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  • Inorganic Chemistry  (3)
  • Octacalcium phosphate  (3)
  • Thermodynamics  (3)
  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 25 (1978), S. 209-216 
    ISSN: 1432-0827
    Keywords: Thermodynamics ; Kinetics ; Apatite ; Octacalcium phosphate ; Tricalcium phosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Summary A thermodynamic analysis has been made of the secondary transition stage in the spontaneous precipitation of calcium phosphate following the amorphous-crystalline transformation. The first formed crystalline material has a solubility similar to that of octacalcium phosphate (OCP) and the computed thermodynamic solubility product remains invariant in the pH range 7.00–8.60. The duration of the secondary stage is sensitive to pH and the transition appears to occur by hydrolysis of the first formed OCP-like phase to a more basic apatitic phase with a tricalcium phosphate (TCP) stoichiometry. The crystalline material at the end of this transition has an invariant solubility product, in the pH range 7.00 to 8.60, when the TCP-like molecular formula is assumed. Changes in the solution chemistry which accompany the solid-tosolid transitions are consistent with the above conclusions. The results of this study are also consistent with those of a previous study which suggest that the stability of the amorphous calcium phosphate phase is dependent upon the instability of the solution phase with respect to OCP formation.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 23 (1977), S. 259-269 
    ISSN: 1432-0827
    Keywords: Amorphous calcium phosphate ; Apatite ; Calcification ; Octacalcium phosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Summary The maturation of calcium phosphate crystals formed by the conversion of spontaneously precipitated amorphous calcium phosphate (ACP) was studied in aqueous media at temperatures ranging from 20° to 37°. Reaction pH was kept at 7.4 with either Hepes buffer or by the pH-stat addition of base. Reaction kinetics were followed by monitoring solution calcium and total phosphate, and, in the pH-stat controlled reaction, by recording the amount of KOH needed to maintain pH. Reaction products were examined chemically and by X-ray diffraction and transmission electron microcopy. The first crystals to form deviated markedly from apatite in morphology, composition, structure, and solubility. They were extremely thin and flaky in appearance, had a low Ca/P molar ratio (1.4), contained an appreciable amount of acid phosphate (16%), and had an exceptionally largea-axis (10.5 Å vs. 9.4 Å for apatite). With maturation, the crystals became thicker but smaller in lateral dimensions, more apatitelike in structure and composition, and less soluble. However, this ripening of the crystals was accompanied by unusual inflections in the solution Ca and total PO4 curves, and, in the case of the pH-stat experiments, in the OH consumption profiles as well. These anomalous post-ACP solution changes suggest that a phase change had taken place during crystal maturation. Although the observed structural and compositional changes are not inconsistent with the perfection of an initially defective apatite, the changes in crystal morphology and the anomalous behavior of the reaction solution may more accurately reflect a conversion of the ACP first into an OCP-like crystalline phase which subsequently hydrolyzes into apatite.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 25 (1978), S. 59-68 
    ISSN: 1432-0827
    Keywords: Amorphous calcium phosphate ; Thermodynamics ; Apatite ; Octacalcium phosphate ; Tricalcium phosphate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Summary A thermodynamic analysis of the precipitation of amorphous calcium phosphate (ACP) and its transformation to crystalline apatite has been made. A nearly constant ion product, over a wide variety of conditions, was obtained for a tricalcium phosphate (TCP)-like phase suggesting that the molecular unit which governs the solubility of ACP may be similar in composition to TCP. The introduction of 10% acid phosphate into the formula for the TCP ion product improves the fit of experimental data and results in an invariant ion product. The stability of ACP in solution was found to be dependent upon its thermodynamic instability with respect to an octacalcium phosphate (OCP)-like phase. The dependence of the induction period for the amorphous to crystalline transformation upon the pH and the Ca/P ratio of the solution is best explained by the assumption that an OCP-like phase is initially nucleated on the surfaces of the ACP particles. The events that occur in the immediate post-transition period suggest the hydrolysis of this OCP-like material to an apatitic phase.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Calcified tissue international 27 (1979), S. 153-160 
