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The synthesis, characterization, and photophysical and photochemical properties of a family of high-nuclearity gold(I) chalcogenides, specifically, the gold(I) sulfido and selenido complexes containing different bridging diphosphine ligands with nuclearities of ten ([Au10{µ-Ph2PN(R)PPh2}4(µ3-E)4](2+)) and six ([Au6{µ-Ph2PN(R)PPh2}3(µ3-E)2](2+)), are reported. The X-ray crystal structures of the complex cations of Au10 and Au6 are found to be propeller-like structures and distorted cubane structures, respectively, with the presence of short intramolecular gold···gold distances. The complexes show intense green and/or orange phosphorescence upon photoexcitation in the solid state and in solution at ambient and low temperature. The emission properties are found to be strongly dependent on the nuclearities and the chalcogenido ligands, but are rather insensitive to the substituents on the bis(diphenylphosphino)amines. The emissions are tentatively assigned to originate from the excited states derived from the phosphine-centered intraligand (IL) transition or metal-centered (ds/dp) mixed with ligand-to-metal-metal charge transfer (LMMCT) (EâAu) transition. The photochemical properties of the complexes were also studied by transient absorption spectroscopy.
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BACKGROUND: Manual microscopy is the current reference method for white blood cell (WBC) differential counts. However, manual counts are time and labor intensive, difficult in patients with low WBC counts, and can misclassify cells having difficult morphology. We investigated an 8-color, single-tube, lyse no-wash flow cytometric method to perform an extended 8-part differential as a potential replacement reference method for WBC differential enumeration. METHODS: Whole blood was stained using a panel of antibodies including CD45APC-Cy7, CD16+CD19FITC, CD33+CD64PE-Cy5, CD123PE, HLA-DRPE-Cy7, CD34+CD117APC, and CD38A594 with the membrane permeant DNA binding dye Hoechst 34580 to generate an 8-part differential (lymphocytes, granulocytes, monocytes, eosinophils, basophils, immature granulocytes, blasts, and nucleated RBCs) using TruCount beads to generate absolute counts for all populations. Manual and instrument differentials were generated for 300 blood samples ranging from normal to complex. Results were compared with the flow cytometric differential. RESULTS: The flow cytometric WBC and differential correlated well with the Sysmex XE2100 hematology analyzer and gave comparable results to the manual differential. Areas of greatest discordance included enumeration of populations present at low numbers and misclassification of cells with unusual morphology by the manual method. This study describes a novel single-tube flow cytometric method for performing a WBC count and 8-part differential that performs well with both normal and difficult patient samples. These findings confirm the results of prior studies supporting the use of a flow cytometric differential as an improved reference method for the WBC differential and extend prior efforts by allowing positive identification of most cell populations. © 2010 International Clinical Cytometry Society.
Assuntos
Citometria de Fluxo/métodos , Contagem de Leucócitos/métodos , Anticorpos/imunologia , Corantes Fluorescentes/análise , HumanosRESUMO
A series of soluble trinuclear copper(I) and silver(I) complexes containing bicapped diynyl ligands, [M(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CR)(2)]PF(6) (M = Cu, R = Ph, C(6)H(4)-CH(3)-p, C(6)H(4)-OCH(3)-p, (n)C(6)H(13), H; M = Ag, R = Ph, C(6)H(4)-OCH(3)-p), has been synthesized and their electronic, photophysical, and electrochemical properties studied. The X-ray crystal structures of [Cu(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CPh)(2)]PF(6) and [Cu(3)(micro-dppm)(3)(micro(3)-eta(1)-C triple bond CC triple bond CH)(2)]PF(6) have been determined.
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A novel series of luminescent heterodecanuclear mixed-metal alkynyl complexes, [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(N--N)(CO)3]4](PF6)2, (N--N = tBu2bpy, Me2bpy, phen, Br2phen), have been successfully synthesized; the X-ray crystal structures of [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Me2bpy)(CO)3]4](PF6)2 and [Ag6(mu-dppm)4[mu3-C[triple bond]CC[triple bond]C-Re(Br2phen)(CO)3]4](PF6)2 have also been determined.
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[Cu4(mu-dppm)4(mu4-eta1,eta2-C[triple bond]C-)]2+ has been shown by 31P and 1H NMR studies to undergo two fluxional processes in solution, the oscillation of the C[triple bond]C2- unit inside the copper rectangle and the flipping of the diphosphines, and this has been supported by DFT(B3LYP) calculations.
