Synthesis of New Lithium Ionic Conductor Thio-LISICON—Lithium Silicon Sulfides System

The new lithium ionic conductors, thio-LISICON (LIthium SuperIonic CONductor), were found in the ternary Li₂S-SiS₂-Al₂S₃ and Li₂S-SiS₂-P₂S₅ systems. Their structures of new materials, Li_4+xSi_1−xAl_xS₄ and Li_4−xSi_1−xP_xS₄ were determined by X-ray Rietveld analysis, and the electric and electrochemical properties were studied by electronic conductivity, ac conductivity and cyclic voltammogram measurements. The structure of the host material, Li₄SiS₄ is related to the γ-Li₃PO₄-type structure, and when the Li⁺ interstitials or Li⁺ vacancies were created by the partial substitutions of Al³⁺ or P⁵⁺ for Si⁴⁺, large increases in conductivity occur. The solid solution member x=0.6 in Li_4−xSi_1−xP_xS₄ showed high conductivity of 6.4×10^-4 S cm⁻¹ at 27°C with negligible electronic conductivity. The new solid solution, Li_4−xSi_1−xP_xS₄, also has high electrochemical stability up to ∼5 V vs Li at room temperature. All-solid-state lithium cells were investigated using the Li_3.4Si_0.4P_0.6S₄ electrolyte, LiCoO₂ cathode and In anode.     

Thermal analysis graphite intercalation compounds with dichlorides of some d-elements: A.S. Skoropanov,G.S. Petrov,A.A. Vecher,Yu.N. Novikov and M.E. Vol'pin,Thermochim. Acta, 90 (1985) 339-342

Kinetic and thermodynamic aspects of the axial base dissociation of solid Co(salen) (X-py) complexes, X = H (1), 3-Me (2), 4-Me (3), 3,4-Me₂ (4), 3,5-Me₂ (5), 3-NH₂ (6), 3-Cl (7), 3-CN (8), 4-CN (9), have been investigated by means of TG-DSC and isothermal weight-loss measurements. These adducts endothermically dissociate the axial base giving rise to the oxygen-active Co(salen) complex. The axial base dissociation reactions fit the contracting disc equation and the kinetic compensation effect is observed for all the adducts excepting Adducts 4–6. For the remaining adducts the kinetic and thermodynamic stabilities of the Co-(X-py) bond are found to increase linearly with increasing Hammett's substitution constants of X except for Adducts 3 and 9. These results are discussed in terms of the σ and π interactions between cobalt(II) and substituted pyridine. Factors dominating the kinetic bond stability are briefly discussed.     

Flow amperometric detection of indigo for enzyme-linked immunosorbent assays with use of screen-printed electrodes

A simple and automated methodology for a sensitive electrochemical detection of enzyme immunoassays that employ alkaline phosphatase (AP) as label has been developed. A flow injection system with programmable pump, valve and cell functions, amperometric detection of indigo and screen-printed electrodes (SPEs) are responsible for the advantages of this methodology. Amperometric detection at a low potential of indigo, the product of the enzymatic hydrolysis of the substrate 3-indoxyl phosphate (IP), is combined with a flow injection system. This incorporates in the flow cell a disposable screen-printed board provided with a graphite working electrode. No electrode pretreatment is necessary to obtain reproducible signals. The system was applied to the determination by an enzyme-linked immunosorbent assays (ELISA) of pneumolysin (PLY), a toxin related to respiratory infections. Linear calibration curves for low and high concentration ranges were obtained. These were also performed in a proteic matrix and linearity was also obtained.     

Photoinduced ionic polymerization. III. Cationic polymerization and copolymerization of cyclohexene oxide and α-methylstyrene in the presence of pyromellitic dianhydride

The photoinduced ionic polymerization of cyclohexene oxide was studied in the presence of pyromellitic dianhydride. The polymerization is initiated by the excited chargetransfer complex between cyclohexene oxide and the electron-acceptor and proceeds by a cationic mechanism. Photoinduced cationic polymerization of α-methylstyrene was also observed in the presence of pyromellitic dianhydride. The initiation mechanism of the polymerization was elucidated by means of electron spin resonance measurements. The concentration of pyromellitic dianhydride anion-radicals measured in this way was found to be proportional to the rate of polymerization. This result shows clearly that the photopolymerization is initiated by cation-radicals formed from photoexcited donoracceptor complexes. The attempted photocopolymerization of cyclohexene oxide and α-methylstyrene gave a mixture of homopolymers. The composition of the product depends on the wavelength of the light used.     

Photoinduced ionic polymerization. II. Cationic polymerization of α-methylstyrene in the presence of tetracyanobenzene

The dependence of the rate of polymerization on light intensity and the stereoregularity of the polymer was studied to elucidate the propagation and termination mechanisms of the photoinduced cationic polymerization of α-methylstyrene in the presence of tetracyanobenzene in methylene chloride. The rate of polymerization was proportional to the light intensity. The polymer is highly syndiotactic, and the stereoregularity is similar to that of polymers obtained by radiation-induced cationic polymerization. The initiation mechanism was also studied by electron spin resonance, by which the anion radical of tetracyanobenzene formed from a photoexcited complex between α-methylstyrene and tetracyanobenzene was observed. The cation radical of α-methylstyrene, counterpart of the anion radical, is believed to initiate the polymerization.     

