Behavior of Nonalternating Maleic Acid Copolymers in Aqueous Solution

Chiţanu, Gabrielle Charlotte; Rinaudo, Marguerite; Desbrières, Jacques; Milas, M.; Carpov, Adrian

doi:10.1021/la981509z

Cited by 25 publications

(20 citation statements)

References 17 publications

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“…Maleic acid is known to have p K a values in the range of 1.8–6.1 (p K 1 = 1.83; p K 2 = 6.07). 56,57 The carboxylic acid groups of the polymers are largely deprotonated at pH > 4, which renders the polymers water soluble for the entire temperature range (Figures 1B, S2 and Table S1).…”

Section: Resultsmentioning

confidence: 99%

Soluble–Insoluble–Soluble Transitions of Thermoresponsive Cryptand-Containing Graft Copolymers

et al. 2018

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Cryptand-containing alternative copolymers were first made from copolymerization of styrenic derivatives and maleic anhydride and then chemically modified in this work by grafting methoxy poly(ethylene glycol) (MPEG) onto the maleic functional groups. These graft copolymers show interesting multistep soluble–insoluble–soluble (S–I–S) transitions in acidic aqueous media at a cloud point ( T cp ) and a subsequent mixing temperature ( T mix ). Turbidity measurements and dynamic light scattering studies indicate that such complex transitions may be attributed to the entropic contribution associated with the dehydration and aggregation of the MPEG groups and then the enthalpic contribution associated with the hydrogen bonding between ethylene glycol and carboxylic acid groups. More importantly, the phase transition temperatures and insoluble temperature ranges are very sensitive to changes in subtle hydrophobic–hydrophilic balance of the copolymers, such as the variation of pH, the cryptand size, and the length of the MPEG graft. The understanding of the S–I–S transition in relation to the structure of the copolymers and the external conditions may be useful in the design of smart materials and sensors.

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Section: Resultsmentioning

confidence: 99%

Soluble–Insoluble–Soluble Transitions of Thermoresponsive Cryptand-Containing Graft Copolymers

et al. 2018

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“…If no transition is existent a monotonic increasing function can be observed (i.e., poly(acrylic acid)) 43. It is already well established that the shapes of the p K app versus α for polymers such as poly(methacrylic acid),44–46 xanthan,47 poly( L ‐aspartic acid),48 poly(maleic acid)49–53 and poly(fumaric acid)52, 53 show an unusual dissociation behavior, where the curve shape itself directly reflects the additional work required for a conformational change due to ionization.…”

Section: Resultsmentioning

confidence: 99%

The Electrostatic Origin of Low‐Hydration Polymorphism in DNA

Mazur

2008

ChemPhysChem

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In recent years, significant progress has been made towards uncovering the physical mechanisms of low-hydration polymorphism in double-helical DNA. The effect appears to be mechanistically similar in different biological systems, and it is due to the ability of water to form spanning H-bonded networks around biomacromolecules via a quasi-two-dimensional percolation transition. In the case of DNA, disintegration of the spanning H-bonded network leads to electrostatic condensation of DNA strands because, below the percolation threshold, water loses its high dielectric permittivity, whereas the concentration of neutralizing counterions becomes high. In this Concept article arguments propose that this simple electrostatic mechanism represents the universal origin of low-hydration polymorphism in DNA.

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“…If no transition is existent a monotonic increasing function can be observed (i.e., poly(acrylic acid)). [ 43 ] It is already well established that the shapes of the p K app versus α for polymers such as poly(methacrylic acid), [44][45][46] xanthan, [ 47 ] poly( L -aspartic acid), [ 48 ] poly(maleic acid) [49][50][51][52][53] and poly(fumaric acid) [ 52 , 53 ] show an unusual dissociation behavior, where the curve shape itself directly refl ects the additional work required for a conformational change due to ionization. Figure 2 -4 illustrate the dependence of p K app for PalH, PalPh and PalPhBisCarb as a function of α at different ionic strengths (an example titration curve obtained for PalH in 1 M NaCl can be found in the Supporting Information).…”

Section: Potentiometric Titrationmentioning

confidence: 99%

Potentiometric Behavior of Polyampholytes Based on N,N′‐diallyl‐N,N′‐dimethylammonium Chloride and Maleamic Acid Derivatives

Fechner

Koetz

2011

Macro Chemistry & Physics

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Strongly alternating copolymers (PalH, PalPh, PalPhBisCarb) composed of N , N ´-diallyl-N , N ´-dimethyl-ammonium chloride (DADMAC) and maleamic acid derivatives (MAD) are synthesized by a water-based free radical copolymerization using 4,4-azobis(4-cyanovaleric acid) (V501) as the initiator. The structure of the copolymers is verifi ed by 1 H-NMR, elemental analysis, and thermogravimetric measurements, and the physicochemical properties are investigated by viscometric and potentiometric techniques. Potentiometric titration curves show that the acidity of the carboxylic groups strongly depends on the degree of dissociation and the ionic strength. Since all copolymers behave as polycations at low degree of dissociation, a transition from an extended chain to a coil conformation can be identifi ed by reaching the isoelectric point (IEP). screening effect) [ 1 , 5 , 6 ] accompanied by the formation of a globular structure at the isoelectric point (IEP). In this context the net charge and thus the conformation can be infl uenced via the sequence of the monomer units as well as the pH, the ionic strength and the temperature. [ 4 ] By changing one of these parameters different structural transitions [ 7 , 8 ] can be promoted that may be of interest for special dynamic systems. A charge imbalance can lead to necklace-like structures in water, whereas a low charge density (weak electrostatic forces) promotes a Gaussian conformation. A change of the pH to lower or higher values (that means away from the IEP) leads to a charge asymmetry and thus a behavior that can be described in terms of polyelectrolyte theories, [9][10][11][12][13][14][15] where chain expansion and network swelling occurs due to the repulsion of equal charges. However, salt addition to a polyampholyte solution at or near the IEP leads to a screening of electrostatic attractive forces between the complementary charges and, therefore, a chain expansion becomes possible. Since synthetic PA can be regarded as model systems for biopolymers, a deeper insight concerning the nature of electrostatic interactions is of growing interest.

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Behavior of Nonalternating Maleic Acid Copolymers in Aqueous Solution

Cited by 25 publications

References 17 publications

Soluble–Insoluble–Soluble Transitions of Thermoresponsive Cryptand-Containing Graft Copolymers

Soluble–Insoluble–Soluble Transitions of Thermoresponsive Cryptand-Containing Graft Copolymers

The Electrostatic Origin of Low‐Hydration Polymorphism in DNA

Potentiometric Behavior of Polyampholytes Based on N,N′‐diallyl‐N,N′‐dimethylammonium Chloride and Maleamic Acid Derivatives

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