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Phosphate Anions (phosphate + anion)
Kinds of Phosphate Anions Selected AbstractsCyanide-Catalyzed Additions of Acyl Phosphonates to Aldehydes: A New Acyl Donor for Benzoin-Type ReactionsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2005Abstract Acyl phosphonates have been utilized as new acyl donors for cyanide-catalyzed benzoin-type reactions. Cyanation of acyl phosphonates, followed by a [1,2]-phosphoryl migration generates the active acyl anion intermediate. The presumed (cyano)phosphate anion reacts with a variety of aryl aldehydes to yield phosphate ester-protected, unsymmetrical benzoins in good to excellent yields. The unsymmetrical benzoin product can be obtained after deprotection of the phosphate ester with an aqueous amine solution. [source] The entrapment of corrosion products from CoCr implant alloys in the deposits of calcium phosphate: A comparison of serum, synovial fluid, albumin, EDTA, and waterJOURNAL OF ORTHOPAEDIC RESEARCH, Issue 8 2006A. C. Lewis Abstract Physical wear of orthopedic implants is inevitable. CoCr alloy samples, typically used in joint reconstruction, corrode rapidly after removal of the protective oxide layer. The behavior of CoCr pellets immersed in human serum, foetal bovine serum (FBS), synovial fluid, albumin in phosphate-buffered saline (PBS), EDTA in PBS, and water were studied using X-ray Photoelectron Spectroscopy (XPS) and Time-of-Flight Secondary Ion Mass Spectroscopy (ToF-SIMS). The difference in the corrosive nature of human serum, water, albumin in PBS and synovial fluid after 5 days of immersion was highlighted by the oxide layer, which was respectively 15, 3.5, 1.5, and 1.5 nm thick. The thickness of an additional calcium phosphate deposit from human serum and synovial fluid was 40 and 2 nm, respectively. Co and Cr ions migrated from the bulk metal surface and were trapped in this deposit by the phosphate anion. This may account for the composition of wear debris from CoCr orthopedic implants, which is known to consist predominantly of hydroxy-phosphate compounds. Known components of synovial fluid including proteoglycans, pyrophosphates, phospholipids, lubricin, and superficial zone protein (SZP), have been identified as possible causes for the lack of significant calcium phosphate deposition in this environment. Circulation of these compounds around the whole implant may inhibit calcium phosphate deposition. © 2006 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 24:1587,1596, 2006 [source] Raman spectroscopy of hydrotalcites with phosphate in the interlayer: implications for the removal of phosphate from waterJOURNAL OF RAMAN SPECTROSCOPY, Issue 7 2006Ray L. Frost Abstract Hydrotalcites with phosphate in the interlayer were prepared at different pH values. At pH > 11.0 (PO4)3, was the intercalated ionic species, whereas at pH < 11.0 a mixture of (PO4)3, and (HPO4)2, ions was intercalated. Powder X-ray diffraction shows that the hydrotalcite formed at pH 9.5 is poorly diffracting with a d-spacing of 11.9 Å; whereas the d(003) spacing for the phosphate interlayered hydrotalcite formed at pH 11.9 and 12.5 was 8.0 and 7.9 Å respectively. The addition of a thermally activated ZnAl-HT to a phosphate solution resulted in the uptake of the phosphate and the reformation of the hydrotalcite. Raman spectroscopy of the phosphate interlayered hydrotalcites shows that the interlayered anion is pH dependent and only above pH 11.9 is the orthophosphate anion intercalated. At lower pH, the monohydrogen phosphate anion is intercalated. Raman spectroscopy shows that upon addition of the thermally activated hydrotalcite to an aqueous phosphate solution, results in the uptake of phosphate anion from the solution. Copyright © 2006 John Wiley & Sons, Ltd. [source] Structures of three diphtheria toxin repressor (DtxR) variants with decreased repressor activityACTA CRYSTALLOGRAPHICA SECTION D, Issue 5 2001Ehmke Pohl The diphtheria toxin repressor (DtxR) from Corynebacterium diphtheriae regulates the expression of the gene on corynebacteriophages that encodes diphtheria toxin (DT). Other genes regulated by DtxR include those that encode proteins involved in siderophore-mediated iron uptake. DtxR requires activation by divalent metals and holo-DtxR is a dimeric regulator with two distinct metal-binding sites per three-domain monomer. At site 1, three side chains and a sulfate or phosphate anion are involved in metal coordination. In the DtxR,DNA complex this anion is replaced by the side chain of Glu170 provided by the third domain of the repressor. At site 2 the metal ion is coordinated exclusively by constituents of the polypeptide chain. In this paper, five crystal structures of three DtxR variants focusing on residues Glu20, Arg80 and Cys102 are reported. The resolution of these structures ranges from 2.3 to 2.8,Å. The side chain of Glu20 provided by the DNA-binding domain forms a salt bridge to Arg80, which in turn interacts with the anion. Replacing either of the salt-bridge partners with an alanine reduces repressor activity substantially and it has been inferred that the salt bridge could possibly control the wedge angle between the DNA-binding domain and the dimerization domain, thereby modulating repressor activity. Cys102 is a key residue of metal site 2 and its substitution into a serine abolishes