Effect of included guest molecules on the normal state conductivity and superconductivity of beta''-(ET)(4)[(H(3)O)Ga(C(2)O(4))(3)].G (G = pyridine,nitrobenzene)

Normal state conductivity and superconductivity together with bulk magnetic susceptibility and magnetization measurements have been measured for two molecular charge-transfer salts: beta' '-(ET)4[(H3O)Ga(C2O4)3]G (ET = bis(ethylenedithio)tetrathiafulvalene, G = pyridine for compound I and nitrobenzene for compound II). With the exception of the included guest molecules (G) the crystal structures are almost identical. Both show minima in their electrical transport at 130 K for I and at 160 K for II, but at lower temperatures their behaviors differ markedly. The resistance of I reaches a maximum at 50 K with a further small peak at 2 K and possible superconductivity only below 2 K, whereas that of II increases continuously down to 7.5 K, where an abrupt transition to a superconducting state occurs.     

Les reactions de redistribution dans la chimie du bore. Etude des reactions de competition des groupements NMe2, Cl,SMe, OMe,F sur des centres bore mono et difonctionnels R2B- ET RB<

A quantitative ¹H and ¹¹B NMR study of the redistribution equilibria between the NMe₂ group and the Cl, SMe,OMe and F substituents on the mono and difunctional boron centers (R₂B- and RB<) is reported. The preferential affinity of the amino group towards dialkylated boron centers is shown by the examination of the “intersystem” constant sets. A relative affinity scale is proposed.     

缓慢炭化部分氧化对制备煤质活性炭的影响

研究了炭化升温速度、炭化低温区引入空气部分氧化对活性炭制备过程中炭化阶段、炭化物结构、活性炭性能等的影响。结果表明，炭化时低温部分氧化可提高炭化物得率，使炭化物微晶的ｄ００２值升高和Ｌｃ值减小；而较慢的炭化升温速度有利于制备优质活性炭。缓慢炭化、部分氧化可以在一定程度上控制炭化路径，使炭化向生成取向性差、难石墨化、各向同性、呒定形炭多的炭化物的方向进行；并讨论了它们控制炭化的作用机理。以此为指导，     

Electrophoretic separations of twelve phenothiazines and N-demethyl derivatives by using capillary zone electrophoresis and micellar electrokinetic chromatography with non ionic surfactant

We focused our work on the separation of phenothiazines that are important drugs used for the treatment of psychic diseases. For a better understanding of the metabolism of these solutes, we wanted to separate not only a mixture of 12 phenothiazines but also a mixture containing phenothiazines and their N-demethyl metabolites by capillary electrophoresis. Separations in capillary zone electrophoresis were performed using 3 x 10(-2) mol/L H3PO4 (pH 2.5) but the obtained resolutions were not entirely satisfactory especially with regard to phenothiazine -N-demethyl derivative pairs. To improve the obtained results, we have performed separations by using micellar electrokinetic chromatography. In this approach, we used a running electrolyte containing 3 x 10(-2) mol/L H3PO4 electrolyte (pH 2.5) and octaethylene glycol monododecyl ether (C12E8) as neutral surfactant. By introducing 2 x 10(-3) mol/L C12E8 in the electrolyte, 11 out of 12 phenothiazines have been baseline separated. With respect to the separation of a mixture containing 3 phenothiazines and their 3 demethyl derivatives, we obtained an excellent separation by using a running electrolyte prepared with 7.5 x 10(-4) mol/L C12E8 and 3 x 10(-2) mol/L H3PO4.     

Sterically controlled reductive oligomerisations of CO by activated magnesium(i) compounds: deltate vs. ethenediolate formation