    ISSN: 1432-0827
    Keywords: Hydroxide ; Hydroxyapatite ; Titration ; Precipitation ; Thermodynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Summary A method is described for determination of the titratable hydroxide ion in calcium phosphate precipitates. The procedure requires accurate analysis of the other titratable species in the crystal lattice but is unaffected by the presence of other lattice constituents or impurities. The method was applied to precipitates that had been previously analyzed by solution thermodynamic techniques, and the results were consistent with the earlier observations. The hydroxide content of the precipitates increased with crystal maturity and with increasing pH of the precipitation medium. The hydroxide content of the amorphous phase and the immediate post-amorphous-crystalline transformation phase was shown to be nearly zero. After 3 to 4 days' maturation, the hydroxide content of precipitates prepared at pH values of 7, 8, and 9 was shown to increase to approximately 23, 40, 56% of that required for pure hydroxyapatite.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Neue Perspektiven in der Polyoxometallatchemie durch Isolierung von Verbindungen mit sehr großen übertragbaren Baueinheiten: (NMe4)5[As2Mo8V4AsO40] · 3H2O, (NH4)21[H3Mo57V6(NO)6O183(H2O)18] · 65 H2O, (NH2Me2)18(NH4)6[Mo57V6(NO)6O183(H2O)18] · 14 H2O und (NH4)12[Mo36(NO)4O108(H2O)16] · 33 H2ODie Verbindungen (NMe4)5[As2Mo8V4AsO40] · 3 H2O 2a, (NH4)21[H3Mo57V6(NO)6O183(H2O)18] · 65 H2O 3a, (NH2Me2)18(NH4)6[Mo57V6(NO)6O183(H2O)18] · 14 H2O 3b und (NH4)12[Mo36(NO)4O108(H2O)16] · 33 H2O 4a (3a und 4a sind in der Literatur bezüglich ihrer Zusammensetzung, Strukturen und der Oxidationszustände der Metallzentren nicht korrekt beschrieben worden), die zum Teil extrem große isolierte anionische Spezies enthalten, wurden dargestellt (darunter 3a, 3b und 4a in relativ hoher Ausbeute) und durch vollständige Kristallstrukturanalyse sowie durch IR-/Raman-, UV/VIS/NIR- und ESR-spektroskopische Methoden sowie mit Hilfe von vorläufigen magnetischen Suszeptibiltätsmessungen, Redoxtitrationen, Bindungsvalenzsummierungen, Elementaranalysen und thermogravimetrischen Studien charakterisiert. Perspektiven hinsichtlich der Synthese besonders großer nanodimensionierter Spezies werden im Zusammenhang mit den, in den Verbindungen 3a, 3b und 4a auftretenden, großen übertragbaren {Mo17} Baueinheiten diskutiert. Diese {Mo17} Baueinheit ist auch am Aufbau der Verbindung Na3(NH4)12[H15Mo57Fe6(NO)6O183(H2O)18] · 76 H2O 7a beteiligt.
    Notes: The compounds (NMe4)5[As2Mo8V4AsO40] · 3 H2O 2a, (NH4)21[H3Mo57V6(NO)6O183(H2O)18] · 65 H2O 3a, (NH2Me2)18(NH4)6[Mo57V6(NO)6O183(H2O)18] · 14 H2O 3b and (NH4)12[Mo36(NO)4O108(H2O)16] · 33 H2O 4a (3a and 4a were not correctly reported in the literature regarding to their composition, structures and the oxidation states of the metal centres) which contain large isolated anionic species, have been prepared (among them 3a, 3b, and 4a in rather high yield) and characterized by complete crystal structure analysis as well as IR/Raman, UV/VIS/NIR, ESR spectroscopy and magnetic susceptibility measurements, redox titrations, bond valence sum calculations, elemental analyses and thermogravimetric studies. Perspectives for polyoxometalate chemistry referring to the synthesis of “extremely” large nanoscaled species are discussed, together with the occurrence of a large transferable {Mo17} building block in the compounds 3a, 3b and 4a which also exists in the corresponding iron compound Na3(NH4)12[H15Mo57Fe6(NO)6O183(H2O)18] · 76 H2O 7a.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 313 (1961), S. 107-116 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The GRIGNARD reaction between silicon halides and alkyl-Mg-halides with steric hindering alkyl groups does not run in the usual manner. Thus from SiBr4 and secondary or tertiary butyl—MgBr only the corresponding butyl-tribromosilanes (C4H9)SiBr3 could be prepared in low yields. To a great extent, there are side reactions which produce silanes with Si—H-bonds by developing butene (C4H8) and high molecular polysilanes with, Si—Si-bonds by cleaving off octane (C8H18).
    Notes: Die Grignard-Reaktion zwischen Silicium-halogeniden und Alkyl-Mg-halogeniden mit sterisch hindernden Alkylgruppen verläuft anormal. So konnten aus SiBr4 und sekundärem oder tertiärem Butyl—MgBr nur die entsprechenden Butyl-tribrom-silane (C4H9)SiBr3 in geringen Ausbeuten gewonnen werden. Es finden in großem Umfange Nebenreaktionen statt, die unter Abspaltung von Buten(C4H8) zu Silanen mit Si—H-Bindungen, sowie unter Entwicklung von Octan (C8H18) zu hochmolekularen Polysilanen mit Si—Si-Bindungen führen.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 45 (1912), S. 3702-3705 
    ISSN: 0365-9496
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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