repressor activity. The crystal structures of Zn-Glu20Ala-DtxR, Zn-Arg80Ala-DtxR, Cd-Cys102Ser-DtxR and apo-Cys102Ser-DtxR in two related space groups reveal that none of these substitutions leads to dramatic rearrangements of the DtxR fold. However, the five crystal structures presented here show significant local changes and a considerable degree of flexibility of the DNA-binding domain with respect to the dimerization domain. Furthermore, all five structures deviate significantly from the structure in the DtxR,DNA complex with respect to overall domain orientation. These results confirm the importance of the hinge motion for repressor activity. Since the third domain has often been invisible in previous crystal structures of DtxR, it is also noteworthy that the SH3-like domain could be traced in four of the five crystal structures. [source] Pyrazino[2.3- g]quinoxaline-Bridged Indole-Based Building Blocks: Design, Synthesis, Anion-Binding Properties, and Phosphate-Directed Assembly in the Solid StateCHEMISTRY - A EUROPEAN JOURNAL, Issue 15 2010Ting Wang Abstract Strategies for exploring anionic templates to direct sophisticated supramolecular assembly have attracted attention. Herein, a series of new anion receptors 1,3 containing two indole-based binding sites bridged by linking spacer pyrazino[2.3- g]quinoxaline (PQ) have been rationally designed and prepared from the precursors 2,3-diindol-3,-yl quinoxaline (DIQ) and 5,6-dihydrodiindolo[3,2- a:2,,3,- c]phenazine (DIPZ). X-ray analyses showed a self-connected network and dimeric packing through hydrogen bonding and ,,, stacking interaction in the solid state in the structures of 1 and 2, respectively. All three receptors exhibited a series of prominent absorption bands from the expanded ,,system. The indole-based expanded receptors were found to strongly and selectively bind F,, AcO,, and H2PO4, among the tested anions (F,, Cl,, Br,, AcO,, H2PO4,, HSO4,, NO3,, and ClO4,), and operated as efficient colorimetric sensors for naked-eye detection of fluoride anions in DMSO. These tailored building blocks captured two anions located at far-spaced binding sites, and adopted noninterfering anion-binding processes to guarantee the anion-binding affinity, topology, and dimensionality. Solid-state studies elucidated that the neutral 1,3 interacted with the tetrahedral dihydrogen phosphate anion in proper proportions and designed topologies, thus leading to the formation of a series of multidimensional networks by self-assembly in the solid state. The observations showed a well-characterized phosphate-directed assembly of multidimensional metal-free coordination polymers in the solid state, in which the formed phosphate aggregates, including dimer encapsulated in an indole-mediated hydrogen-bonded pocket and an infinite chain, behaved as anionic templates to direct the self-assembly. However, no evidence proved the presence of such phosphate-directed infinite coordination polymers in solution. [source] NMR and Luminescence Binding Studies of Ytterbium, Thulium, and Europium Macrocyclic Complexes with Phosphorus(V) Oxy AnionsHELVETICA CHIMICA ACTA, Issue 3 2005Paul Atkinson The binding of a series of phosphate anions to coordinatively unsaturated macrocyclic complexes of Yb, Tm, and Eu was studied by 1H-NMR, emission and circularly polarized luminescence (CPL) spectroscopy. Each ternary adduct was distinguished by its spectral profile. With O -phosphorylated amino acids and peptides, chemoselective ligation of the phosphate moiety was favored by Eu over chelation involving the terminal amino group, which was competitive for Tm and Yb. A preference for binding O -phosphono- L -tyrosine sites was found with various Eu complexes, and was signalled by ratiometric changes in metal-based emission and CPL spectra. [source] Chemically Bonded Phosphate Ceramics: I, A Dissolution Model of FormationJOURNAL OF THE AMERICAN CERAMIC SOCIETY, Issue 11 2003Arun S. Wagh This is the first of three papers in which the kinetics of formation of chemically bonded phosphate ceramics is discussed. A literature survey indicates that the formation of such ceramics is a three-step process. First, oxides dissolve in a phosphoric acid or an acid phosphate solution and metal ions are released into the solution. The aquoions formed from these cations then react with phosphate anions and form a gel of metal hydrophosphates. In the last step, the saturated gel crystallizes into a ceramic. In this paper, we have proposed that the dissolution is the controlling step and developed a general dissolution model of the kinetics of formation of these ceramics. As an example, the model is used to discuss the kinetics of formation of magnesium phosphate ceramics in detail. In the second and third papers, the model has been used to develop processes to form ceramics of alumina and iron oxides. [source] A solid-state NMR investigation of the structure of nanocrystalline hydroxyapatiteMAGNETIC RESONANCE IN CHEMISTRY, Issue 6 2006Christian Jäger Abstract Nanocrystalline hydroxyapatite (HAp) prepared by a precipitation route was investigated. The X-ray diffraction (XRD) powder patterns of the elongated nanocrystals with a typical diameter of about 10 nm and length of 30,50 nm (by transmission electron microscopy (TEM)) revealed the presence of HAp with significantly broadened XRD reflections. However, Ca