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Chelates
Kinds of Chelates Terms modified by Chelates Selected AbstractsChelate [2-(Iminoethyl)pyridine N -oxide]metal Complexes , Synthesis and Structural Comparison with Their Chemically Related 2-(Iminoethyl)pyridine-Derived SystemsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2006Katrin Nienkemper Abstract The N,O-chelate ligands 2-(iminoethyl)pyridine N -oxide (2a) and 2-(iminoethyl)-6-isopropylpyridine N -oxide (2b) were prepared by conventional synthetic routes, the latter involving a variant of the Reissert,Henze reaction. Treatment of 2a with FeCl2 resulted in a deoxygenation reaction of the ligand and formation of the salt [bis{2-(iminoethyl)pyridine}FeCl]+[FeCl4], (18a). In contrast, the reaction of 2a with PdCl2 or CoCl2 cleanly furnished the six-membered chelate [,N,O -2(iminoethyl)pyridine N -oxide]MCl2 complexes (19a, M = Pd) or (20a, M = Co), respectively, which were both characterised by X-ray diffraction. Treatment of 2b with [NiBr2(dme)], followed by crystallisation from THF, gave the complex [(,N,O - 2b)NiBr2(THF)] (21b), which features a distorted trigonal-bipyramidal coordination geometry of the central metal atom. The reaction of 2a with [NiBr2(dme)] gave the structurally related complex [(,N,O - 2a)NiBr2(,O - 2a)] (21a). The N,O-chelate Pd complex 19a was shown to be an active catalyst for the Suzuki coupling reaction. The ligand systems 2a,b and their related 2-(iminoethyl)pyridines 3a,b and a variety of metal complexes of ligands 3 were also prepared and characterised for comparison by X-ray diffraction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Deposition of Carbonated Hydroxyapatite (CO3HAp) on Poly(Methylmethacrylate) Surfaces by Decomposition of Calcium,EDTA ChelateJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 10 2008Yusuf Yusufoglu Inspired from the nature, the development of organic,inorganic composites between polymers and hydroxyapatite (HAp) has been investigated extensively. In this study, bone-like apatite (carbonated hydroxyapatite, CO3HAp) was precipitated on poly(methylmethacrylate) (PMMA) films by the oxidative decomposition of Ca,EDTA (calcium,ethylenediamine tetraacetate) chelates. Corona-treated PMMA films were soaked in a Ca,EDTA,PO4,H2O2 solution and aged at 63°C and pH,9 for times ranging from 1 to 24 h. Apatite formed on PMMA films was characterized by X-ray diffraction, Fourier transform infrared (FTIR), Scanning electron microscope, energy-dipersive X-ray spectroscopy, and carbon analysis. The apatite was found to be CO3HAp with Ca/P atomic ratio ranging between 1.3 and 1.9. Elemental analyses indicated that the carbonate content of the apatite phase was around 6.5 wt% after 24 h of aging time. Lattice parameters were estimated using a Rietveld profile-analysis and found to be a=0.9438 nm and c=0.6901 nm. Furthermore, FTIR spectra indicated that the apatite deposited on PMMA was B-type CO3HAp, in which carbonate ions occupy the phosphate sites. In the first 3 h of aging, isolated rod-like HAp particles were observed. With time, the needle-like crystallites radiate from a nucleus to form double-spherulite shape particles. The crystallites grew into a continuous layer with a thickness of ,15 ,m after 24-h aging. The adhesive strength between the PMMA substrate and the apatite layer was determined to be around 1.7 MPa. [source] Effect of pH on the Carbonate Incorporation into the Hydroxyapatite Prepared by an Oxidative Decomposition of Calcium,EDTA ChelateJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 1 2008Yusuf Yusufoglu In this study, the carbonate incorporation into the hydroxyapatite (HAp) lattice under various pH conditions was investigated. Crystalline-sodium and carbonate-containing calcium HAp (NaCO3HAp) powders were prepared using an oxidative decomposition of calcium,EDTA chelates in a sodium phosphate solution with hydrogen peroxide. The powders obtained were characterized by X-ray diffraction, infrared spectroscopy, thermal gravimetric analysis, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and elemental analysis. Depending on pH, spherical particles approximately 3.5 ,m in diameter or hexagonal prismatic particles measuring 3,9 ,m in length were obtained. Various characterization techniques showed that the precipitates were a single-phase NaCO3HAp. The carbonate content and the lattice parameters of the HAp were a function of solution pH. Maximum carbonate incorporated into the HAp lattice was at pH=10, corresponding to lattice parameters of a=0.93880 nm and c=0.69070 nm. Furthermore, spectroscopic analyses indicate that the as-prepared samples are B-type carbonated HAp, in which carbonate ions occupy the phosphate sites. After heat treatment at 965°C, most of the carbonate is removed from the HAp lattice. [source] Efficient Preparation of 1,4,8-Trimethylcyclam and Its Conversion into a Thioalkyl-Pendant Pentadentate Chelate.CHEMINFORM, Issue 10 2004Jason A. Halfen No abstract is available for this article. [source] Supramolecular Assembly of an Amphiphilic GdIII Chelate: Tuning the Reorientational Correlation Time and the Water Exchange RateCHEMISTRY - A EUROPEAN JOURNAL, Issue 3 2006Susana Torres Abstract We report the synthesis and characterization of the novel ligand H5EPTPA-C16 ((hydroxymethylhexadecanoyl ester)ethylenepropylenetriaminepentaacetic acid). This ligand was designed