Synthesis and molecular structure of [Al(CH3)2]2[C10H22N4] [Al(CH3)3]2: Condensation product of trimethylaluminum and a multidentate open-chain amine

The crystalline condensation product [Al(CH₃)₂]₂[C₁₀H₂₂N₄][Al(CH₃)₃]₂ is prepared from reaction of the multidentate open-chain amine 1,4-bis(3-aminopropyl)piperazine with trimethylaluminum in methylene chloride. The compound crystallized in the monoclinic space groupC2/c with unit cell parametersa=25.166(12),b=7.268(4),c=17.316(4) Å,=115.3(4)°, andD _c =1.06 g cm^–3 forZ=4. Least-squares refinement based on 1054 observed reflections with intensitiesI 3(I) in the range 2<2<45° led to a finalR factor of 0.053 (R _w =0.064). The title compound resides on a crystallographic center of symmetry with independent Al-N distances of 1.889(5), 2.058(5), and 2.030(5) Å.     

Hydration Structure Around the Carboxyl Group Studied by Neutron Diffraction with 12C/13C and H/D Isotopic Substitution Methods

Time-of-Flight (TOF) neutron diffraction measurements have been carried out on aqueous 8 mol% sodium acetate solutions in D₂O. Scattering cross sections that were observed for sample solutions involving ¹²C/¹³C and H/D isotopically substituted acetate ions were used to derive the first-order difference functions, Δ_H(Q) and Δ_C(Q), and corresponding distribution functions, G _H(r;r) and G _C(r;r), which describe the environmental structure around the methyl and the carboxyl groups within the acetate ion, respectively. Structural parameters concerning the first hydration shell of the carboxyl group within the acetate ion were obtained through the least squares fit to the observed intermolecular difference function, Δ_C ^inter(Q). The nearest neighbor C _O...D _W1 (C_O: carboxyl carbon atom, D_W1: water deuterium atom) distance, r(C _O...D _W1 ), and the angle, ∠ C _O ...D _W1 -O _W (O _W : water oxygen atom), were determined to be 2.63(1) Å and 120(1)°, respectively. The coordination number, n(C _O ...D _W1 ), was obtained to be 4.0(1). These results are consistent with the hydration structure in which water molecules in the first hydration shell of the carboxyl group are hydrogen-bonded with oxygen atoms of the carboxyl group.     

The interface of the Ising model and the Brownian sheet

We study the limit theorem related to the interface of the three-dimensional Ising model. Dobrushin proved that the interface does not fluctuate and becomes rigid for sufficiently large. We define the random fieldX ^L (t, s), 0t, s1, on the interface, and prove that X^L(t, s) converges to the Brownian sheet as L for sufficiently large, whereL denotes the size of the system. This result does not mean that the interface itself converges to the Brownian sheet.     

Formation of the unusual alkynyl carboxamide complex, C2H5N(H)C(O)CC[Co2(CO)6]CCo3(CO)9

The reaction of the cluster complex HCC[Co₂(CO)₆]CCo₃(CO)₉ with (or without) BrCCo₃(CO)₉ under Cadiot-Chodkiewicz coupling conditions gave the unusual alkynyl carboxamide complex C₂H₅N(H)C(O)CC[Co₂(CO)₆]CCo₃(CO)₉ rather than a coupled product containing two tricobalt cluster units. Steric demands imposed by the Co₃ cluster allow attack at the least hindered alkyne carbon and stabilise the formed ynamine, so allowing subsequent CO insertion. The product has been characterised by X-ray crystallography.     

Simultaneous determination of clebopride and a major metabolite N-desbenzylclebopride in plasma by capillary gas chromatography-negative-ion chemical ionization mass spectrometry

A procedure for the simultaneous assay of clebopride and its major metabolite N-desbenzylclebopride in plasma has been developed. The method utilizes capillary gas chromatography-negative-ion chemical ionization mass spectrometry with selected-ion monitoring of characteristic ions. Employing 2-ethoxy analogues as internal standards, the benzamides were extracted from basified plasma using dichloromethane. Subsequent reaction with heptafluorobutyric anhydride produced volatile mono- and diheptafluorobutyryl derivatives of clebopride and N-desbenzylclebopride, respectively. The methane negative-ion mass spectra of these derivatives exhibited intense high-mass ions ideal for specific quantitation of low levels in biological fluids. Using this procedure the recovery of the drug and metabolite from human plasma was found to be 84.4 +/- 1.5% (n = 3) and 77.4 +/- 4.7% (n = 3), respectively, at 0.5 ng/ml. Measurement of both compounds down to 0.10 ng/ml with a coefficient of variation of less than 10.5% is described. Plasma levels are reported in four volunteers up to 24 h following oral administration of 1 mg of clebopride malate salt.     

Core-shell type polymer microspheres prepared by domain fixing of block copolymer films

Well-defined poly[styrene(S)-b-isoprene(I)] diblock copolymers were prepared by sequential anionic addition. The crosslinking reactions of polyisoprene (PI) spherical domains of these block copolymers were carried out in a n-hexane solution of sulfur monochloride (S₂Cl₂). Electron micrograph of crosslinked products indicates the structure of core-shell type polymer microspheres. It is found from NMR and turbi+imetric measurements that the solubility of core-shell type polymer microspheres depends strongly on that of block chains comprising the shell portion. The particle size of these microspheres shows a narrow distribution.