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  • 1
    ISSN: 1434-4475
    Keywords: Ternary complexes ; Nickel(II) ; AMP ; ADP ; ATP ; Polybasicoxygen acids ; Potentiometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Es wurde die Wechselwirkung von Adenosin-5′-mono-, -di- und -triphosphat (AMP,ADP undATP) und Ni(II) mit biologisch relevanten Säuren als Sekundärliganden (Äpfel-, Malein-, Bernstein-, Wein-, Zitronen- und Oxalsäure) im Verhältnis 1:1:1 mittels potentiometrischer Gleichgewichtsmessungen bei 25±0.1 °C und μ=0.1 mol dm−3 KNO3 untersucht. Aus den potentiometrischepH-Titrationen ergaben sich verschiedene 1:1:1-Komplexe mit gemischten Liganden. Zunächst abgeschätzte Komplexbildungskonstanten und Säuredissoziations-konstanten vonAMP,ADP,ATP mit den als Sekundärliganden eingesetzten Säuren wurden über das SUPERQUAD-Rechenprogramm verfeinert. In einigen Systemen sind die Werte von ΔlogK positiv, was bedeutet, daß die ternären Komplexe stabiler sind als die entsprechenden binären Komplexe. In einige ternären Komplexen scheinen die Wasserstoffbrücken zwischen den Liganden entscheidend zu sein. Die Stabilitäten der gemischten Liganden steigen in der ReiheAMP〈ADP〈ATP an. Bezüglich der Sekundärliganden ergibt sich die absteigende Stabilitätsreihung Bernsteinsäure〉Maleinsäure〉Weinsäure〉Äpfelsäure〉Zitronensäure〉Oxalsäure.
    Notes: Summary Potentiometric equilibrium measurements have been made at 25±0.1 °C (μ=0.1 mol dm−3 KNO3) for the interaction of adenosine-5′-mono-, -di-, and-triphosphate (AMP,ADP, andATP) and Ni(II) with biologically important secondary ligand acids (malic, maleic, succinic, tartaric, citric and oxalic acids) in a 1:1:1 ratio and the formation of various 1:1:1 mixed ligand complex species inferred from the potentiometricpH titration curves. Initial estimates of the formation constants of the resulting species and the acid dissociation constants ofAMP,ADP,ATP and secondary ligand acid, have been refined with SUPERQUAD computer program. In some systems Δ logK values are positive, i.e. the ternary complexes are found to be more stable than the corresponding binary complexes. H-bond formation seems to be most effective in deciding the stability of the ternary complexes formed in solution. Stabilities of mixed ligand complexes increases in the orderAMP〈ADP〈ATP. With respect to the secondary ligands, the formation constants of the mixed lignads complexes decrease in the order succinic〉maleic〉tartaric〉malic〉citric〉oxalic acid.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1434-4475
    Keywords: Formation equilibria ; Cobalt(II) ; AMP ; ADP ; ATP ; Polybasic acids ; Potentiometry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Zusammenfassung Die Wechselwirkung vonAMP,ADP undATP mit Co(II) und einigen biologisch interessanten Sekundärliganden (Bernsteinsäure, Hydroxybernsteinsäure, Maleinsäure, Weinsäure, Zitronensäure und Oxalsäure) wurde bei 25°C und einer lonenstärke von 0.1M KNO3 potentiometrisch untersucht. Die Titrationskurven zeigen das Vorliegen von Species der Zusammensetzung 1:1:1 an. Die geschätzten Bildungskonstanten der Komplexe und die Dissoziationskonstanten der Liganden wurden mittels eines Computerprogramms optimiert. In einigen der untersuchten Systeme sind die ternären Komplexe stabiler als die sekundären. Die Stabilität der Verbindungen hängt im wesentlichen von Interligandwechselwirkungen — möglicherweise der Ausbildung von Wasserstoffbrückenbindungen — ab. Die Stabilität der Komplexe mit gemischten Liganden steigt in der ReihenfolgeAMP 〈ADP 〈ATP und fällt entsprechend der Serie Bernsteinsäure 〉 Maleinsäure 〉 Weinsäure 〉 Hydroxybernsteinsäure 〉 Zitronensäure 〉 Oxalsäure.
