Direct transformation of ice VII′ to low-density amorphous ice

Vibrational spectra reveal that ice VII′ transforms to low-density amorphous ice (LDA) at low temperature on release of pressure to ambient pressure and low temperature. The measurements were obtained using in situ Raman spectroscopy of samples of ice VII′ as a function of pressure at 135 K. The observation of this direct decompression-induced VII′-LDA transition complements the previously observed pressure-induced reversible transition between LDA and high-density amorphous ice (HDA) at 120–140 K and the temperature-induced amorphization of metastable ice VII and ice VIII at 0.1 MPa.     

Charge-induced spin alignment in diradical donor molecules: numerical calculations of correlated many-electron-spin systems

The mechanism of charge-induced high spin is studied in pi-conjugated molecules by means of a model-Hamiltonian approach. Intersite Coulomb interactions are taken into account in a pi-conjugated moiety, which is coupled with two localized spins through exchange interactions. We clarify spin alignment in neutral and oxidized states by exact numerical calculations including all the correlation effects. In thianthrene-based molecules, one-electron oxidation induces strong ferromagnetic correlation between the localized spins irrespective of the spin alignment in the neutral state. The localized spins are coupled to the delocalized hole spin ferromagnetically, leading to a high-spin state in the oxidized molecule. Our calculations on structural dependence and effective exchange interaction are consistent with the recent experiment of thianthrene bis(nitronyl nitroxide). By comparing the thianthrene-based molecule with the anthracene-based one, we clarify the role of superexchange interactions via the sulfur atoms.     

Study on multimers and their structures in molecular association mixture

Self-association system of(R)-1,3-butanediol in dilute carbon tetrachloride(CCl4)solution is studied as a model of molecular association mixture.Analysis methods including FSMWEFA(fixed-size moving window evolving factor analysis)combined with PCA(principal component analysis),SIMPLISMA (simple-to-use interactive self-modeling mixture analysis),and ITTFA(iterative target transformation factor analysis)are adopted to resolve infrared spectra of(R)-1,3-butanediol solution.Association number and equilibrium constant are computed.(R)-1,3-butanediol in dilute inert solution is determined as a monomer-trimer equilibrium system.Theoretical investigation of trimer structures is carried out with DFT(density functional theory),and structural factors are analyzed.     

Adsorption and reactions of NO on clean and CO-precovered Ir(111)

Adsorption and reactions of NO on clean and CO-precovered Ir(111) were investigated by means of X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HR-EELS), infrared reflection absorption spectroscopy (IRAS), and temperature-programmed desorption (TPD). Two NO adsorption states, indicative of fcc-hollow sites and atop sites, were present on the Ir(111) surface at saturation coverage. NO adsorbed on hollow sites dissociated to Na and Oa at temperatures above 283 K. The dissociated Na desorbed to form N2 by recombination of Na at 574 K and by a disproportionation reaction between atop-NO and Na at 471 K. Preadsorbed CO inhibited the adsorption of NO on atop sites, whereas adsorption on hollow sites was not affected by the coexistence of CO. The adsorbed CO reacted with dissociated Oa and desorbed as CO2 at 574 K.     

Separation of N2-ethyl-2'-deoxyguanosine-5'-monophosphate and four native deoxyribonucleoside monophosphates using capillary zone electrophoresis with polyethylene glycol as buffer additive

We investigated the separation of five deoxyribonucleoside monophosphates: 2'-deoxyguanosine-5'-monophosphate (dGMP), 2'-deoxyadenosine-5'-monophosphate (dAMP), 2'-deoxycytosine-5'-monophosphate (dCMP), 2'-deoxythymidine-5'-monophosphate (dTMP) and a dGMP adduct possessing N2-ethyl-guanine, which has been noted in relation to mutagenesis of alcohol, using capillary zone electrophoresis (CZE). The concentration of polyethylene glycol (PEG) as a modifier and the pH of the running solutions can efficiently control the observed separation. Interaction of PEG with analytes was quantitatively evaluated. PEG worked effectively as a hydrophobic selector in these separations. The values of pKa of the acidic-NH-groups in the base moieties of dGMP, dTMP, and the dGMP adduct are close to that of boric acid used as buffer of the running solutions. The control of their charge was facilitated, enabling improved separations. A more sufficient and fast separation was achieved by both optimization of pH of the running solutions and PEG concentration compared with that obtained by pH control alone. On-line concentration using a stacking method followed by the PEG-assisted CZE was briefly studied.     

