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  • 1975-1979  (11)
  • 1920-1924
  • Analytical Chemistry and Spectroscopy  (8)
  • Apatite  (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
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 7 (1975), S. 470-474 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The diastereomers of 16 1,3-oxa-, 1,3-aza- and 1,3- thiaphospholanes were assigned by means of the coupling constants 2J(P—C—H) and 3J(P—C—CH3) and the linewidths of the 31P signals and 1H chemical shifts of CH3 groups. It is shown that the change in the 31P chemical shifts allows the estimation of the relative configuration in these compounds.
    Notes: Die Diastereomeren von 16 1,3 Oxa-, 1,3-Aza-und 1,3-Thiophospholanen wurden mit Hilfe der Kopplungs-konstanten 2J(P—C—H) und 3J(P—C—CH3), der Signalbreite der 31P-Signale und der 1H-chemischen Verschiebungen der CH3-Gruppen zugeordnet. Es wird gezeigt, daß auch die 31P-chemischen Verschiebungen eine Bestimmung der relativen Konfiguration dieser Verbindungen gestatten.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 12 (1977), S. 706-709 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Competitive fragementations of doubly charged ions formed by charge stripping have been observed for some hydrocarbon ions. The reproducibility of the abundance ratios indicates that they may be used to characterize the structural identity or non-identity of non-decomposing monocharged positive ions.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A novel approach to utilising digital computers and a collection of reference data for the interpretation of 13CNMR spectra is outlined. Because of the almost unlimited possibilities of molecular structures in organic chemistry, a matching of subspectra with substructures seems most appropriate, followed by an iterative confirmation of the suggested structures. For this purpose the possibility of a search for structure increments and the accompanying chemical shifts is provided by linking the spectroscopic and structural information using a formulae reading machine and generating the topological connectivity table. Three practical examples demonstrate the application of this set of programs and some of the experiences gained during operation.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 10 (1977), S. 172-174 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: The structures of 1- and 2-substituted 1,2-diphospholanes and of 1,5-diphosphabicyclo[3.3.0]octane and its P-derivatives are elucidated, using their 13C and 13P-n.m.r. spectra. In case of the latter compounds the 31P-chemical shifts indicate an additional, sterically caused, interaction of the phosphorus atoms. Within the limits of n.m.r. sensitivity all compounds are sterically uniform.
    Notes: Anhand von 13C- und 31P-Spektren wird die Struktur 1- sowie 2-substituierter 1,2-Diphospholane, des 1,5-Diphosphabicyclo[3.3.0]octans und dessen P-Derivate ermittelt. Die 31P-chemischen Verschiebungen zeigen für letztere eine zusätzliche sterisch bedingte Wechselwrikung der Phosphoratome. Sämtliche Verbindungen sind innerhalb der NMR-spektroskopischen Nachweisgrenze sterisch einheitlich.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 13 (1978), S. 207-208 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Collision induced dissociations of some molecular ions generated by electron impact or charge exchange from methane plasma are compared.
    Notes: Les dissociations induites par collisions d'ions moléculaires créés par impact d'électrons et par échange de charges dans une source d'ionisation chimique (méthane) sont comparés.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Organic Magnetic Resonance 11 (1978), S. 50-51 
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The complete assignment of the 13C NMR spectrum of a conformationally rigid camphane phosphonate derivative leads to a Karplus-type function for the vicinal 3J(CCCP) coupling constants in phosphonates. The general applicability of this relationship is demonstrated.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Biological Mass Spectrometry 12 (1977), S. 196-199 
    ISSN: 0030-493X
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: ions generated from a number of different presursors have been studied by high kinetie energy ion - molecule reations. It has been shown that at least four distinct stable species oeeur, of which acetonitrile and methyl isoeyanide retain their original structure. With imidazole or pyrazole as precursors, a mixture of open thain radical cations, not identical to the above species and probably interconvertible via the 1H-azirine radocal cation, is formed. From butrynitrile, pyrrole, crotonitrile, allyl interconvertible via the and cyanocyopropane a fourth species, probably the vinylidenimine ion, is formed.
    Additional Material: 3 Tab.
    Type of Medium: Electronic Resource
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