Metallic behavior and periodical valence ordering in a MMX chain compound, Pt(2)(EtCS(2))(4)I.

A new one-dimensional (1-D) halogen-bridged mixed-valence diplatinum(II,III) compound, Pt(2)(EtCS(2))(4)I (3), has been successfully synthesized from [Pt(2)(EtCS(2))(4)] (1) and [Pt(2)(EtCS(2))(4)I(2)] (2). These three compounds have been examined using UV-visible-near-IR, IR, polarized Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray crystal structure analyses (except for 1). Compound 3 was further characterized through electrical transport measurements, determination of the temperature dependence of lattice parameters, X-ray diffuse scattering, and SQUID magnetometry. 3 crystallizes in the monoclinic space group C2/c and exhibits a crystal structure consisting of neutral 1-D chains with a repeating -Pt-Pt-I- unit lying on the crystallographic 2-fold axis parallel to the b axis. The Pt-Pt distance at 293 K is 2.684 (1) A in the dinuclear unit, while the Pt-I distances are essentially equal (2.982 (1) and 2.978 (1) A). 3 shows relatively high electrical conductivity (5-30 S cm(-1)) at room temperature and undergoes a metal-semiconductor transition at T(M-S) = 205 K. The XPS spectrum in the metallic state reveals a Pt(2+) and Pt(3+) mixed-valence state on the time scale of XPS spectroscopy ( approximately 10(-17) s). In accordance with the metal-semiconductor transition, anomalies are observed in the temperature dependence of the crystal structure, lattice parameters, X-ray diffuse scattering, and polarized Raman spectra near T(M-S). In variable-temperature crystal structure analyses, a sudden and drastic increase in the Pt-I distance near the transition temperature is observed. Furthermore, a steep increase in U(22) of iodine atoms in the 1-D chain direction has been observed. The lattice parameters exhibit significant temperature dependence with drastic change in slope at about 205-240 K. This was especially evident in the unit cell parameter b (1-D chain direction) as it was found to lengthen rapidly with increasing temperature. X-ray diffraction photographs taken utilizing the fixed-film and fixed-crystal method for the metallic state revealed the presence of diffuse scattering with line shapes parallel to the a* axis indexed as (-, n + 0.5, l) (n; integer). Diffuse scattering with k = n + 0.5 is considered to originate from the 2-fold periodical ordering corresponding to -Pt(2+)-Pt(2+)-I-Pt(3+)-Pt(3+)-I- or -Pt(2+)-Pt(3+)-I-Pt(3+)-Pt(2+)-I- in an extremely short time scale. Diffuse lines corresponding to 2-D ordering progressively decrease in intensity below 252 K and are converted to the diffuse planes corresponding to 1-D ordering near T(M-S). Furthermore, diffuse planes condensed into superlattice reflections below T(M-S). Polarized Raman spectra show temperature dependence through a drastic low-energy shift of the Pt-I stretching mode and also through broadening of bands above T(M-S).     

Determination of bithionol, bromophen, nitroxynil, oxyclozanide, and tribromsalan in milk with liquid chromatography coupled with tandem mass spectrometry

LC/MS/MS was developed to determine the residues of bithionol (BTN), bromofen (BMF), nitroxynil (NTX), oxyclozanide (OCZ), and tribromsalan (TBS) in milk. Samples were extracted with ethyl acetate and cleaned up by liquid-liquid separation with acetonitrile and n-hexane. The compounds were determined by RP-LC using a C18 column with 0.1% formic acid-methanol. Mass spectral acquisition was performed in the negative mode by applying selected-reaction monitoring. The method was validated in milk spiked with these compounds at 5-600 microg/kg; average recoveries were in the range 83.8-97.1%, with RSD values of 1.4-8.0%. The interassay RSDs were less than 11%. The LODs of these compounds in milk were 0.1 microg/kg. The method was applied to 24 raw milk samples. The concentration of these compounds in all samples was lower than the Japanese maximum residue limits. The method is rapid, sensitive, and specific for monitoring residues of BTN, BMF, NTX, OCZ, and TBS in milk.     

Parametrization of calcium binding site in proteins and molecular dynamics simulation on phospholipase A2

The empirical energy parameters for a calcium ion and its ligands in proteins were determined within a pairwise additive framework. The interaction energies of Ca²⁺-water, Ca²⁺-peptide group and Ca²⁺-carboxyl group systems were calculated using the ab initio molecular orbital method with basis sets of double zeta quality including polarization or diffuse functions. The resulting potential energy surfaces served as references for the determination of the nonbonded parameters in the empirical energy function. The nonadditive corrections for the Ca²⁺-ligand pair potentials are incorporated implicitly in the nonbonded paremeters by treating three-body (1:2 complex) or seven-body (1:6 complex) systems in reference calculations. Ligand polarizations induced by Ca²⁺ are estimated from the partial atomic charges of two-body (1:1 complex) systems. The charge sets were determined by scaling so as to reproduce the reference potential energy surfaces. The newly determined parameter set was used in a stochastic boundary molecular dynamics simulation of phospholipase A₂. The solvated structure of the Ca²⁺-binding site obtained from an X-ray crystallographic study is well reproduced by the parameter set.