂L2, TET from ³BP* to ⁵D₀ state of two Eu³⁺ ions is accelerated, thus leading to higher luminescence intensity. Another notable feature of Eu₂L2 is the luminescence quantum yield independent of its concentration. In contrast, for EuL1 system, an intermolecular BET occurs from ⁵D₂ state of Eu³⁺ to the ground-state BP conjugated to another EuL1 complex, resulting in a yield decrease with the concentration increase.     

Biospecific thermal analyzer coupled with a flowthrough immobilized enzyme column

A thermal analyzer consisting of a pair of glass thermistors was coupled with a flowthrough immobilized enzyme reactor for the determination of ATP concentration. Hexokinase was covalently bound to poly(chloromethyl-styrene-divinyl benzene) beads and packed in the reactor. The thermal analyzer was designed so as to respond to heat generation in the reactor. A maximum temperature change was exhibited within 1.5 min after the injection of a sample solution containing ATP together with glucose. Thermal decay occurred within 1 min. The thermal analyzer responded reproducibly to ATP at a constant concentration. Assays could be repeated at 3-min intervals. The effects of sample volume and flow rate on the response were examined with regard to an empirical equation. Concentration of ATP was determined with the thermal analyzer in the range of 0-10 mM. The thermal analyzer may be a simple device for the rapid determination of ATP concentration.     

1-vinylbenzene 1,2- and 3,4-oxides

Synthesis of highly unstable vinyl-substituted benzene oxides has been established.     

Temperature dependence of local density augmentation for acetophenone N,N,N',N'-tetramethylbenzidine exciplex in supercritical water

Local density augmentation around exciplex between acetophenone and N,N,N',N'-tetramethylbenzidine in supercritical water was measured by observing the peak shift of transient absorption spectrum at temperatures from 380 to 410 degrees C and at pressures from 6 to 37 MPa. Large local density augmentation was observed at lower solvent densities. Local density augmentation was evaluated by the excess density, which was defined as the difference between local density and bulk density, and the density enhancement factor, which was defined by the ratio of the local density to the bulk density. The number of solvating molecules was estimated with a Langmuir adsorption model. The excess density was found to exhibit a maximum at approximately 0.15 g cm(-3), which decreased with increasing temperature. The density enhancement factor was found to decrease with increasing temperature; however, its value was much greater than unity at 410 degrees C, which provides evidence that exciplex-water interactions still exist at these conditions. The temperature dependence of local density augmentation around the exciplex in supercritical water was comparable with that in supercritical carbon dioxide, which suggests that the ratios of the solute-solvent and solvent-solvent interactions are comparable between these two systems.     

Electrochemical typing of blood using affinity membranes

Human blood group substance of the ABO system was immobilized in a mebrane matrix. The membrane-bound blood group substance retained its binding ability against the corresponding antibody (agglutinin) in serum. The transmembrane potential changed drastically with the agglutination of the membrane-bound blood group substance. Electrochemical typing of blood was performed with sera, using a pair of membranes with immobilized A- and B-type blood group substances. The blood type was determined by measuring the transmembrane potential across these membranes before and after the agglutination reaction. A possible re-use of the membrane-bound blood group substance by treatment with galactose is discussed.     

Magnetic field effect on the pairing state competition in quasi-one-dimensional organic superconductors (TMTSF)2X

We study the effect of the magnetic field on the pairing state competition in organic conductors (TMTSF)₂X by applying random phase approximation to a quasi-one-dimensional extended Hubbard model. We show that the singlet pairing, triplet pairing and the Fulde–Ferrell–Larkin–Ovchinnikov (FFLO) superconducting states may compete when charge fluctuations coexist with spin fluctuations. This rises a possibility of a consecutive transition from singlet pairing to FFLO state and further to S_z = 1 triplet pairing upon increasing the magnetic field. We also show that the singlet and S_z = 0 triplet components of the gap function in the FFLO state have “d-wave” and “f-wave” forms, respectively, which are strongly mixed.