to chelate the GdIII ion in a kinetically and thermodynamically stable way while ensuring an increased water exchange rate (kex) on the GdIII complex owing to steric compression around the water-binding site. The attachment of a palmitic ester unit to the pendant hydroxymethyl group on the ethylenediamine bridge yields an amphiphilic conjugate that forms micelles with a long tumbling time (,R) in aqueous solution. The critical micelle concentration (cmc = 0.34 mM) of the amphiphilic [Gd(eptpa-C16)(H2O)]2, chelate was determined by variable-concentration proton relaxivity measurements. A global analysis of the data obtained in variable-temperature and multiple-field 17O NMR and 1H NMRD measurements allowed for the determination of parameters governing relaxivity for [Gd(eptpa-C16)(H2O)]2,; this is the first time that paramagnetic micelles with optimized water exchange have been investigated. The water exchange rate was found to be = 1.7×108 s,1, very similar to that previously reported for the nitrobenzyl derivative [Gd(eptpa-bz-NO2)(H2O)]2, ( = 1.5×108 s,1). The rotational dynamics of the micelles were analysed by using the Lipari,Szabo approach. The micelles formed in aqueous solution show considerable flexibility, with a local rotational correlation time of = 330 ps for the GdIII segments, which is much shorter than the global rotational correlation time of the supramolecular aggregates, = 2100 ps. This internal flexibility of the micelles is responsible for the limited increase of the proton relaxivity observed on micelle formation (r1 = 22.59 mM,1,s,1 for the micelles versus 9.11 mM,1,s,1 for the monomer chelate (20 MHz; 25,°C)). [source] Evaluation of rHA labeled with Gd,DTPA for blood pool imaging and targeted contrast deliveryCONTRAST MEDIA & MOLECULAR IMAGING, Issue 1 2010Jim M. Wild Abstract A new contrast agent was developed by linking Gd,DTPA chelate to recombinant human albumin in the laboratory. The molar relaxivity of the new agent was tested in aqueous solution at B0 1.5,T and temperature 20°C. The soluble compound had a higher molar longitudinal relaxivity and molar transverse relaxivity in water (r1,=,7.2,s,1,mM,1, r2,=,18.4,s,1,mM,1) than those measured for Gd,DTPA solution (r1,=,3.5,s,1,mM,1, r2,=,5.5,s,1,mM,1). The performance of the compound as a blood pool agent was investigated with soluble and microparticulate forms of the compound and comparisons were made with Gd,DTPA and the polymeric blood-pool agent, Gadomer. T1 -weighted imaging experiments show that the soluble compound acts as a highly effective blood pool agent with hyperintensity in the vasculature persisting beyond 2,h post administration, compared with free Gd,DTPA, which was cleared from the blood pool after approximately 10,min. The clearance kinetics of the new agents were examined, due to the incomplete elimination within 14 days post injection; both rHA labeled compounds are probably not suitable for development as routine blood pool contrast media. However, with free sites on the Gd-loaded rHA molecule, there are possibilities for binding the agent to antibodies in the laboratory, which was demonstrated, and thus there exist potential applications for in vivo molecular imaging with this agent. Copyright © 2010 John Wiley & Sons, Ltd. [source] Novel Enantioselective Synthesis of Functionalized Pyridylarsanes by a Chiral Palladium Template Promoted Asymmetric Hydroarsanation ReactionEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 27 2009Fengli Liu Abstract The asymmetric hydroarsanation reactions between diphenylarsane and (E)-1-phenyl-3-(pyridin-2-yl)-2-propenone and (E)-1-methyl-3-(pyridin-2-yl)-2-propenoate have been achieved by use of the organopalladium complex containing ortho -metalated (R)-[1-(dimethylamino)ethyl]naphthalene as the chiral reaction template in high regio- and stereoselectivities under mild conditions. Hydroarsanation of (E)-1-phenyl-3-(pyridin-2-yl)-2-propenone with diphenylarsane generated two stereoisomeric products in the ratio of 3:1 as five-membered As,N bidentate chelates on the chiral naphthylamine palladium template. Using the same chiral metal template, the corresponding hydroarsanation reaction with (E)-1-methyl-3-(pyridin-2-yl)-2-propenoate gave only one product as a six-membered As,N bidentate chelate. The naphthylamine auxiliary could be removed chemoselectively by treatment with concentrated hydrochloric acid to form the corresponding optically pure neutral complexes. Subsequent ligands displacement from the palladium using aqueous potassium cyanide generated the optically pure keto- and ester-functionalized chiral pyridylarsane ligands. The absolute configuration and the coordination properties of the pyridylarsanes have been established by single-crystal X-ray analysis.