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21.
Cheng Zhang Laurence Bensaid Donna McGregor Xikui Fang Robertha C. Howell Benjamin Burton-Pye Qunhui Luo Louis Todaro Lynn C. Francesconi 《Journal of Cluster Science》2006,17(2):389-425
Lanthanide complexes of polyoxometalates, including the α2-P2W17O61
10− ligand, have been pioneered by Michael T. Pope, to whom this paper is dedicated. Examination of the solid-state and solution behavior of lanthanide complexes of the α2-P2W17O61
10− ligand are reported here to identify trends that will facilitate rational synthesis of hybrid organic lanthanide polyoxometalate complexes. Therefore, combining our data with that obtained by Pope and others a number of trends come into view. It is clear that there are two structural types for the 1:1 or 2:2 [Ln(H2O)X(α2-P2W17O61)]2
14− species. The early lanthanides show a “cap to cap” structure that allows the Ln ion to be 9 coordinate and accommodates the longer bond lengths. The mid-late lanthanides show a “cap to belt” structure that allows the lanthanides to be 8 coordinate; this structural type is appropriate for the shorter bond lengths of the later lanthanides. The 1:1⇌1:2 equilibrium, that was observed by Pope for the Ce(III) analog is prevalent for the early- mid lanthanides. This equilibrium is slightly dependent on pH; however, cations have a major influence on this equilibrium. Larger, poorly hydrated cations appear to favor the 1:2 species for the early to mid lanthanides. Cations do not appear to influence the equilibrium for the later lanthanides; for all counterions, the 1:1 species was stable with no trace of the 1:2 species. Stability constants, K1 and K2, for the early to mid lanthanides were measured in this study by a competitive method and compared well with other published stability constant determinations. We suggest that the stability constants are not only dependent on the strength of interaction of the Ln with the α2-P2W17O61
10− ligand, but are also significantly influenced by the medium. The medium may bias the equilibria of the early-mid lanthanides and later lanthanides. The log K1/log K2 ratios are very close, suggesting that it is difficult to separate the 1:1 and 1:2 Ln: α2-P2W17O61
10− species.Electronic Supplementary Material Supplementary material for this article is available at and is accessible for authorized users.This paper is dedicated to Professor Michael T. Pope in honor of his substantial and sustained contributions to polyoxometalate chemistry and his inspiration to scientists working in the field. 相似文献
22.
Lee LF Adronov A Schaller RD Fréchet JM Saykally RJ 《Journal of the American Chemical Society》2003,125(2):536-540
Near-field scanning optical microscopy (NSOM) has been used to investigate the photophysical characteristics of first- to fourth-generation (G1 to G4) light-harvesting dendrimer thin films containing coumarin-343 and coumarin-2 as the core and peripheral chromophores, respectively. Thin film photoluminescence (PL) spectra exhibit a significant red shift in the lower generations (G1, G2, and G3) as compared to their respective solution PL spectra, implying the formation of excimers. Spatially resolved PL NSOM images exhibit pronounced nanoscopic domains in G1, which become more homogeneous in higher generations due to site-isolation of the core chromophore. G4 exhibits complete site-isolation for these light-harvesting dendrimer films. 相似文献
23.
Autoverification is a process in which computer software will automatically evaluate laboratory test results, verify result integrity, and then release the results to the hospital interface without any technologist intervention. Autoverify release criteria are user defined and can be customized. The process of developing, implementing, and monitoring autoverify is achievable for most test results in laboratory medicine. The use of autoverification will improve result quality, increase revenue, and create faster turn-around times. All of this put together will ultimately lead to improved customer satisfaction. Computers and autoverification are survival tools in the competitive market of laboratory diagnostics services.Presented at the 8th Conference on Quality in the Spotlight, 17–18 March 2003, Antwerp, Belgium 相似文献
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Luo Q Howell RC Bartis J Dankova M Horrocks WD Rheingold AL Francesconi LC 《Inorganic chemistry》2002,41(23):6112-6117
We have isolated the 1:1 Ln:[alpha-2-P2W17O61]10- complexes for a series of lanthanides. The single-crystal X-ray structure of the Eu3+ analogue reveals two identical [Eu(H2O)3(alpha-2-P2W17O61)]7- moieties connected through two Eu-O-W bonds, one from each polyoxometalate unit. An inversion center relates the two polyoxometalate units. The Eu(III) ion is substituted for a [WO]4+ unit in the "cap" region of the tungsten-oxygen framework of the parent Wells-Dawson ion. The point group of the dimeric molecule is Ci. The extended structure is composed of the [Eu(H2O)3(alpha-2-P2W17O61)]214- anions linked together by surface-bound potassium cations. The space group is P, a = 12.7214(5) A, b = 14.7402(7) A, c = 22.6724(9) A, alpha = 71.550(3), beta = 84.019(3)degrees, gamma = 74.383(3), V = 3883.2(3) A3, Z = 1. The solution studies, including 183W NMR spectroscopy and luminescence lifetime measurements, show that the molecules dissociate in solution to form monomeric [Ln(H2O)4(alpha-2-P2W17O61)]7- species. 相似文献
26.
