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81.
Daniel Tholen Roderick Chappel Barbara Francis 《Accreditation and quality assurance》2006,11(8-9):400-407
International requirements for PT and EQA state that providers must demonstrate that samples are homogeneous and stable. However, testing for homogeneity and stability can be expensive, use samples that could otherwise serve as quality-control materials, and can also fail to detect significant inhomogeneity and instability. In some situations it may be preferable to use the results from participants to identify problems with sample lots, if historic results follow predictable distributions and a statistical decision rule can be produced. An unusually high proportion of incorrect results may indicate that samples were inhomogeneous or unstable. Conditions under which this can be demonstrated are discussed, and the efficacy of the proposal is demonstrated with two examples. This procedure is especially effective when there are a large number of participants and/or a historic small proportion of incorrect results. Providers who adopt this proposal will need to retain samples for testing and assume the risk of distributing bad samples.Presented at the Eurachem PT Workshop September 2005, Portorož, Slovenia 相似文献
82.
Martinho M Banse F Bartoli JF Mattioli TA Battioni P Horner O Bourcier S Girerd JJ 《Inorganic chemistry》2005,44(25):9592-9596
The green complex S=1 [(TPEN)FeO]2+ [TPEN=N,N,N',N'-tetrakis(2-pyridylmethyl)ethane-1,2-diamine] has been obtained by treating the [(TPEN)Fe]2+ precursor with meta-chloroperoxybenzoic acid (m-CPBA). This high-valent complex belongs to the emerging family of synthetic models of Fe(IV)=O intermediates invoked during the catalytic cycle of biological systems. This complex exhibits spectroscopic characteristics that are similar to those of other models reported recently with a similar amine/pyridine environment. Thanks to its relative stability, vibrational data in solution have been obtained by Fourier transform infrared. A comparison of the Fe=O and Fe=(18)O wavenumbers reveals that the Fe-oxo vibration is not a pure one. The ability of the green complex to oxidize small organic molecules has been studied. Mixtures of oxygenated products derived from two- or four-electron oxidations are obtained. The reactivity of this [FeO]2+ complex is then not straightforward, and different mechanisms may be involved. 相似文献
83.
Claiser N Souhassou M Lecomte C Gillon B Carbonera C Caneschi A Dei A Gatteschi D Bencini A Pontillon Y Lelièvre-Berna E 《The journal of physical chemistry. B》2005,109(7):2723-2732
High-resolution X-ray diffraction and polarized neutron diffraction experiments have been performed on the Y-semiquinonate complex, Y(HBPz3)2(DTBSQ), in order to determine the charge and spin densities in the paramagnetic ground state, S = (1/2). The aim of these combined studies is to bring new insights to the antiferromagnetic coupling mechanism between the semiquinonate radical and the rare earth ion in the isomorphous Gd(HBPz3)2(DTBSQ) complex. The experimental charge density at 106 K yields detailed information about the bonding between the Y3+ ion and the semiquinonate ligand; the topological charge of the yttrium atom indicates a transfer of about 1.5 electrons from the radical toward the Y3+ ion in the complex, in agreement with DFT calculations. The electron density deformation map reveals well-resolved oxygen lone pairs with one lobe polarized toward the yttrium atom. The determination of the induced spin density at 1.9 K under an applied magnetic field of 9.5 T permits the visualization of the delocalized magnetic orbital of the radical throughout the entire molecule. The spin is mainly distributed on the oxygen atoms [O1 (0.12(1) mu B), O2(0.11(1) mu B)] and the carbon atoms [C21 (0.24(1) mu B), C22(0.20(1) mu B), C24(0.16(1) mu B), C25(0.12(1) mu B)] of the carbonyl ring. A significant spin delocalization on the yttrium site of 0.08(2) mu B is observed, proving that a direct overlap with the radical magnetic orbital can occur at the rare earth site and lead to antiferromagnetic coupling. The DFT calculations are in good quantitative agreement with the experimental charge density results, but they underestimate the spin delocalization of the oxygen toward the yttrium and the carbon atoms of the carbonyl ring. 相似文献
84.