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Control of Intramolecular Ether-Oxygen Coordination in the Crystal Structure of Copper(II) Complexes With Dipicolylamine-Based LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2007Yuji Mikata Abstract Thirteen crystal structures of copper(II) complexes with a series of dipicolylamine (DPA)-derived ligands, N -(2-methoxyethyl)- N,N -bis(2-pyridylmethyl)amine (L1), N -[2-(2-hydroxyethyloxy)ethyl]- N,N -bis(2-pyridylmethyl)amine (L2) and N -(3-methoxypropyl)- N,N -bis(2-pyridylmethyl)amine (L3), have been determined and the factors that control the coordination of the ether-oxygen atom of these ligands to the copper centre are discussed. Complexes that have +1 or +2 charges exhibit coordination of the ether-oxygen atom, whereas neutral complexes in which two anions are bound to the copper(II) centre tend to lose the oxygen coordination. Upon chelation of the oxygen atom, L3 forms a six-membered chelate ring with respect to the 3-aminopropyl ether moiety whereas L1 and L2 form a five-membered chelate. This difference, especially in the nitrate and bromide complexes, determines whether the ether-oxygen atom chelates to the metal centre to give a monocationic complex, or the second anion coordinates to the metal centre to form the ether-free, neutral complex. The terminal anchor hydroxy group of L2 facilitates the ether-oxygen coordination via a hydrogen bond interaction to the donor atom located trans to the aliphatic nitrogen atom in the basal plane. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Synthesis and Structural Characterisation of Palladium and Group-12 Metal Complexes with a Hybrid Phosphanylphosphonate Ferrocene LigandEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 5 2006Abstract Diethyl [1,-(diphenylphosphanyl)ferrocenyl]phosphonate (1) was synthesised by stepwise metallation/functionalisation of 1,1,-dibromoferrocene and studied as a ligand for palladium(II) and group-12 metals. Treatment of [PdCl2(cod)] (cod = ,2:,2 -cycloocta-1,5-diene) with 1 in 1:1 or 1:2 molar ratios gave, respectively, the dinuclear, chloride-bridged complex [{Pd(,-Cl)Cl(1 -,P2)}2] (2) and the mononuclear complex trans -[PdCl2(1 -,P2)2] (3), where 1 coordinates exclusively through the phosphane function. The reactions between 1 and group-12 metal bromides MBr2 in a 1:1 molar ratio gave the adducts [MBr2(1)] [M = Zn (4), Cd (5), and Hg (6)], whose crystal structures change considerably with the metal ion. Thus, whereas 4 is a molecular complex with 1 coordinating as an O1,P2 -chelate, its cadmium(II) analogue is a polymer built up from symmetric {CdBr(,-Br)}2 units interconnected by pairs of O1,P2 -bridging phosphanylphosphonate ligands. Finally, the mercury(II) complex 6 is a halide-bridged dimer, [{Hg(,-Br)Br(1 -,P2)}2]. However, this compound is structurally fluxional in solution (NMR spectra) and, in the crystal, it attains a structure similar to 5 owing to weak interactions between mercury and phosphonate-O1 atoms from adjacent molecules. An isomer to 6, [{HgBr2(1 -,2O1,P2)}2] (7), was isolated from attempted alkylation of 6 and structurally characterised as a dimer, where ligands 1 bridge two {HgBr2} units. All compounds were studied by spectroscopic methods (IR, NMR, mass) and the solid-state structures of 1, 2·,H2O, 3·4,CHCl3, 4, 5, 6·5,C6H6, and 7 have been determined by single-crystal X-ray diffraction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Chelate [2-(Iminoethyl)pyridine N -oxide]metal Complexes , Synthesis and Structural Comparison with Their Chemically Related 2-(Iminoethyl)pyridine-Derived SystemsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2006Katrin Nienkemper Abstract The N,O-chelate ligands 2-(iminoethyl)pyridine N -oxide (2a) and 2-(iminoethyl)-6-isopropylpyridine N -oxide (2b) were prepared by conventional synthetic routes, the latter involving a variant of the Reissert,Henze reaction. Treatment of 2a with FeCl2 resulted in a deoxygenation reaction of the ligand and formation of the salt [bis{2-(iminoethyl)pyridine}FeCl]+[FeCl4], (18a). In contrast, the reaction of 2a with PdCl2 or CoCl2 cleanly furnished the six-membered chelate [,N,O -2(iminoethyl)pyridine N -oxide]MCl2 complexes (19a, M = Pd) or (20a, M = Co), respectively, which were both characterised by X-ray diffraction. Treatment of 2b with [NiBr2(dme)], followed by crystallisation from THF, gave the complex [(,N,O - 2b)NiBr2(THF)] (21b), which features a distorted trigonal-bipyramidal coordination geometry of the central metal atom. The reaction of 2a with [NiBr2(dme)] gave the structurally related complex [(,N,O - 2a)NiBr2(,O - 2a)] (21a). The N,O-chelate Pd complex 19a was shown to be an active catalyst for the Suzuki coupling reaction. The ligand systems 2a,b and their related 2-(iminoethyl)pyridines 3a,b and a variety of metal complexes of ligands 3 were also prepared and characterised for comparison by X-ray diffraction. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Iminohydroxamato Early and Late Transition Metal Halide Complexes , New Precatalysts for Aluminoxane-Cocatalyzed Olefin Insertion PolymerizationEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 8 2004Alexander Krajete Abstract We report on new families of non-metallocene metal precatalysts for olefin polymerization with titanium, zirconium, vanadium and nickel as the active metal sites. The novel ligand design concept is based on iminohydroxamic acids and their derivatives as the principal chelating units. Various anionic and neutral [N,O] and [N,N] ligand systems are easily accessible by a modular synthetic sequence of imidoyl chlorides with substituted hydroxylamines or hydrazines, respectively. Steric protection of the metal coordination site, a necessary requirement for suppression of chain termination pathways of non-metallocene catalysts, is brought about by bulky aryl substituents on the imino nitrogen atoms. Crystal structures of some of the hydroxamato ligands reveal interesting intermolecular hydrogen-bridged structures, whereas in the solid-state structure of one titanium precatalyst a five-membered chelate was observed, in line with the design principle of these systems. Preliminary ethylene polymerization studies with methylaluminoxane-activated metal complexes (M = Ti, Zr, V, Ni) show that the most active systems are [N,O]NiBr2 catalysts containing neutral O -alkyl iminohydroxamate ligands. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] A Rigid Molecular Scaffold Affixing a (Polypyridine)ruthenium(II)- and a Nickel(II)-Containing Complex: Spectroscopic Evidence for a Weakly Coupled Bichromophoric SystemEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 10 2003Yann Pellegrin Abstract The synthesis of DppztBuSalH2 (7), a rigid conjugated ditopic ligand containing a Dppz (dipyrido[3,2- a:2,,3,- c]phenazine) skeleton and a salophen-type chelate, is reported. The complexes DppztBuSalNi (10), [Ru(bpy)2(DppztBuSalH2)]2+ (11), and [Ru(bpy)2(DppztBuSalNi)]2+ (12) have been prepared and characterised using common spectroscopic methods. Electrochemical, UV/Vis spectroelectrochemical and EPR studies were conducted on compounds 7, 10, 11, and 12. The singly reduced radical forms of 7 and 10 can be generated electrochemically, with the lone electron located on the low-lying phenazine ,*-molecular orbital. Complexes 11 and 12 show several reduction waves and electronic and EPR data obtained for the electrogenerated singly reduced species show them to be closely related to the radical species 7·, and 10·,, respectively. The presence of nickel(II) in compound 12 renders the addition of the second electron on the phenazine group reversible. Both 11 and 12 show common features on the cathodic side of their cyclic voltammograms, with reversible one-electron ruthenium-centred oxidation. An additional low-potential reversible-oxidation wave is observed for 12, and this is ascribed to oxidation of the nickel(II) ion. The combined spectroscopic data best describe the ruthenium-containing complexes as weakly coupled bichromophoric systems. Photophysical studies attest to the formation of a charge-separated state for 11, whereas a strong quenching is detected for 12. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Photochromic Properties of a Spirooxazine and a Spiropyran in Alcoholic Solutions of Zirconium and Aluminium Alkoxides: Influence of the Ethyl Acetoacetate Chelating Agent on the Optical PropertiesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 2 2003Aurélie Lafuma Abstract The photochromism of two spiro compounds, a spiropyran and a spirooxazine, dissolved in alcoholic solutions of metal alkoxides M(OR)n (M = Zr, Al) has been studied. In the case of the aluminium alkoxide Al(OsBu)3, special photochromic behaviour is observed characteristic of complexation between the coloured form of the dyes and the aluminium. This chemical interaction induces a considerable shift in the absorption spectra and a significant retardation rate in the dark. Addition of ethyl acetoacetate, a bidentate chelate of aluminium, leads to the disappearance of this particular photochromic behaviour. (© Wiley-VCH Verlag GmbH & Co KGaA, 69451 Weinheim, Germany, 2003) [source] A Synthesis Detour to Planar-Diastereoisomeric Ferrocene Derivatives around an Unexpected Rearrangement of ortho -Lithiated Kagan's Template [S(S)] - (p -Tolylsulfinyl)ferroceneHELVETICA CHIMICA ACTA, Issue 4 2007Immo Weber Abstract Usually, ortho lithiation of Kagan's template 1 and quenching with electrophiles leads highly diastereoselectively to planar-chiral 1,2-disubstituted ferrocenes. Surprisingly, lithiation of 1 with lithium diisopropylamide (LDA) followed by addition of paraformaldehyde afforded regioisomer (+)-{[S(S)] - [4-(2-hydroxyethyl)phenyl]sulfinyl}ferrocene (2), which was converted to (+)-{[S(S)] - {4-{2-[(methylsulfonyl)oxy]ethyl}phenyl}sulfinyl}ferrocene (3) (Scheme,1). The desired diastereoisomer (l)-1-(hydroxymethyl)-2-(p -tolylsulfinyl)ferrocene (5) in turn could also be obtained by ortho lithiation of 1 with LDA but by quenching with DMF to yield aldehyde 4 first, which then was reduced with NaBH4 to 5. Finally, target compound (l)-1-[(dimethylamino)methyl]-2-(p -tolylsulfinyl)ferrocene (6) was obtained by substitution of the OH group of 5 under mild conditions or directly by ortho lithiation of 1 with lithio-2,4,6-triisopropylbenzene (=2,4,6-triisopropylphenyl)lithium; LTP) followed by quenching with N,N -dimethylmethyleneiminium chloride. At low temperatures, reaction of 1 with LDA leads, via the preferred diastereoisomeric transition state ,exo'- 7 and under extrusion of a (diisopropylamine)lithium complex of type 8, in a highly selective manner, to diastereoisomeric ortho -lithiated chelate (l)- 9 (Scheme,2). The reaction of 1 to 2 is explained by a rearrangement of (l)- 9 to {[S(S)],[4-(lithiomethyl)phenyl]sulfinyl}ferrocene 10, which is acid-catalyzed by coordinated diisopropylamine in complexes of type 8. This rearrangement is not observed if LTP is used as base or, in case LDA is applied, if the electrophile is sufficiently reactive at low temperatures. [source] Stereodivergent Formation of Alkenylsilanes: syn or anti Hydrosilylation of Alkynes Catalyzed by a Cyclopentadienylcobalt(I) Chelate Bearing a Pendant Phosphane TetherADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 7-8 2006Li Yong Abstract The hydrosilylation of alkynes is catalyzed by the di- tert -butylphosphanylethylcyclopentadienylcobalt chelate 1. While the reaction of internal alkynes exclusively affords syn hydrosilylation products with triethylsilane, the reaction with triethoxysilane shows predominant anti stereoselectivity. Reactions of terminal alkynes are less selective with triethylsilane and result in cyclotrimerization when triethoxysilane is used. [source] Detecting microdamage in boneJOURNAL OF ANATOMY, Issue 2 2003T. C. Lee Abstract Fatigue-induced microdamage in bone contributes to stress and fragility fractures and acts as a stimulus for bone remodelling. Detecting such microdamage is difficult as pre-existing microdamage sustained in vivo must be differentiated from artefactual damage incurred during specimen preparation. This was addressed by bulk staining specimens in alcohol-soluble basic fuchsin dye, but cutting and grinding them in an aqueous medium. Nonetheless, some artefactual cracks are partially stained and careful observation under transmitted light, or epifluorescence microscopy, is required. Fuchsin lodges in cracks, but is not site-specific. Cracks are discontinuities in the calcium-rich bone matrix and chelating agents, which bind calcium, can selectively label them. Oxytetracycline, alizarin complexone, calcein, calcein blue and xylenol orange all selectively bind microcracks and, as they fluoresce at different wavelengths and colours, can be used in sequence to label microcrack growth. New agents that only fluoresce when involved in a chelate are currently being developed , fluorescent photoinduced electron transfer (PET) sensors. Such agents enable microdamage to be quantified and crack growth to be measured and are useful histological tools in providing data for modelling the material behaviour of bone. However, a non-invasive method is needed to measure microdamage in patients. Micro-CT is being studied and initial work with iodine dyes linked to a chelating group has shown some promise. In the long term, it is hoped that repeated measurements can be made at critical sites and microdamage accumulation monitored. Quantification of microdamage, together with bone mass measurements, will help in predicting and preventing bone fracture failure in patients with osteoporosis. [source] Biological evaluation and comparison of three different procedures for labelling of amino acids tyrosine and lysine with technetium-99mJOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, Issue 3 2007D. Djoki Abstract The 99mTc-labelling of the amino acids tyrosine (Tyr) and lysine (Lys), fundamental building blocks of proteins and peptides, as well as biological properties of the labelled compounds are investigated. Three different approaches for the labelling with 99mTc have been investigated: direct reduction with stannous tin in the presence of the amino acids, the preformed chelate approach through polydentate chelates DTPA and GH, and the ,organometallic approach' using [99m Tc(CO)3(H2O)3]+ precursor. The direct labelling approach was not successful and the yield was poor. In the presence of DTPA and GH, the labelling efficiency was between 43.6 and 97.8%, depending on the amino acid and the polydentate chelate. The use of [99mTc(CO)3(H2O)3]+ precursor point at the formation of 99m Tc(I) co-ordinated complexes with high yield. In this approach, pH and heating influenced the yields. The results of organ distribution study for [99mTc(Tyr)(H2O)(CO)3] and [99mTc(Lys)(H2O)(CO)3] show accumulation in liver, kidneys and intestine. Copyright © 2007 John Wiley & Sons, Ltd. [source] Heavy-metal displacement in chelate-treated soil with sludge during phytoremediationJOURNAL OF PLANT NUTRITION AND SOIL SCIENCE, Issue 6 2006Stanley Liphadzi Abstract Heavy metals (HMs) in domestic sewage sludge, applied to land, contaminate soils. Phytoremediation is the use of plants to clean-up toxic HMs from soil. Chelating agents are added to soil to solubilize the metals for enhanced uptake. Yet no studies report the displacement of HMs in soil with sludge following solubilization with chelates. The objective of this work was to determine the uptake or leaching of HMs due to a chelate added to a soil from a sludge farm that had received sludge for 25 y. The soil was placed in long columns (105,cm long; , 39,cm) in a greenhouse. Columns either had a plant (hybrid poplar; Populus deltoides Marsh. × P. nigra L.) or no plant. After the poplar seedlings had grown for 144 d, the tetrasodium salt of the chelating agent EDTA was irrigated onto the surface of the soil at a rate of 1 g per,kg of soil. Drainage water, soil, and plants were analyzed for three toxic HMs (Cd, Ni, Pb) and four essential HMs (Cu, Fe, Mn, Zn). At harvest, extractable and total concentrations of each HM in the soil with EDTA were similar to those in soil without EDTA. The chelate did not affect the concentrations of HMs in the roots or leaves. With or without plants, EDTA mobilized all seven HMs and increased their concentrations in drainage water. Lower concentrations of Cd, Cu, Fe, Ni, and Zn in leachate from columns with EDTA and plants compared to columns with EDTA and no plants showed that poplars can reduce groundwater contamination by intercepting these HMs in the soil. But the poplar plants did not reduce Pb and Mn in the leachate from columns with EDTA. Concentrations of Cd and Pb in the leachate mobilized by EDTA remained above drinking-water