    Notes: Summary Potentiometric equilibrium measurements have been made for the interaction of adenosine-5′-mono-,-di-, and -triphosphate, and Co(II) with biologically important secondary ligands (malic, maleic, succinic, tartaric, citric, and oxalic acid). The formation of various 1:1:1 mixed ligand complexes inferred from the potentiometric titration curves. Initial estimates of the formation constants of the resulting species and the acid dissociation constants ofAMP,ADP,ATP and the secondary ligand acids have been refined with a computer program. In some systems, the ternary complexes are found to be more stable than the corresponding binary ones. In some ternary systems studied, interligand interactions or some cooperativity between the coordinate ligands, possibly H bond formation, have been found to be most effective in deciding the stability of the complexes formed in solution. Stabilities of mixed ligand complexes increase in the orderAMP 〈ADP 〈ATP. With respect to the secondary ligands, the formation constants of the mixed ligand complexes decrease in the following order: succinic 〉 maleic 〉 tartaric 〉 malic 〉 citric 〉 oxalic acid.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1435-1536
    Keywords: Aqueous solutions ; polyvinyl alcohol ; hydroxypropyl methylcellulose ; interactions ; plasticizer ; partitioning ; solubility ; diethylene glycol
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The interactions and partitioning of diethylene glycol (DEG) in polyvinyl alcohol (PVA), hydroxypropyl methylcellulose (HPMC) and their blends has been studied. DEG acted as efficient plasticizer for both homopolymers, lowering theirT g and relative rigidity. Kelly-Bueche-type equations were fitted successfully to the experimental data and yielded an interaction parameter,K Φ, between DEG and each polymer. Incorporation of DEG into two-phase blends of PVA and HPMC with 40, 50 and 60% PVA did not change the significant incompatibility of the two components and plasticized both phases. Composition calculations based on Kelley-Bueche-type expressions fitted to the experimental data afforded determination of the partition coefficients of DEG into the two phases of the blends. In the case of the 50∶50 weight% system, it partitioned almost equally into both phases. The results are discussed in terms of the DEG affinity to interact with the two polymers by means of the dispersive, polar and hydrogen-bonding contribution to the solubility parameters.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 1435-1536
    Keywords: Aqueous ; polyvinyl alcohol ; hydroxypropyl methylcellulose ; interactions ; plasticizer ; partitioning ; solubility ; polyethylene glycol
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The interactions and partitioning of polyethylene glycol 400 (PEG400) in hydroxypropyl methylcellulose (HPMC), polyvinyl alcohol (PVA) and their blends have been investigated by means of torsional braid analysis (TBA). PEG400 was shown to be a better plasticizer for HPMC than PVA, in agreement with solubility parameter predictions. Incorporation of PEG400 in blends of PVA and HPMC did not alter the incompatibility between the two homopolymers and plasticized both phases. The PEG400 content in the two phases was calculated by fitting Kelley-Bueche and quadratic expressions to the experimental data, enabling determination of the PEG400 partition coefficient. The data showed a selective partitioning of PEG400 in the HPMC phase for plasticizer contents less than 20% w/w. At higher concentrations, PEG400 continued to partition selectively into the HPMC phase for blends with 60 and 80% PVA but started partitioning in the PVA phase for blends with 20 and 40% PVA.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 1435-1536
    Keywords: Aqueous ; polyvinyl alcohol ; hydroxypropyl methylcellulose ; interactions ; plasticizer ; partitioning ; solubility ; glycerol
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The interactions and partitioning of glycerol in polyvinyl alcohol (PVA), hydroxypropyl methylcellulose (HPMC) and their blends has been studied by means of torsional braid analysis (TBA). Glycerol was shown to be a more efficient plasticizer for PVA than HPMC in agreement with solubility parameter prediction. Kelley-Bueche-type equations were fitted to the experimentalTg data and initial slopes yielded an interaction parameter,Kø, between glycerol and the two polymers. Incorporation of glycerol in PVA/HPMC blends did not alter the incompatibility of the two polymers and plasticized both phases. The compositions of the two plasticized phases were calculated from Kelley-Bueche expressions fitted to the experimental data, enabling determination of the glycerol partition coefficients into the two phases. In blends with 20–60% PVA, glycerol partitioned selectively into the PVA-rich phase whereas in the system with 80% PVA, glycerol partitioned selectively into the HPMC-rich inclusions.
    Type of Medium: Electronic Resource
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