Syntheses and physical properties of quasi-one-dimensional halogen-bridged Cu(II)(-)Pt(IV) mixed-metal complexes [Cu(chxn)(2)][PtX(2)(chxn)(2)]X(4).

Quasi-one-dimensional halogen-bridged Cu(II)-Pt(IV) mixed-metal complexes of the form [Cu(chxn)(2)][PtX(2)(chxn)(2)]X(4), where chxn = 1R,2R-diaminocyclohexane and X is either Cl or Br, have been synthesized. The crystal structures of these compounds have been determined by single-crystal X-ray diffraction. The Cl-bridged compound crystallizes in the space group I222 with dimensions a = 24.237(1) A, b = 5.103(1) A, c = 6.854(1) A, and V = 847.7(1) A(3) and with Z = 1. The Br-bridged complex crystallizes in the space group I222 with dimensions a = 23.700(8) A, b = 5.344(5) A, c = 6.978(8) A, and V = 883.8(8) A(3) and with Z = 1. These structures are isomorphic to each other and to homometal [Pt(chxn)(2)][PtX(2)(chxn)(2)]X(4) complexes. In these complexes, the planar [Cu(chxn)(2)] and the octahedral [PtX(2)(chxn)(2)] groups are stacked alternatively with the axial bridging halogen ions, forming linear chain structures. The neighboring [Cu(chxn)(2)] and [PtX(2)(chxn)(2)] moieties along the chains are linked by hydrogen bonds between amino hydrogens and the counteranions (X). Moreover, there are hydrogen bonds among the neighboring chains that form a two-dimensional hydrogen-bonded network parallel to the bc plane. Therefore, the Cu(II) and Pt(IV) units are two-dimensionally ordered. The b axes correspond to the Cu(II)-Pt(IV) separations, which are shorter than those of [Pt(chxn)(2)][PtX(2)(chxn)(2)]X(4) due to the smaller ionic radius of the Cu(II) ions. In the XP spectra, the Pt(IV) 4f(7/2) and Pt(IV) 4f(5/2) binding energies in homometal [Pt(chxn)(2)][PtX(2)(chxn)(2)]X(4) are lower than those of [Cu(chxn)(2)][PtX(2)(chxn)(2)]X(4) (X = Cl and Br), indicating that the electron-phonon interaction in Cu(II)-Pt(IV) compounds is stronger than that in Pt(II)-Pt(IV) compounds. In the Raman spectra, nu(Pt(IV)(-)X) of the homometal Pt(II)-Pt(IV) complexes is lower than that of the Cu(II)-Pt(IV) complexes, indicating again that the electron-phonon interaction in Cu(II)-Pt(IV) compounds is stronger than that of Pt(II)-Pt(IV) compounds. The temperature-dependent magnetic susceptibilities of the Cu(II)-Pt(IV) complexes show weak antiferromagnetic interactions between Cu(II) components along the chain axes.

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).

Changes in subjective sleepiness, subjective fatigue and nocturnal sleep after anaesthesia with propofol.

The purpose of this study was to clarify the changes in psycho-physiological functions after anaesthesia with propofol (PF). The subjects were seven healthy male volunteers and the duration of the anaesthesia was 1 h (14:00-15:00 h). The plasma concentration of PF immediately decreased after the anaesthesia. The subjective sleepiness and VAS (visual liner analogue scale) scores (i.e. effort to do something) increased significantly at 20 min after the anaesthesia. However, these changes were improved at 80 min after the anaesthesia. The sleep latency at the nocturnal sleep 8 h after the anaesthesia was prolonged significantly, but the other parameters including the distributions of stage 3 + 4 and the rapid eye movement 'REM' stage were not changed.

[Differential reactivities of three kinds of carbon dioxide absorbents with high concentration of sevoflurane].

The differential reactivities of three kinds of carbon dioxide absorbents, sodalime, Sodalime A and Baralyme with 5% sevoflurane were investigated in a closed system under administration of 5% carbon dioxide. The degradation products in the closed system were determined by gas chromatography and the temperature of the glass container which was filled with each carbon dioxide absorbent was monitored. The degradation products, P1, P3 and P5 were produced by every carbon dioxide absorbents even after one-hour circulation. Especially P3 and P5 were produced by Baralyme more than the others after two or four-hour circulation. The significant differences of the temperature among glass containers were not recognized. Previously we found that the reactivity of Sodalime A is the highest among the three kinds of carbon dioxide absorbents when low concentration of sevoflurane (2 or 3%) is used. Possible explanation for this result is that the increasing temperature of glass container filled with each carbon dioxide absorbent is different from each other, and Sodalime A is the highest. The reactivity was thought to depend on the temperature of glass container. However, with this high concentration of sevoflurane (5%), Baralyme has the highest reactivity. Baralyme contains higher proportion of KOH which has the highest reactivity with sevoflurane than the other constituents of carbon dioxide absorbents. The reactivity of sodalime, Sodalime A and Baralyme with 5% sevoflurane was thought to depend not on their temperature but on their chemical constitutions. These results suggested that the using high concentration sevoflurane with Baralyme should be reconsidered.