standards with or without plants. The results showed that a chelate (EDTA) should not be added to a soil at a sludge farm to enhance phytoremediation. The chelate mobilized HMs that leached to drainage water and contaminated it. [source] Chromatographic methods for the separation of biocompatible iron chelators from their synthetic precursors and iron chelatesJOURNAL OF SEPARATION SCIENCE, JSS, Issue 17-18 2004Petra Kova, íková Abstract Chromatographic methods have been developed for the separation of the three novel biocompatible iron chelators pyridoxal isonicotinoyl hydrazone (PIH), salicylaldehyde isonicotinoyl hydrazone (SIH), and pyridoxal 2-chlorobenzoyl hydrazone (o-108) from their synthetic precursors and iron chelates. The chromatographic analyses were achieved using analytical columns packed with 5 ,m Nucleosil 120-5 C18. For the evaluation of all chelators in the presence of the synthetic precursors, EDTA was added to the mobile phase at a concentration of 2 mM. The best separation of PIH and its synthetic precursors was achieved using a mixture of phosphate buffer (0.01 M NaH2PO4, 5 mM 1-heptanesulfonic acid sodium salt; pH 3.0) and methanol (55 : 45, v/v). For separation of SIH and its synthetic precursors, the mobile phase was composed of 0.01 M phosphate buffer (pH 6.0) and methanol (60 : 40, v/v). o-108 was analyzed employing a mixture of 0.01 M phosphate buffer (pH 7.0), methanol, and acetonitrile (60 : 20 : 20, v/v/v). These mobile phases were slightly modified to separate each chelator from its iron chelate. Furthermore, a RP-TLC method has also been developed for fast separation of all compounds. The chromatographic methods described herein could be applied in the evaluation of purity and stability of these drug candidates. [source] Preparation and Electrical Properties of an Anodized Al2O3,BaTiO3 Composite FilmJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 7 2008Xianfeng Du A highly stable, water-based barium titanate BaTiO3, BT, sol was synthesized using a sol,gel route through a chelate lactate technique. Dried BT precursor powders were measured by thermal gravimetry,differential thermal analysis and X-ray diffraction. It was found that BT powders first converted into barium carbonate BaCO3, Ti complex, and intermediate phase Ba2Ti2O5CO3, and then transformed into perovskite phase BaTiO3. The crystallization temperature was about 550°C. The low-voltage etched aluminum foils were covered with BT sol by dip coating, and then annealed at 600°C for 30 min in air. After that, the samples were anodized in a 15 wt% aqueous solution of ammonium adipate. The voltage,time variations during anodizing were monitored, and the electrical properties of the anodic oxide film were examined. It was shown that the specific capacitance, the product of specific capacitance and withstanding voltage, and leakage current of samples with a BT coating were about 48.93%, 38.50%, and 167% larger than that without a BT coating, respectively. [source] Fine Patterning of Hybrid Titania Films by Ultraviolet IrradiationJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 5 2003Hiyoro Segawa Photosensitive hybrid titania films have been prepared from titanium butoxide modified with ,-diketone and methacrylic acid. When this film is exposed to UV light, the ,-diketonato chelate from the alkoxide and ,-diketone is dissociated, and the unsaturated hydrocarbon of methacrylic acid is polymerized. These structural changes in the gel film have led to a difference between the solubility of irradiated and unirradiated parts in the film; therefore, a fine patternable hybrid titania film has been fabricated. [source] Root cadmium desorption methods and their evaluation with compartmental modelingNEW PHYTOLOGIST, Issue 1 2010Wayne T. Buckley Summary ,Desorption of plant roots is often employed in studies of plant physiology and nutrition; however, there have been few studies on the validity of desorption procedures. ,Branched and in-line kinetic models with five compartments , cadmium (Cd)-chelate, Cd2+, root apoplast, root symplast and vacuole , were developed to evaluate the efficacy of diethylenetriaminepentaacetic acid (DTPA) and CaCl2 methods for the desorption of Cd from roots of durum wheat seedlings. Solution Cd2+ could exchange with apoplast and symplast Cd simultaneously in the branched model and sequentially in the in-line model. ,A 10-min desorption with 1 × 10,6 M DTPA at room temperature or cold (0°C) 5 × 10,3 M CaCl2 was required to achieve 99% recovery of apoplast-bound 109Cd when experimental results were interpreted with the branched model. However, when the same data sets were analysed with the in-line model, only partial desorption was achieved. Arguments are presented that suggest that the branched model is correct. ,It is suggested that compartmental modeling is a suitable tool for the study of plant root uptake and desorption kinetics, and that there are advantages over more commonly used calculation procedures. [source] Gd(III)-EPTPAC16, a new self-assembling potential liver MRI contrast agent: in vitro characterization and in vivo animal imaging studies,NMR IN BIOMEDICINE, Issue 4 2008Suzana Torres Abstract The recently reported amphiphilic chelate, [Gd(EPTPAC16)(H2O)]2,, forms supramolecular aggregates in aqueous solution by self-assembly of the monomers with a relaxometrically determined critical micellar concentration (CMC) of 0.34,mM. The effect of sonication on the aggregate size was characterized by dynamic light scattering and relaxometry, indicating the presence of premicellar aggregates and an overall decrease in aggregate size and polydispersity upon sonication, slightly below the CMC. {[153Sm](EPTPAC16)(H2O)}2, radiotracer was evaluated in vivo from , scintigraphy and biodistribution in Wistar rats. It was found to depend strongly on the sample concentration, below or above the CMC, and its sonication, in a way that correlates with the effect of the same factors on the size of the aggregates formed in solution. Below CMC, the very large aggregates of the [153Sm]3+ -labeled chelate were persistently and mainly taken up by the lungs, and also by the macrophage-rich liver and spleen. Sonication of this solution led to loss of the lung uptake. Above CMC, the metal chelate was mainly taken up by the liver, with very little uptake by the spleen and lungs. In vivo, dynamic contrast-enhanced (DCE)-MRI evaluation of the micellar [Gd(EPTPAC16)(H2O)]2, compound in Wistar rats showed a persistent hepatic positive-contrast effect in T1 -weighted images, qualitatively similar to the clinically established GdIII -based hepatobiliary-selective agents. No enhancement effect was observed in the lungs because of the scarcity of mobile protons in this organ, despite the scintigraphic evidence of significant lung retention of the [153Sm]3+ -labeled chelate at concentrations below the CMC. Copyright © 2007 John Wiley & Sons, Ltd. [source] Structure correlation study of four-coordinate copper(I) and (II) complexesACTA CRYSTALLOGRAPHICA SECTION B, Issue 3 2000Paul R. Raithby The geometries of four-coordinate CuI and CuII complexes in the Cambridge Structural Database (CSD) have been analysed systematically and compared using symmetry-deformation coordinates and principal component analysis. The observed stereochemistries have been rationalized in terms of the d -electron configurations, interligand repulsion and ,-bonding effects. The results confirm that the majority of four-coordinate copper(I) complexes in the CSD adopt tetrahedral geometries and deviations from tetrahedral symmetry are caused by the presence of chelating ligands or by the incorporation of copper centres into dimeric or polymeric structures. Four-coordinate copper(II) complexes generally adopt geometries close to square planar; this is particularly evident for bis(chelate) complexes where ,-bonding is important. Distortions towards tetrahedral geometries are attributable to steric interactions of bulky substituents in the bidentate ligands. [source] Poly[[tetraaqua(,7 -pyridine-2,3,5,6-tetracarboxylato)dicadmium(II)] monohydrate]ACTA CRYSTALLOGRAPHICA SECTION C, Issue 4 2010Sitang Yan The title compound, {[Cd2(C9HNO8)(H2O)4]·H2O}n, consists of two crystallographically independent CdII cations, one tetrabasic pyridine-2,3,5,6-tetracarboxylate (pdtc) anion, four coordinated water molecules and one solvent water molecule. The CdII cations have distorted square-antiprismatic (one pyridine N, six carboxylate O and one water O atom) and octahedral (three carboxylate O and three water O atoms) coordination environments. Each pdtc ligand employs its pyridine and carboxylate groups to chelate and bridge seven CdII cations. The square-antiprismatic coordinated CdII cations are linked by pdtc ligands into a lamellar framework structure, while the octahedral coordinated CdII cations are bridged by the ,2 -carboxylate O atoms and the pdtc ligands into a chain network that further joins neighbouring lamellae into a three-dimensional porous network. The cavities are filled with solvent water molecules that are linked to the host through complex hydrogen bonding. [source] Poly[(acetone)tetraaqua[,6 -ethyl (dichloromethylene)diphosphonato][,5 -ethyl (dichloromethylene)diphosphonato]tribarium(II)]ACTA CRYSTALLOGRAPHICA SECTION C, Issue 4 2009Jonna Jokiniemi The novel title compound, [Ba3(C3H5Cl2O6P2)2(C3H6O)(H2O)4]n, has a polymeric two-dimensional network structure which lies parallel to the (10) plane. The asymmetric unit consists of three independent Ba2+ ions, two of them eight-coordinated and the third nine-coordinated, and two independent ethyl (dichloromethylene)diphosphonate(3,) ligands, one acetone ligand and four aqua ligands. The coordination environments around the BaO8 polyhedra are best described as bicapped trigonal prismatic, while the BaO9 polyhedron is in a distorted tricapped trigonal prismatic geometry. The two diphosphonate ligands adopt different coordination modes. Both ligands chelate three metal cations, but one is coordinated to six metal cations in total and forms two six-membered and one four-membered chelate ring, while the other is coordinated to five metal cations in total and forms one six-membered and two four-membered chelate rings, the fifth unsubstituted O atom remaining uncoordinated. [source] A Paramagnetic Contrast Agent for Detecting Tyrosinase ActivityCHEMBIOCHEM, Issue 14 2007Manuel Querol MRI imaging of tyrosinase. A paramagnetic bifunctional chelate that contained tyramide residues was oxidized, polymerized, and linked to albumin by using tyrosinase, as illustrated in the scheme. This technique enabled the magnetic resonance (MR) imaging of tyrosinase catalytic activity. [source] Analysis of Platinum Adducts with DNA Nucleotides and Nucleosides by Capillary