deficiency was found, as the Ca/P ratio was 1.5 only (so-called calcium-deficient hydroxyapatite (CDHA)), and not 1.67. This Ca deficiency of nanocrystalline HAp is explained using NMR. It is shown unambiguously that (i) the nanocrystals consist of a crystalline core and a (disordered) surface region with a relative phosphate content of about 1:1, (ii) the crystalline core is HAp, and (iii) the surface region is dominated by hydrogen phosphate anions (with no hydroxyapatite-like structural motif) and structural water (hydrate). From the relative phosphate content and taking into account the crystal shape, the thickness of the surface layer along the main crystal axis could be estimated to be about 1 nm, and the average chemical composition of the surface layer has been determined. Finally, a Ca/P ratio of 1.52 was estimated from the NMR data that compares well with the value of 1.51 from chemical analysis. The important consequences are that the surface of nanocrystalline HAp has nothing in common with the bulk composition and that the chemistry of such materials (e.g. the binding of protein molecules to phosphate surfaces) must be reconsidered. Copyright © 2006 John Wiley & Sons, Ltd. [source] Dihydrogen phosphate mediated supramolecular frameworks in 2- and 4-chloroanilinium dihydrogen phosphate saltsACTA CRYSTALLOGRAPHICA SECTION C, Issue 3 2010P. Balamurugan The title compounds, 2-chloroanilinium dihydrogen phosphate (2CADHP) and 4-chloroanilinium dihydrogen phosphate (4CADHP), both C6H7NCl+·H2PO4,, form two-dimensional supramolecular organic,inorganic hybrid frameworks. In 2CADHP, the dihydrogen phosphate anions form a double-stranded anionic chain generated parallel to the [010] direction through O,H...O hydrogen bonds, whereas in 4CADHP they form a two-dimensional supramolecular net extending parallel to the crystallographic (001) plane into which the cations are linked through strong N,H...O hydrogen bonds. [source] Codeine dihydrogen phosphate hemihydrateACTA CRYSTALLOGRAPHICA SECTION C, Issue 8 2009Christoph Langes The cation of the title structure [systematic name: (5,,6,)-6-hydroxy-7,8-didehydro-4,5-epoxy-3-methoxy-17-methylmorphinanium dihydrogen phosphate hemihydrate], C18H22NO3+·H2PO4,·0.5H2O, has a T-shaped conformation. The dihydrogen phosphate anions are linked by O,H...O hydrogen bonds to give an extended ribbon chain. The codeine cations are linked together by O,H...O hydrogen bonds into a zigzag chain. There are also N,H...O bonds between the two types of hydrogen-bonded units. Addditionally, they are connected to one another via O...H,O,H...O bridging water molecules. The asymmetric unit contains two codeine hydrogen cations, two dihydrogen phosphate anions and one water molecule. This study shows that the water molecules are firmly bound within a complex three-dimensional hydrogen-bonded framework. [source] Structure of the Methanothermobacter thermautotrophicus exosome RNase PH ringACTA CRYSTALLOGRAPHICA SECTION D, Issue 5 2010C. Leong Ng The core of the exosome, a versatile multisubunit RNA-processing enzyme found in archaea and eukaryotes, includes a ring of six RNase PH subunits. This basic architecture is homologous to those of the bacterial and archaeal RNase PHs and the bacterial polynucleotide phosphorylase (PNPase). While all six RNase PH monomers are catalytically active in the homohexameric RNase PH, only half of them are functional in the bacterial PNPase and in the archaeal exosome core and none are functional in the yeast and human exosome cores. Here, the crystal structure of the RNase PH ring from the exosome of the anaerobic methanogenic archaeon Methanothermobacter thermautotrophicus is described at 2.65,Å resolution. Free phosphate anions were found for the first time in the active sites of the RNase PH subunits of an exosome structure and provide structural snapshots of a critical intermediate in the phosphorolytic degradation of RNA by the exosome. Furthermore, the present structure highlights the plasticity of the surfaces delineating the polar regions of the RNase PH ring of the exosome, a feature that can facilitate both interaction with the many cofactors involved in exosome function and the processive activity of this enzyme. [source] The Reaction of Hydrogen Atoms with Methionine Residues: A Model of Reductive Radical Stress Causing Tandem Protein,Lipid DamageCHEMBIOCHEM, Issue 11 2006Carla Ferreri Dr. Abstract The occurrence of tandem damage, due to reductive radical stress involving proteins and lipids, is shown by using a biomimetic model. It is made of unsaturated lipid vesicle suspensions in phosphate buffer in the presence of methionine, either as a single amino acid or as part of a protein such as RNase A, which contains four methionine residues. The radical process starts with the formation of H. atoms by reaction of solvated electrons with dihydrogen phosphate anions, which selectively attack the thioether function of methionine. The modification of methionine to ,-aminobutyric acid is accompanied by the formation of thiyl radicals, which in turn cause the isomerization of the cis fatty acid residues to the trans isomers. The relationship between methionine modification and lipid damage and some details of the reductive radical stress obtained by proteomic analysis of irradiated RNase A are presented. [source] | ||||||||||||||||||||||