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781.
Börzel H Comba P Hagen KS Kerscher M Pritzkow H Schatz M Schindler S Walter O 《Inorganic chemistry》2002,41(21):5440-5452
Copper(I) and copper(II) complexes of two mononucleating and four dinucleating tetradentate ligands with a bispidine backbone (2,4-substituted (2-pyridyl or 4-methyl-2-pyridyl) 3,7-diazabicyclo[3.3.1]nonanone) have been prepared and analyzed structurally, spectroscopically, and electrochemically. The structures of the copper chromophores are square pyramidal, except for two copper(I) compounds which are four-coordinate with one noncoordinated pyridine. The other copper(I) structures have the two pyridine donors, the co-ligand (NCCH(3)), and one of the tertiary amines (N3) in-plane with the copper center and the other amine (N7) coordinated axially (Cu-N3 > Cu-N7, approximately 2.25 A vs 2.20 A). The copper(II) compounds with pyridine donors have a similar structure, but the axial amine has a weaker bond to the copper(II) center (Cu-N3 < Cu-N7, approximately 2.03 A vs 2.30 A). The structures with methylated pyridine donors are also square pyramidal with the co-ligands (Cl(-) or NCCH(3)) in-plane. With NCCH(3) the same structural type as for the other copper(II) complexes is observed, and with the bulkier Cl(-) the co-ligand is trans to N7, leading to a square pyramidal structure with the pyridine donors rotated out of the basal plane and only a small difference between axial and in-plane amines (2.15, 2.12 A). These structural differences, enforced by the rigid bispidine backbone, lead to large variations in spectroscopic and electrochemical properties and reactivities. Oxygenation of the copper(I) complexes with pyridine-substituted bispidine ligands leads to relatively stable mu-peroxo-dicopper(II) complexes; with a preorganization of the dicopper chromophores, by linking the two donor sets, these peroxo compounds are stable at room temperature for up to 1 h. The stabilization of the peroxo complexes is to a large extent attributed to the square pyramidal coordination geometry with the substrate bound in the basal plane, a structural motif enforced by the rigid bispidine backbone. The stabilities and structural properties are also seen to correlate with the spectroscopic (UV-vis and Raman) and electrochemical properties. 相似文献
782.
Deconvoluting the functions of polypeptide N-alpha-acetylgalactosaminyltransferase family members by glycopeptide substrate profiling 总被引:4,自引:0,他引:4
Pratt MR Hang HC Ten Hagen KG Rarick J Gerken TA Tabak LA Bertozzi CR 《Chemistry & biology》2004,11(7):1009-1016
The polypeptide N-alpha-acetylgalactosaminyltransferases (ppGalNAcTs) play a key role in mucin-type O-linked glycan biosynthesis by installing the initial GalNAc residue on the protein scaffold. The preferred substrates and functions of the >20 isoforms in mammals are not well understood. However, current data suggest that glycosylated mucin domains are created by the successive, often hierarchical, action of several specific ppGalNAcTs. Herein we analyzed the glycopeptide substrate preferences of several ppGalNAcT family members using a library screening approach. A 56-member glycopeptide library designed to reflect a diversity of glycan clustering was assayed for substrate activity with ppGalNAcT isoforms using an azido-ELISA. The data suggest that the ppGalNAcTs can be classified into at least four types, which working together, are able to produce densely glycosylated mucin glycoproteins. 相似文献
783.
784.
A putatively highly sensitive and selective method for the determination of cobalt in aqueous samples by catalytic adsorptive cathodic stripping voltammetry using methyl thymol blue (MTB) as the ligand has been documented [A. Safavi, E. Shams, Talanta 51 (2000) 1117] and its underlying mechanism has been briefly explored [A. Safavi, E. Shams, Electroanalysis 14 (2002) 708]. In an attempt to adapt the method for application in metalloprotein analysis we obtained erratic results, which were traced down to the redox non-innocence of the free ligand in the potential range prescribed for the metal analysis. On the hanging mercury drop electrode free methyl thymol blue is reversibly one-electron reduced to the semiquinone form with Em,7.0 = −482 mV versus NHE at 22 °C, and the radical is subsequently quasi-reversibly one-electron reduced to the quinol form with Em,7 ≈ −0.9 V. This observation invalidates the use of MTB in electrochemical analysis of metal ions. This is also the first observation ever of a stable quinone methide radical in aqueous solution. 相似文献
785.
An efficient synthesis of the (R)-3-hydroxy- and alkanoyloxytetradecanoic acid components of bacterial lipid A has been achieved using a Ru(II)-Binap-catalyzed low-pressure hydrogenation in the key step. The enantiomeric purity of p-bromophenacyl ester intermediate 4 could be assessed directly by chiral HPLC-obviating separate derivatization steps and/or chiral NMR shift studies. 相似文献
786.