Synthesis and crystal structure of ionic multicomponent complex: ([Cr(I)(PhH)(2)].+))(2)[Co(II)TPP(C(60)(CN)(2))]-[C(60)(CN)(2)](.-).3(o-C(6)H(4)Cl(2)) containing C(60)(CN)(2).- radical anion and sigma-bonded diamagnetic Co(II)TPP(C(60)(CN)(2)) -anion

The ionic multicomponent complex complex: ([Cr(I)(PhH)(2)].+))(2)[Co(II)TPP(C(60)(CN)(2))]-[C(60)(CN)(2)](.-).3(o-C(6)H(4)Cl(2)) (Co(II)TPP: cobalt (II) tetraphenylporphyrin; Cr(PhH)(2): bis(benzene)chromium; o-C(6)H(4)Cl(2): o-dichlorobenzene) containing CoTPP(C(60)(CN)(2)- anion and C(60)(CN)(2).- radical anion was obtained. The complex has the cage structure with channels, which accommodate Cr(I)(PhH)(2)(.+) and o-C(6)H(4)Cl(2) molecules. For the first time the sigma-bonding of Co(II)TPP to the fullerene radical anion with the essentially shortened Co.C(C(60)(CN)(2)) contact of 2.282 A is observed. The sigma-bonding results in the diamagnetism of Co(II)TPP(C(60)(CN)(2))(-) anion. The nonbonded C(60)(CN)(2)(.-) radical anion retains both the C(2)(v)symmetry and the shape of the molecule. The length of the C(triple bond)N bonds is 1.141 and 1.152 A.     

Mechanism of Mukaiyama-Michael Reaction of Ketene Silyl Acetal: Electron Transfer or Nucleophilic Addition?

Mechanism of Mukaiyama-Michael reaction of ketene silyl acetal has been discussed. The competition reaction employing various types of ketene silyl acetals reveals that those bearing more substituents at the beta-position react preferentially over less substituted ones. However, when ketene silyl acetals involve bulky siloxy and/or alkoxy group(s), less substituted compounds react preferentially. The Lewis acids play an important role in these reactions. Enhanced preference for the more sterically demanding Michael adducts is obtained with Bu(2)Sn(OTf)(2), SnCl(4), and Et(3)SiClO(4) in the former reaction while TiCl(4) gives the highest selectivity for the less sterically demanding products in the latter case. These results are interpreted in terms of alternative reaction mechanisms. The reaction of less bulky ketene silyl acetals are initiated by electron transfer from these compounds to a Lewis acid. On the other hand, bulkier ketene silyl acetals undergo a ubiquitous nucleophilic reaction. Such a mechanistic change is discussed based on a variety of experimental results as well as the semiempirical PM3 MO calculations.     

Development of miniaturized multi-channel high-performance liquid chromatography for high-throughput analysis

We have developed miniaturized multi-channel high-performance liquid chromatography (HPLC) system. With this system, we can simultaneously separate multiple samples, using a single high-pressure gradient pump, a chip-based sample injection unit, a monolithic silica capillary column array, and a multi-channel UV detection unit based on fiber optics. The injection unit has a simplified structure composed of brass housing and a quartz microchip having microchannels and access ports, which enable a direct injection of sample to multi-channel by commercial multichannel micropipette. Moreover, that possesses a function of microvalve, and on-chip definition of sample injection plugs achieved with a cross channel injection method, providing each column of monolithic silica capillary array. The substances in channels were simultaneously detected with UV having multiple cells. Standard samples were analyzed for characterizing newly developed system, and sharp peaks were obtained with reproducibility data of < 0.9% (R.S.D.). Analysis of tryptic digestion of casein was also employed. These results show that the novel multi-channel HPLC system has the benefits for the high-throughput analysis in the post-genomic analysis/combinatorial chemistry.