Burdick Brent A. Esders Theodore W. Schaeffer James R. Lynn Shirley 《Applied biochemistry and biotechnology》1987,16(1):145-156
Several hydrophilic polymeric thiols were prepared from aminoactivated polymeric supports by reaction with N-acetylhomocysteinethiolactone.
Supports include agaroses, cellulose, Glycophase™ controlled-pore glass, and Matrex™ acrylic beads. Thiol content in these
polymers was 3–72 μmol SH/g dry polymer. Several were effective solid-phase activators of the sulfhydryl-dependent enzyme
creatine phosphokinase at concentrations comparable to that of monomeric thiol required for enzyme activation. The kinetic
activation curves for the polymeric and the monomeric (thioglucose) activators were similar, suggesting unhindered interaction
of the enzyme with the polymeric activator. 相似文献
27.
DeRider ML Wilkens SJ Waddell MJ Bretscher LE Weinhold F Raines RT Markley JL 《Journal of the American Chemical Society》2002,124(11):2497-2505
Collagen-like peptides of the type (Pro-Pro-Gly)(10) fold into stable triple helices. An electron-withdrawing substituent at the H(gamma)(3) ring position of the second proline residue stabilizes these triple helices. The aim of this study was to reveal the structural and energetic origins of this effect. The approach was to obtain experimental NMR data on model systems and to use these results to validate computational chemical analyses of these systems. The most striking effects of an electron-withdrawing substituent are on the ring pucker of the substituted proline (Pro(i)) and on the trans/cis ratio of the Xaa(i-1)-Pro(i) peptide bond. NMR experiments demonstrated that N-acetylproline methyl ester (AcProOMe) exists in both the C(gamma)-endo and C(gamma)-exo conformations (with the endo conformation slightly preferred), N-acetyl-4(R)-fluoroproline methyl ester (Ac-4R-FlpOMe) exists almost exclusively in the C(gamma)-exo conformation, and N-acetyl-4(S)-fluoroproline methyl ester (Ac-4S-FlpOMe) exists almost exclusively in the C(gamma)-endo conformation. In dioxane, the K(trans/cis) values for AcProOMe, Ac-4R-FlpOMe, and Ac-4S-FlpOMe are 3.0, 4.0, and 1.2, respectively. Density functional theory (DFT) calculations with the (hybrid) B3LYP method were in good agreement with the experimental data. Computational analysis with the natural bond orbital (NBO) paradigm shows that the pucker preference of the substituted prolyl ring is due to the gauche effect. The backbone torsional angles, phi and psi, were shown to correlate with ring pucker, which in turn correlates with the known phi and psi angles in collagen-like peptides. The difference in K(trans/cis) between AcProOMe and Ac-4R-FlpOMe is due to an n-->pi interaction associated with the Bürg-Dunitz trajectory. The decrease in K(trans/cis) for Ac-4S-FlpOMe can be explained by destabilization of the trans isomer because of unfavorable electronic and steric interactions. Analysis of the results herein along with the structures of collagen-like peptides has led to a theory that links collagen stability to the interplay between the pyrrolidine ring pucker, phi and psi torsional angles, and peptide bond trans/cis ratio of substituted proline residues. 相似文献
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