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Second Coordination Sphere (second + coordination_sphere)
Selected AbstractsMolecular recognition of sugars by lanthanide (III) complexes of a conjugate of N, N -bis[2-[bis[2-(1, 1-dimethylethoxy)-2-oxoethyl]amino]ethyl]glycine and phenylboronic acidCONTRAST MEDIA & MOLECULAR IMAGING, Issue 4 2007Elisa Battistini Abstract A novel conjugate of phenylboronic acid and an Ln(DTPA) derivative, in which the central acetate pendant arm was replaced by the methylamide of L -lysine, was synthesized and characterized. The results of a fit of variable 17O NMR data and a 1H NMRD profile show that the water residence lifetime of the Gd(III) complex (150,ns) is shorter than that of the parent compound Gd(DTPA)2, (303,ns). Furthermore, the data suggest that several water molecules in the second coordination sphere of Gd(III) contribute to the relaxivity of the conjugate. The Ln(III) complexes of this conjugate are highly suitable for molecular recognition of sugars. The interaction with various sugars was investigated by 11B NMR spectroscopy. Thanks to the thiourea function that links the phenylboronic acid targeting vector with the DTPA derivative, the interactions are stronger than that of phenylboronic acid itself. In particular, the interaction with N -propylfructosamine, a model for the glucose residue in glycated human serum albumin (HSA), is very strong. Unfortunately, the complex also shows a rather strong interaction with hexose-free HSA (KA,=,705,±,300). Copyright © 2007 John Wiley & Sons, Ltd. [source] Non-Tethered Organometallic Phosphonate Inhibitors for Lipase Inhibition: Positioning of the Metal Center in the Active Site of Cutinase,,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 28 2008Cornelis A. Kruithof Abstract Organometallic NCN-pincer complexes, bearing either a p -nitrophenyl phosphonate ester or a phosphonic acid group directly attached to the aromatic ring of the pincer complex, were synthesized. These compounds were tested as covalent inhibitors for the lipase cutinase. In a stoichiometric reaction of the NCN-pincer platinum phosphonate p -nitrophenyl ester 2 with cutinase, a 94,% conversion to the protein,pincer metal complex hybrid was obtained in 48 h. The NCN-pincer metal phosphonic acid derivatives (3, 4) appeared to be inactive as cutinase inhibitors. In contrast to our previous work which entails propyl tethered phosphonate esters connected to pincer metal complexes, the presented strategy allows positioning of metal complexes inside the active site of lipases. This opens up the possibility for fine-tuning the chemical environment (second coordination sphere) around a synthetic metal center inside the pocket of an enzyme for diagnostic and catalytic purposes.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Enantioselective Proteins: Selection, Binding Studies and Molecular Modeling of Antibodies with Affinity towards Hydrophobic BINOL DerivativesCHEMBIOCHEM, Issue 16 2007Brian Schou Rasmussen Dr. Abstract In this paper, the initial steps towards the design of novel artificial metalloenzymes that exploit proteins as a second coordination sphere for traditional metal,ligand catalysis are described. Phage display was employed to select and study antibody fragments capable of recognizing hydrophobic BINOL derivatives designed to mimic BINAP, a widely used ligand in asymmetric metal-catalyzed reactions. The binding affinities of the selected antibodies towards a series of haptens were evaluated by using ELISA assays. A homology model of one of the most selective antibodies was constructed, and a computer-assisted ligand-docking study was carried out to elucidate the binding of the hapten. It was shown that, due to the hydrophobic nature of the haptens, a higher level of theoretical treatment was required to identify the correct binding modes. A small selection of the antibodies was found to discriminate between enantiomers and small structural modifications of the BINOL derivatives. The selectivities arise from hydrophobic interactions, and we propose that the identified set of antibodies provides a foundation for a novel route to artificial metalloenzymes. [source] A Novel Tripodal Ligand Containing Three Different N -Heterocyclic Donor Functions and Its Application in Catechol Dioxygenase MimickingCHEMISTRY - A EUROPEAN JOURNAL, Issue 22 2009Marit Wagner Dipl.-Chem. Abstract Prominent donors: A pyridyl, an imidazolyl, and a pyrazolyl donor function are part of the novel tripodal ligand depicted, which thus combines three of the most prominent donors applied in ligands for bioinorganic chemistry within one coordination unit. To exploit its behaviour and potential, first investigations have been carried out in relation to catechol dioxygenase mimicry. We describe a novel chiral ligand, L, in which three different N -donor functions are linked to a methoxymethine unit: a methylpyrazole derivative, a methylimidazole unit, and a pyridyl residue. Complexes with FeCl2, FeBr2, and FeCl3 have been synthesized and fully characterized, including with respect to their molecular structures. While in combination with FeCl3L coordinates in a tripodal fashion, with FeX2 (X=Cl, Br) it binds only through two functions and the pyridyl unit remains dangling. For potential modelling of intradiol and extradiol catechol dioxygenase reactivity, the complexes [LFeCl2], 1, and [LFeCl3], 3, have been treated with 3,5-di- tert -butylcatechol, triethylamine, and O2. Both complexes yielded similar results in such investigations, since the LFeII,catecholate complex reacts with O2 through one-electron oxidation in the first step. Employing 3 in acetonitrile solution, intradiol cleavage occurred, although the undesired quinone was formed as the main product. If reagents were added (NaBPh4, H+) or reaction conditions were chosen (CH2Cl2 instead of CH3CN as the solvent) that made the coordination sphere at the iron centre more accessible for a third substrate donor function, an alternative reaction route, presumably involving O2 binding at the metal, became more important, which led to extradiol cleavage. In the extreme case (CH2Cl2 as the solvent and with the addition of NaBPh4), mainly the extradiol cleavage products were formed; the intradiol products were only observed as side products then and quinone formation became negligible. Protonated base functions in the second coordination sphere increased the efficiency of extradiol cleavage only slightly. The obtained results are in line with current understanding of the function of intradiol/extradiol dioxygenases. [source] Ethylene Biosynthesis by 1-Aminocyclopropane-1-Carboxylic Acid Oxidase: A DFT StudyCHEMISTRY - A EUROPEAN JOURNAL, Issue 34 2006Arianna Bassan Dr. Abstract The reaction catalyzed by the plant enzyme 1-aminocyclopropane-1-carboxylic acid oxidase (ACCO) was investigated by using hybrid density functional theory. ACCO belongs to the non-heme iron(II) enzyme superfamily and carries out the bicarbonate-dependent two-electron oxidation of its substrate ACC (1-aminocyclopropane-1-carboxylic acid) concomitant with the reduction of dioxygen and oxidation of a reducing agent probably ascorbate. The reaction gives ethylene, CO2, cyanide and two water molecules. A model including the mononuclear iron complex with ACC in the first coordination sphere was used to study the details of OO bond cleavage and cyclopropane ring opening. Calculations imply that this unusual and complex reaction is triggered by a hydrogen atom abstraction step generating a radical on the amino nitrogen of ACC. Subsequently, cyclopropane ring opening followed by OO bond heterolysis leads to a very reactive iron(IV),oxo intermediate, which decomposes to ethylene and cyanoformate with very low energy barriers. The reaction is assisted by bicarbonate located in the second coordination sphere of the metal. [source] | ||||||||||