Calorimetric study on the formation of polymer complexes through electrostatic interaction and hydrogen bonding

Abe, Kôji; Ohno, Hiroyuki; Nii, Atsushi; Tsuchida, Eishun

doi:10.1002/macp.1978.021790816

Cited by 35 publications

(6 citation statements)

References 10 publications

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“…Previous reports have shown that, under the correct conditions (in terms of pH and ionic strength), PMAA shows increased hydrophobic effects compared to PAA resulting in a larger binding isotherm but under the conditions employed here no statistical difference in terms of binding affinity (K) and enthalpy (H) between samples was seen. 19,39,40 Interaction between tannic acid (TA) and MC showed a considerably higher enthalpy change and binding affinity (Table 1), illustrating increased complexation compared to PAA. Recently we reported greater pH stability of TA-MC complexes compared to PAA-MC.…”

Section: Resultsmentioning

confidence: 99%

“…17 Interactions between poly(carboxylic acids) and non-ionic polymers result in hydrogen-bonded IPCs. Perez-Gramatges et al 18 and Abe et al 19 have shown that the interaction between poly(carboxylic acids) and poly(vinyl pyrrolidone) produces a positive enthalpy change, illustrating the importance of hydrophobic effects in their complexation in addition to hydrogen bonding. Kabanov et al 20 studied complexation between poly(ethylene oxide) and poly(methacrylic acid) using potentiometric titration and established that the complexes are stabilized by hydrogen bonding but that other effects such as hydrophobic and conformational interactions resulted in an overall positive enthalpy change.…”

Section: Introductionmentioning

confidence: 99%

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Thermodynamic and kinetic properties of interpolymer complexes assessed by isothermal titration calorimetry and surface plasmon resonance

2014

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Interpolymer complexes (IPCs) formed between complimentary polymers in solution have shown a wide range of applications from drug delivery to biosensors. This work describes the combined use of isothermal titration calorimetry and surface plasmon resonance to investigate the thermodynamic and kinetic processes during hydrogen-bonded interpolymer complexation. Varied polymers that are commonly used in layer-by-layer coatings and pharmaceutical preparations were selected to span a range of chemical functionalities including some known IPCs previously characterized by other techniques, and other polymer combinations with unknown outcomes. This work is the first to comprehensively detail the thermodynamic and kinetic data of hydrogen bonded IPCs, aiding understanding and detailed characterization of the complexes. The applicability of the two techniques in determining thermodynamic, gravimetric and kinetic properties of IPCs is considered.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Thermodynamic and kinetic properties of interpolymer complexes assessed by isothermal titration calorimetry and surface plasmon resonance

2014

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“…In contrast to the large number of studies into interpolymer complex formation, few attempts have been made to describe the thermodynamics of these processes. − Spontaneous complex formation requires the Gibbs energy of mixing (Δ G M ) to be negative: where Δ H M and Δ S M are the total heat (enthalpy) and total entropy of mixing, respectively. A negative value of Δ G M can be achieved either when Δ H M is negative or when Δ S M is positive and high.…”

Section: Introductionmentioning

confidence: 99%

“…In contrast to the large number of studies into interpolymer complex formation, few attempts have been made to describe the thermodynamics of these processes. [17][18][19] Spontaneous complex formation requires the Gibbs energy of mixing (∆G M ) to be negative:…”

Section: Introductionmentioning

confidence: 99%

pH-Mediated Interactions between Poly(acrylic acid) and Methylcellulose in the Formation of Ultrathin Multilayered Hydrogels and Spherical Nanoparticles

2007

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Poly(acrylic acid) forms insoluble hydrogen-bonded interpolymer complexes with methylcellulose in aqueous solutions under acidic conditions. In this work the reaction heats and binding constants were determined for the complexation between poly(acrylic acid) and methylcellulose by isothermal titration calorimetry at different pH and findings are correlated with the aggregation processes occurring in this system. The principal contribution to the complexation heat results from primary polycomplex particle aggregation. Transmission electron microscopy of nanoparticles produced at pH 1.4 and 2.4 demonstrated that they are spherical and dense structures. The nanoparticles ranged from 80 to 200 nm, whereas particles formed at pH 3.2 were 20−30 nm and were stabilized against aggregation by a network of uncomplexed macromolecules. For the first time, multilayered materials were developed on the basis of hydrogen-bonded complexes of poly(acrylic acid) and methylcellulose using layer-by-layer deposition on a glass surface. The thickness of these films was a linear function of the number of deposition cycles. The materials were subsequently cross-linked by thermal treatment, resulting in ultrathin hydrogels which detached from the glass substrate upon swelling. The swelling capacity of ultrathin hydrogels differed from the swelling of the thicker films of a similar chemical composition.

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“…Such electro-active polymers can be fixed stably by complex formation of the polymers with other electro-active or electro-nonactive polymers on the surface of the electrode applied. The present authors have studied the formation process and the characteristics of interpolymer complexes [16][17][18][19][20][21][22][23][24][25][26][27].…”

Section: Introductionmentioning

confidence: 99%

Electron transfer process in the microdomains of poly(sodium styrenesulfonate)‐poly(alkylene viologen) complexes

1983

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The electron transfer process in the microdomain of a polyion complex composed of poly(sodium styrenesulfonate), (syst. name: poly[sodium 1-(4-~ulfonatophenyl)ethylene]), and poly(alky1ene vio1ogen)s 1 with 3 to 10 methylene groups between two adjacent viologen units was analyzed by means of voltammetry with a rotating disc electrode. Although the stability of 1 on the graphite electrode was improved by the formation of a polyion complex with poly(sodium styrenesulfonate), a smaller surface charge was observed in the polyion complex as compared with the electrode coated with poly(a1kylene viologen) alone. Since the migration of the counter ion was clarified to be indispensable for the electron transfer in this case, the microdomain of polyion complexes should be formed by tightly-shrunk polyelectrolyte chains. Furthermore, the electron transfer in the microdomain of the polyion complex is hardly detected, when the electrode is coated with an excess of the complex. The electron transfer strongly depended on the average distance between two adjacent redox sites in the matrix. These matrixes were suggested to be controlled by the subtle balance of hydrophobicity and charge density of 1.

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Calorimetric study on the formation of polymer complexes through electrostatic interaction and hydrogen bonding

Cited by 35 publications

References 10 publications

Thermodynamic and kinetic properties of interpolymer complexes assessed by isothermal titration calorimetry and surface plasmon resonance

Thermodynamic and kinetic properties of interpolymer complexes assessed by isothermal titration calorimetry and surface plasmon resonance

pH-Mediated Interactions between Poly(acrylic acid) and Methylcellulose in the Formation of Ultrathin Multilayered Hydrogels and Spherical Nanoparticles

Electron transfer process in the microdomains of poly(sodium styrenesulfonate)‐poly(alkylene viologen) complexes

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