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61.
Deacon GB Forsyth CM Gitlits A Skelton BW White AH 《Dalton transactions (Cambridge, England : 2003)》2004,(8):1239-1247
The direct reaction of lanthanoid metals with 3,5-diphenylpyrazole (Ph2pzH) at 300 degrees C under vacuum in the presence of mercury gives the structurally characterized [Ln3(Ph2pz)9] (Ln = La or Nd), [Ln2(Ph2pz)6] (Ln = Er or Lu). Similar reactions provided heteroleptic [Ln(Ph2pz)3(Ph2pzH)2] (Ln = La, Nd, Gd, Tb, Er and Y). The last was obtained only from impure Ph2pzH, but was subsequently prepared by treatment of [Yb(Ph2pz)3(thf)2] with Ph2pzH. Reactions of Yb with Ph2pzH at 200 degrees C gave a poorly soluble divalent species which was converted by 1,2-dimethoxyethane into [Yb(Ph2pz)2(dme)2]. Single crystal X-ray structures established a bowed trinuclear pyrazolate-bridged structure for [Ln3(Ph2pz)9] (Ln = La or Nd), Ln...Ln...Ln being 135.94(1) degrees (La) and 137.41(1) degrees(Nd). There are two eta2-Ph2pz ligands on the terminal Ln atoms and one on the central metal with adjacent Ln atoms linked by one mu-eta2:eta2 and one mu-eta5 (to terminal Ln):eta2 pyrazolate group. Thus the terminal Ln atoms are formally nine-coordinate and the central Ln, ten-coordinate. By contrast, [Ln2(Ph2pz)6] (Ln = Er or Lu) complexes are dimeric with two terminal (eta2) and two bridging (mu-eta2:eta2) pyrazolates and eight-coordinate lanthanoids. All six heteroleptic complexes [Ln(Ph2pz)3(Ph2pzH)2] (Ln = La, Nd, Gd, Tb, Er or Yb) are isomorphous with three equatorial eta2-Ph2pz groups, transoid(N-Ln-N 158.18(6)-161.43(9) degrees) eta1-pyrazole ligands, and eight-coordinate Ln throughout. 相似文献
62.
[formula: see text] Described is a novel, concise, and flexible synthesis of the C3-C14 portion of okadaic acid. A substituted valerolactone (C3-C8) was prepared in three steps and alpha-hydroxylated using Davis' oxaziridine. Conjugate addition of dimethylcuprate upon ynones derived from the C3-C8 lactones followed by intramolecular ketalization provided the C3-C14 fragment and revealed a significant role of the C7 alpha'-ketone substituent upon the efficiency of spiroketalization. 相似文献
63.
Rapid,clean, and mild O-acetylation of alcohols and carbohydrates in an ionic liquid 总被引:2,自引:0,他引:2
Forsyth SA MacFarlane DR Thomson RJ von Itzstein M 《Chemical communications (Cambridge, England)》2002,(7):714-715
Archetypal O-acetylation reactions of alcohols and carbohydrates proceed rapidly in high yield under mild conditions in a dicyanamide based ionic liquid, that is not only an effective solvent but also an active base catalyst. 相似文献
64.
Pulsed discharge detector: theory and applications 总被引:1,自引:0,他引:1
Forsyth DS 《Journal of chromatography. A》2004,1050(1):63-68
The pulsed discharge detector (PDD) is a significant advancement in gas chromatography (GC) detector design which can be operated in three different modes: pulsed discharge helium ionization (He-PDPID), pulsed discharge electron capture (PDECD) and helium ionization emission (PDED). The He-PDPID can detect permanent gases, volatile inorganics and other compounds which give little or no response with the flame ionization detector (FID) and has significantly better limits of detection (minimum detectable quantities (MDQs) in low picogram range) than can be achieved with a thermal conductivity detector (typically not lower than 1 ng). The PDECD has similar or better sensitivity (MDQs of 10(-15) to 10(-12) g) than radioactive source ECD but does not require licensing, wipe tests and other administrative or safety requirements which have increased over security concerns. The PDED shows promise as an extremely selective and sensitive elemental detector but a commercial unit is not presently available. In this report, the theory of operation, applications of the PDD and the practical aspects of using this novel detector are presented. 相似文献
65.
P. MORLIÉRE M. BAZIN L. DUBERTRET R. SANTUS T. SA E. MELO G. HÜPPE J. HAIGLE P. FORLOT A. BERNARD 《Photochemistry and photobiology》1991,53(1):13-19
5-Geranoxypsoralen, commonly called bergamottin, a major furocoumarin contained in bergamot oil, is reported in vitro as a highly photoreactive psoralen. In ethanol, it exhibits quite a high triplet state quantum yield (approximately 0.37). The triplet state is involved in subsequent photochemistry which depends on the initial concentration and on the presence of oxygen. In contrast to most psoralens, absorption and fluorescence data suggest that 5-geranoxypsoralen does not interact with DNA in the dark. No UVA-induced interstrand cross-links in DNA were shown. 相似文献
66.
Robert G.K. Donald Stephen Skwish R. Allyn Forsyth Jennifer W. Anderson Tanya Zhong Colleen Burns Suzy Lee Xin Meng Lynn LoCastro Lisa Wang Jarantow Jesus Martin Sang Ho Lee Ian Taylor David Robbins Cheryl Malone Liangsu Wang Carlos S. Zamudio Philip J. Youngman John W. Phillips 《Chemistry & biology》2009,16(8):826-836
67.
We investigate the thermoelectric properties of GaN with p-and n-type doping by the first principles calculation and the semi-classical Boltzmann theory. We find that the power factors (S2σof p-type GaN (-3500 W/mK2) is about twice that of the n-type (-1750 W/mK2), which indicates the thermoelectric properties of p-type GaN would be better. Thermal conductivity of GaN crystal decreases rapidly as the temperature increases, but it is still too large for thermoelectric applications. The figure of merit (ZT) estimated at 1500 K is 0.134 for p-type GaN crystal and 0.062 for the n-type. 相似文献
68.
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70.
The TDDFT method is first applied in a series of tetra-nuclear transition metal clusters studies for nonlinear optical properties. The results indicate that the charge transfer inside the metal core [MCu3X4] (M=W, Mo; X=S, O, Cl, Se, Br) makes contribution to the optical nonlinearity. It is possible to enhance the hyperpolarizability by substituting the ligands of the clusters. 相似文献