Electrophoresis Coupled to ESI-MS: Indications of Guanosine 5,-Monophosphate O6,N7 ChelationCHEMBIOCHEM, Issue 11 2004Ulrich Warnke Dr. Abstract DNA is the ultimate target of platinum-based anticancer therapy. Since the N7 of guanine is known to be the major binding site of cisplatin and its analogues, adduct formation with model nucleotides, especially 2,-deoxyguanosine 5,-monophosphate (dGMP), has been studied in detail. During the last few years a coupled capillary eletrophoresis/electrospray-ionization mass spectrometry (CE/ESI-MS) method has been advantageously used in order to separate and identify platinum adducts with nucleotides in submillimolar concentrations in aqueous solutions. Beside the bisadduct, [Pt(NH3)2(dNMP)2]2,(NMP=2,-deoxynucleoside 5,-monophosphate), and the well-known monochloro and monohydroxo adducts, [Pt(NH3)2Cl(dNMP)],and [Pt(NH3)2(dNMP)OH],, respectively, a third kind of monoadduct species with a composition of [Pt(NH3)2(dNMP)],can be separated by CE and detected through the m/z values measured with ESI-MS. Different experimental setups indicate the existence of an O6,N7 chelate, whereas the formation of N7,,PO4macrochelates or dinuclear species is unlikely. Additionally, offline MS experiments with 2,-deoxyguanosine (dG) and stabilization of the controversially discussed O6,N7 chelate by oxidation with hydrogen peroxide support the assumption of the existence of O6,N7 chelation. [source] Discrimination in Metal-Ion Binding to RNA Dinucleotides with a Non-Bridging Oxygen or Sulfur in the Phosphate Diester Link,CHEMISTRY - A EUROPEAN JOURNAL, Issue 10 2008Bernd Knobloch Dr. Abstract Replacement of a non-bridging oxygen in the phosphate diester bond by a sulfur has become quite popular in nucleic acid research and is often used as a probe, for example, in ribozymes, where the normally essential Mg2+ is partly replaced by a thiophilic metal ion to reactivate the system. Despite these widely applied rescue experiments no detailed studies exist quantifying the affinity of metal ions to such terminal sulfur atoms. Therefore, we performed potentiometric pH titrations to determine the binding properties of pUp(S)U3, towards Mg2+, Mn2+, Zn2+, Cd2+, and Pb2+, and compared these data with those previously obtained for the corresponding pUpU3, complexes. The primary binding site in both dinucleotides is the terminal phosphate group. Theoretically, also the formation of 10-membered chelates involving the terminal oxygen or sulfur atoms of the (thio)phosphate bridge is possible with both ligands. The results show that Mg2+ and Mn2+ exist as open (op) isomers binding to both dinucleotides only at the terminal phosphate group. Whereas Cd(pUpU), only exists as Cd(pUpU), Cd(pUp(S)U), is present to about 64,% as the S-coordinated macrochelate, Cd(pUp(S)U). Zn2+ forms with pUp(S)U3, three isomeric species, that is, Zn(pUp(S)U), Zn(pUp(S)U), and Zn(pUp(S)U), which occur to about 33, 12 (O-bound), and 55,%, respectively. Pb2+ forms the 10-membered chelate with both nucleotides involving only the terminal oxygen atoms of the (thio)phosphate bridge, that is, no indication of S binding was discovered in this case. Hence, Zn2+ and Cd2+ show pronounced thiophilic properties, whereas Mg2+, Mn2+, and Pb2+ coordinate to the oxygen, macrochelate formation being of relevance with Pb2+ only. [source] Supramolecular Assembly of an Amphiphilic GdIII Chelate: Tuning the Reorientational Correlation Time and the Water Exchange RateCHEMISTRY - A EUROPEAN JOURNAL, Issue 3 2006Susana Torres Abstract We report the synthesis and characterization of the novel ligand H5EPTPA-C16 ((hydroxymethylhexadecanoyl ester)ethylenepropylenetriaminepentaacetic acid). This ligand was designed to chelate the GdIII ion in a kinetically and thermodynamically stable way while ensuring an increased water exchange rate (kex) on the GdIII complex owing to steric compression around the water-binding site. The attachment of a palmitic ester unit to the pendant hydroxymethyl group on the ethylenediamine bridge yields an amphiphilic conjugate that forms micelles with a long tumbling time (,R) in aqueous solution. The critical micelle concentration (cmc = 0.34 mM) of the amphiphilic [Gd(eptpa-C16)(H2O)]2, chelate was determined by variable-concentration proton relaxivity measurements. A global analysis of the data obtained in variable-temperature and multiple-field 17O NMR and 1H NMRD measurements allowed for the determination of parameters governing relaxivity for [Gd(eptpa-C16)(H2O)]2,; this is the first time that paramagnetic micelles with optimized water exchange have been investigated. The water exchange rate was found to be = 1.7×108 s,1, very similar to that previously reported for the nitrobenzyl derivative [Gd(eptpa-bz-NO2)(H2O)]2, ( = 1.5×108 s,1). The rotational dynamics of the micelles were analysed by using the Lipari,Szabo approach. The micelles formed in aqueous solution show considerable flexibility, with a local rotational correlation time of = 330 ps for the GdIII segments, which is much shorter than the global rotational correlation time of the supramolecular aggregates, = 2100 ps. This internal flexibility of the micelles is responsible for the limited increase of the proton relaxivity observed on micelle formation (r1 = 22.59 mM,1,s,1 for the micelles versus 9.11 mM,1,s,1 for the monomer chelate (20 MHz; 25,°C)). [source] | ||||||||||||||||||||||||||||||||||