An extremely bulky, symmetrical three-coordinate magnesium(i) complex, [{(^TCHPNacnac)Mg}₂] (^TCHPNacnac = [{(TCHP)NCMe}₂CH]⁻, TCHP = 2,4,6-tricyclohexylphenyl) has been prepared and shown to have an extremely long Mg–Mg bond (3.021(1) Å) for such a complex. It was shown not to react with either DMAP (4-dimethylaminopyridine) or CO. Three unsymmetrical 1 : 1 DMAP adducts of less bulky Mg–Mg bonded species have been prepared, viz. [(^ArNacnac)Mg–Mg(DMAP)(^ArNacnac)] (^ArNacnac = [(ArNCMe)₂CH]⁻ Ar = 2,6-xylyl (Xyl), mesityl (Mes) or 2,6-diethylphenyl (Dep)), and their reactivity toward CO explored. Like the previously reported bulkier complex, [(^DipNacnac)Mg–Mg(DMAP)(^DipNacnac)] (Dip = 2,6-diisopropylphenyl), [(^DepNacnac)Mg–Mg(DMAP)(^DepNacnac)] reductively trimerises CO to give a rare example of a deltate complex, [{(^DepNacnac)Mg(μ-C₃O₃)Mg(DMAP)(^DepNacnac)}₂]. In contrast, the two smaller adduct complexes react with only two CO molecules, ultimately giving unusual ethenediolate complexes [{(^ArNacnac)Mg{μ-OC(H) C(DMAP^−H)O}Mg(^ArNacnac)}₂] (Ar = Xyl or Mes). DFT calculations show the latter reactions to proceed via reductive dimerizations of CO, and subsequent intramolecular C–H activation of Mg-ligated DMAP by “zig–zag” [C₂O₂]²⁻ fragments of reaction intermediates. Calculations also suggest that magnesium deltate complexes are kinetic products in these reactions, while the magnesium ethenediolates are thermodynamic products. This study shows that subtle changes to the bulk of the reacting 1 : 1 DMAP–magnesium(i) adduct complexes can lead to fine steric control over the products arising from their CO reductive oligomerisations. Furthermore, it is found that the more activated nature of the adduct complexes, relative to their symmetrical, three-coordinate counterparts, [{(^ArNacnac)Mg}₂], likely derives more from the polarisation of the Mg–Mg bonds of the former, than the elongated nature of those bonds.

Subtle changes to the bulk of 1 : 1 adducts of DMAP with magnesium(i) complexes leads to steric control over the products arising from their reductive oligomerisations of carbon monoxide.      

Pt- (and Co-) Promoted Molybdena-Alumina Catalysts: Analysis of the Impregnation Steps

The equilibrium parameters for the adsorption of Mo(VI) on gamma-Al(2)O(3) and of Co(II) and Pt(IV) on MoO(3)/gamma-Al(2)O(3) were determined. The adsorption isotherms were performed from aqueous solutions of the corresponding precursors on two different alumina supports. According to the classification given by Giles, L-type-shaped, subgroup 2, adsorption curves were found for the system Mo on gamma-Al(2)O(3), L-type, subgroup 1, for the Pt on MoO(3)/gamma-Al(2)O(3), and S-type for Co on the MoO(3)/gamma-Al(2)O(3) system. Numerical calculations were carried out for all the isotherms to find the equilibrium parameters. These constants are being used to model the development of Pt, Co, and Mo profiles on MoO(3)/gamma-Al(2)O(3) or gamma-Al(2)O(3) extrudates, respectively, which belong to the new generation of noble-metal-MoO(3)/gamma-Al(2)O(3)-supported catalysts to be used in oil-refining processes. Copyright 2001 Academic Press.     

Matched/Mismatched interaction of a cyclic hexapeptide with ion pairs containing chiral cations and chiral anions

The binding of a chiral quaternary ammonium ion to a cyclopeptide containing aromatic amino acid subunits is affected not only by the configuration of the cation but also by the configuration of the chiral counterion. Analysis of the binding equilibria shows that complex formation involves interaction of the whole ion pair with the host indicating that steric requirements of the anion influence complex geometry and stability.     

Immunoassay of P-glycoprotein on single cell by capillary electrophoresis with laser induced fluorescence detection

The cellular mechanism based on P-glycoprotein (PGP) for its drug pump function has become very important in multidrug resistance (MDR) research. A method has been established to characterize PGP on single K562 cell by coupling capillary electrophoresis with laser induced fluorescence detection. A permeable intact cell after the immunoassay binding with fluorescence labeling antibody was injected into the capillary and directly separated without lysis. It was found that once 5-10 optional cells were detected in batch, the PGP amount on this cell line could be outlined and calculated clearly. The PGP amount on K562 MDR cell line is 3.88 times higher than that on K562 sensitive cell line. These two cell lines with immunoassay binding were also analyzed by injection of multi-cells in order to improve the throughput. A resistance factor so called multidrug resistance multiple (MRM) was introduced to evaluate the MDR difference between cell lines. The MRM values of the cell line K562 measured by single cell analysis are well correlated with those by flow cytometry, which also prove the validity of our method in single cell analysis for the possibility of cancer diagnosis, pharmacokinetics and drug screening in future.