85.
David Kessel Kevin M. Smith R. K. Pandey F.-Y. Shiau Barbara Henderson 《Photochemistry and photobiology》1993,58(2):200-203
Abstract— Biophysical and photobiological properties of a group of bacteriochlorins were compared with efficacy of these products for photodynamic therapy of murine tumors. Predictive factors for selective photosensitization in vivo include affinity binding to lipoproteins greater than albumin, extinction coefficient at the wavelength of irradiation and tumor/skin distribution. Efficacy was correlated with circulating plasma levels of the different sensitizers but not with the photodynamic therapy response in cell culture. 相似文献
86.
Laila Čakare Marija Kosec Barbara Malič 《Journal of Sol-Gel Science and Technology》2000,19(1-3):603-606
PbZrO3 (PZ) thin films have been prepared by 2-methoxyethanol route from lead oxide or lead acetate and zirconium n-butoxide. The use of lead oxide as lead source and the seeding layer of TiO2 on Pt/TiO2/SiO2/Si substrate facilitate the formation of the perovskite phase. 相似文献
87.
S. Dirè P. Egger M. L. Di Vona M. Trombetta S. Licoccia 《Journal of Sol-Gel Science and Technology》2004,32(1-3):57-61
The preparation of nanostructured organic-inorganic materials by assembling of nanobuilding blocks allows controlling the extent of phase interaction, which in its turn governs structure-properties relationships. We present here the synthesis of siloxane-based nanobuilding blocks prepared by reacting diphenylsilanediol with vinyltriethoxysilane and triethoxysilane. The reaction products were obtained by non-hydrolytic condensation between silanediol and ethoxide groups in inert atmosphere, in the presence of pyridine, triethylamine or butyl lithium. Different synthetic conditions were examined by means of ATR-FTIR and NMR spectroscopies, showing the formation of siloxane bonds. In the case of triethoxysilane the reaction carried out in the presence of pyridine leads to Si–H bond preservation in the final product. Air stable products with improved Si–O–Si hydrolytic stability can be obtained by removal of the base after the reaction completion. The condensation products can be described as a mixture of siloxane rings involving difunctional and trifunctional silicon units. 相似文献
88.
Leclerc E Buchmann W Taphanel MH Morizur JP 《Rapid communications in mass spectrometry : RCM》2002,16(7):686-695
Ion/molecule reactions between O=P(OCH(3))(2)(+) phosphonium ions and six aromatic hydrocarbons (benzene, toluene, 1,2,4-trimethylbenzene, naphthalene, acenaphthylene and fluorene) were performed in a quadrupole ion trap mass spectrometer. The O=P(OCH(3))(2)(+) phosphonium ions, formed by electron impact from neutral trimethyl phosphite, were found to react with aromatic hydrocarbons (ArHs) to give (i) an adduct [ArH, O=P(OCH(3))(2)](+) and (ii) for ArHs which have an ionization energy below or equal to 8.14 eV, a radical cation ArH(+ *) by charge transfer reaction. Collision-induced dissociation experiments, which produce fragment ions other than the O=P(OCH(3))(2)(+) ions, indicate that the adduct ions are covalent species. Isotope-labeled ArHs were used to elucidate fragmentation mechanisms. The charge transfer reactions were investigated using density functional theory at the B3LYP/6-311 + G(3df,2p)//B3LYP/6-31G(d,p) level of theory. The potential energy surface obtained from B3LYP/6-31G(d,p) calculations for the reaction between O=P(OCH(3))(2)(+) and benzene is described. 相似文献
89.
Applied Biochemistry and Biotechnology - Biological systems can convert renewable resources, including lignocellulosic biomass, starch crops, and carbon dioxide, into fuels, chemicals, and... 相似文献
90.