Charge Interaction of Synthetic Polycarboxybetaines in Bulk and Solution

Abstract

Various polycarboxybetaines were synthesized using controlled radical polymerization processes followed by polymer analogous transformations. Structural variation of these exclusively aromatic or heteroaromatic systems includes distance between charges, hybridization and substitution of the ammonium moiety, and additional alkyl chains between the charges. For the first time capillary electrophoresis was used for systematic characterization of the solution properties. It was found to be a very sensitive method to detect even small structural differences and the resulting pH-dependent solution behavior. The electrophoretical mobility compared with an internal standard and the amount of its pH dependence are direct measures for the interaction of charges of polycarboxybetaines in solution. This method clearly reveals a gradual and more or less predictable content of “free” cationic charges dependent on structural and solution parameters. Results obtained coincide in a fairly good way with data from FTIR measurement and charge titration.

Structures and Synthesis of Zwitterionic Polymers

“…The pK a values the carboxyl groups was found to stay below 2.5 even for large spacer groups (x  8) separating the ammonium and carboxylate sites [76]. In contrast, another study observes the preservation of a clear spacer effect on the aciditiy of the carboxyl group in such polybetaines [77].…”

“…Under physiological conditions pH is about 7-8, thus for related uses, the only moderate acidity of the -COOH group will not endanger the zwitterionic state. However in other, more acidic or less defined environments, deprotonation of the anionic site may be partially or even fully suppressed, turning thus the supposed polyzwitterion into a polycation [77,78].…”

“…Scheme 5, path 3b). Noteworthy, in the case of polycarboxybetaines derived from vinylpyridines, post-polymerization modification following this strategy seems to be virtually the only path realized up to now [9,77,78,[392][393][394][395][396][397]. The polymeric amine itself may result from a previous modification step (cf.…”

Synthesis and Self-Assembly of [60]Fullerene Containing Sulfobetaine Polymer in Aqueous Solution

“…28 Different kinds of polyzwitterionic polymers and its copolymers have been developed and their aqueous solution properties were studied. [29][30][31][32][33] Armes and coworkers studied the salt dependency on chain expansion of micellar aggregates produced from betainized PDMAEMA-b-PMMA. 34 However, a detailed study on the dependence of UCST on salt concentration has not been reported.…”

A regular, hydrophobically modified polyampholyte as novel pour point depressant

“…An alternative convenient route to hydrophobically modified polyampholytes is offered by the chemical modification of polymers, enabling variable strategies. [21][22][23][24][25] However, the simplicity of these two strategies is counterbalanced by the less-defined molecular structure of the resulting products. An attractive compromise between these two extremes is offered by the alternating copolymerization of appropriate monomer pairs, to incorporate anionic moieties, cationic moieties, and hydrophobic groups into the same polymer in a regular way.…”