Henk Hagen Santiago Reinoso Ed J. Reijerse Ernst E. van Faassen Martin Lutz Anthony L. Spek Gerard van Koten 《无机化学与普通化学杂志》2004,630(12):2097-2105
In order to study the effect of steric bulk on the vanadium coordination geometry in O, N‐chelated vanadium oxo (bis)phenolates, six different ortho‐aminophenolate ligands have been used. The ortho‐aminophenolate system was changed at three different places, i.e. 1) the second ortho position (C6) of the arene ring (R), 2) the substituents at the amino nitrogen (R′ and R″), and 3) the benzylic carbon atom (R*). The phenols were used in the preparation of the vanadium oxo (bis)phenolate complexes. In order to study whether it is possible to predict geometrical features of these vanadium complexes, UV/Vis, solution and frozen state EPR and 14N ESEEM spectroscopic data was measured and compared to the structural features of four structurally characterized vanadium oxo (bis)phenolates. Unfortunately, it turned out that is was not possible to correlate the EPR parameters, the UV/Vis HOMO‐LUMO transitions or 14N hyperfine couplings to the structural parameters. 相似文献
787.
Hagen H Bezemer C Boersma J Kooijman H Lutz M Spek AL van Koten G 《Inorganic chemistry》2000,39(18):3970-3977
Two different monoanionic O,N-chelating ligand systems, i.e., [OC6H2(CH2NMe2)-2-Me2-4,6]- (1) and [OCMe2([2]-Py)]- (2), have been applied in the synthesis of vanadium(V) complexes. The tertiary amine functionality in 1 caused reduction of the vanadium nucleus to the 4+ oxidation state with either [VOCl3], [V(=NR)Cl3], or [V(=NR)(NEt2)3] (R = Ph, (3a, 5a), R = p-Tol (3b, 5b)), and applying 1 as a reducing agent resulted in the synthesis of the vanadium(IV) complexes [VO(OC6H2(CH2NMe2)-2-Me2-4,6)2] (4) and [V(=NPh)(OC6H2(CH2NMe2)-2-Me2-4,6)2] (6). In the case of [V(=N-p-Tol)(NEt2)(OC6H2(CH2NMe2)-2-Me2-4,6)2] (7b), the reduction was sufficiently slow to allow its characterization by 1H NMR and variable-temperature studies showed it to be a five-coordinate species in solution. Although the reaction of 1 with [V(=N-p-Tol)(O-i-Pr)3] (9b) did not result in reduction of the vanadium nucleus, vanadium(V) compounds could not be isolated. Mixtures of the vanadium(V) (mono)phenolate, [V(=N-p-Tol)(O-i-Pr)2(OC6H2(CH2NMe2)-2-Me2-4,6)] (10), and the vanadium(V) (bis)phenolate, [V(=N-p-Tol)(O-i-Pr)(OC6H2(CH2NMe2)-2-Me2-4,6)2] (11), were obtained. With the pyridylalkoxide 2, no reduction was observed and the vanadium(V) compounds [VOCl2(OCMe2([2]-Py))] (12) and [V(=N-p-Tol)Cl2(OCMe2([2]-Py)] (13) were obtained. 51V NMR showed 7b and 12 to be five-coordinate in solution, whereas for 10, 11, and 13 a coordination number of 6 was found. Compounds 12 and 13 showed decreased activity compared to their nonchelated vanadium(V) analogues when applied as catalysts in ethene polymerization. Two polymorphic forms with a difference in the V-N-C angle of 12.5 degrees have been found for 6. Crystal data: 6.Et2O, triclinic, P1, a = 11.1557(6) A, b = 12.5744(12) A, c = 13.1051(14) A, alpha = 64.244(8) degrees, beta = 70.472(7) degrees, gamma = 87.950(6) degrees, V = 1547(3) A3, Z = 2; 6.C6H6, triclinic, P1, a = 8.6034(3) A, b = 13.3614(4) A, c = 15.1044(5) A, alpha = 98.182(3) degrees, beta = 105.618(2) degrees, gamma = 107.130(2) degrees, V = 1551.00(10) A3, Z = 2; 12, orthorhombic, Pbca, a = 11.8576(12) A, b = 12.6710(13) A, c = 14.722(2) A, V = 2211.9(4) A3, Z = 8. 相似文献
788.
A new method for the determination of absolute fluorescence quantum yields based on simple relative measurements is described. This energy transfer method is particularly suited for studies of dyes in systems of monomolecular layers. The application of the new method to an investigation of the deactivation of excited thiacyanine dye molecules in monolayers gave evidence for radiationless deactivation processes other than thermal equilibration occurring in higher vibronic levels of the excited singlet state. 相似文献
789.
Germund Höjer Sara Meza-Höjer Gisela Hernández de Pedrero 《Chemical physics letters》1976,37(2):301-306
The orbital order, the bonding properties of the orbitals and the orbital populations are discussed. It is concluded that the orbital order in the valence shell in all the ions is 1a1, 1t2, 2a1, 2t2, 1e, 3t2 and 1t1. The results are compared when possible with experimental data and ab initio results. 相似文献
790.