Effects of Ligand Binding on Relative Stability of Subchain Conformations of Weakly Charged N-Isopropylacrylamide Gels in Swollen and Shrunken States

Tatiana V. Burova, Natalia V. Grinberg, Alexander S. Dubovik, Kazunori Tanaka, Valerij Ya Grinberg, Alexander Yu Grosberg

    Research output: Contribution to journalArticle

    Abstract

    The thermotropic collapse of the hydrogel of copolymer N-isopropylacrylamide with acrylic acid (NIPA-AAc) upon heating has been studied by high-sensitivity differential scanning calorimetry. Curves of the polymer partial heat capacity have been measured at different pH (from pH 2 to 11) and different concentrations of cationic ligands: CaCl 2, dodecyltrimethylammonium bromide (DTAB), and cetyltrimethylammonium bromide (CTAB). Dependencies of the main thermodynamic parameters of the gel collapse-temperature, enthalpy, and width of the transition on pH and ligand concentration-have been obtained, It has been found that the collapse is characterized by a negative value of the heat capacity increment Δ tC p Its average value determined over all variables studied is Δ tC p = -0.62 ± 0.02 J/(g K). This result is in accordance with the observed correlation between the transition enthalpy and temperature of the NIPA-AAc gel. The free energy of the collapse has been calculated as a function of pH and concentration of CaCl 2, DTAB, and CTAB and analyzed using the model of macromolecular binding on the independent equivalent sites. Parameters characterizing affinity of the gel in swollen and collapsed state with respect to the ionic ligands have been determined. A preferential electrostatic binding of protons, Ca 2+, and surfactant ions by subchains in collapsed gel has been evaluated. The results also reveal a weak affinity of the subchains in swollen gel to amphiphilic ligands.

    Original languageEnglish (US)
    Pages (from-to)9115-9121
    Number of pages7
    JournalMacromolecules
    Volume36
    Issue number24
    DOIs
    StatePublished - Dec 2 2003

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    Conformations
    Gels
    Ligands
    Acrylics
    Specific heat
    Enthalpy
    Acids
    Hydrogel
    Hydrogels
    Surface-Active Agents
    Free energy
    Protons
    Differential scanning calorimetry
    Electrostatics
    Polymers
    Surface active agents
    Copolymers
    N-isopropylacrylamide
    Thermodynamics
    Ions

    ASJC Scopus subject areas

    • Materials Chemistry

    Cite this

    Effects of Ligand Binding on Relative Stability of Subchain Conformations of Weakly Charged N-Isopropylacrylamide Gels in Swollen and Shrunken States. / Burova, Tatiana V.; Grinberg, Natalia V.; Dubovik, Alexander S.; Tanaka, Kazunori; Grinberg, Valerij Ya; Grosberg, Alexander Yu.

    In: Macromolecules, Vol. 36, No. 24, 02.12.2003, p. 9115-9121.

    Research output: Contribution to journalArticle

    Burova, Tatiana V. ; Grinberg, Natalia V. ; Dubovik, Alexander S. ; Tanaka, Kazunori ; Grinberg, Valerij Ya ; Grosberg, Alexander Yu. / Effects of Ligand Binding on Relative Stability of Subchain Conformations of Weakly Charged N-Isopropylacrylamide Gels in Swollen and Shrunken States. In: Macromolecules. 2003 ; Vol. 36, No. 24. pp. 9115-9121.
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    abstract = "The thermotropic collapse of the hydrogel of copolymer N-isopropylacrylamide with acrylic acid (NIPA-AAc) upon heating has been studied by high-sensitivity differential scanning calorimetry. Curves of the polymer partial heat capacity have been measured at different pH (from pH 2 to 11) and different concentrations of cationic ligands: CaCl 2, dodecyltrimethylammonium bromide (DTAB), and cetyltrimethylammonium bromide (CTAB). Dependencies of the main thermodynamic parameters of the gel collapse-temperature, enthalpy, and width of the transition on pH and ligand concentration-have been obtained, It has been found that the collapse is characterized by a negative value of the heat capacity increment Δ tC p Its average value determined over all variables studied is Δ tC p = -0.62 ± 0.02 J/(g K). This result is in accordance with the observed correlation between the transition enthalpy and temperature of the NIPA-AAc gel. The free energy of the collapse has been calculated as a function of pH and concentration of CaCl 2, DTAB, and CTAB and analyzed using the model of macromolecular binding on the independent equivalent sites. Parameters characterizing affinity of the gel in swollen and collapsed state with respect to the ionic ligands have been determined. A preferential electrostatic binding of protons, Ca 2+, and surfactant ions by subchains in collapsed gel has been evaluated. The results also reveal a weak affinity of the subchains in swollen gel to amphiphilic ligands.",
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    AU - Dubovik, Alexander S.

    AU - Tanaka, Kazunori

    AU - Grinberg, Valerij Ya

    AU - Grosberg, Alexander Yu

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    AB - The thermotropic collapse of the hydrogel of copolymer N-isopropylacrylamide with acrylic acid (NIPA-AAc) upon heating has been studied by high-sensitivity differential scanning calorimetry. Curves of the polymer partial heat capacity have been measured at different pH (from pH 2 to 11) and different concentrations of cationic ligands: CaCl 2, dodecyltrimethylammonium bromide (DTAB), and cetyltrimethylammonium bromide (CTAB). Dependencies of the main thermodynamic parameters of the gel collapse-temperature, enthalpy, and width of the transition on pH and ligand concentration-have been obtained, It has been found that the collapse is characterized by a negative value of the heat capacity increment Δ tC p Its average value determined over all variables studied is Δ tC p = -0.62 ± 0.02 J/(g K). This result is in accordance with the observed correlation between the transition enthalpy and temperature of the NIPA-AAc gel. The free energy of the collapse has been calculated as a function of pH and concentration of CaCl 2, DTAB, and CTAB and analyzed using the model of macromolecular binding on the independent equivalent sites. Parameters characterizing affinity of the gel in swollen and collapsed state with respect to the ionic ligands have been determined. A preferential electrostatic binding of protons, Ca 2+, and surfactant ions by subchains in collapsed gel has been evaluated. The results also reveal a weak affinity of the subchains in swollen gel to amphiphilic ligands.

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