Effect of the intramolecular charge separation distance on the solution properties of betaines and sulfobetaines

Weers, Jeffry G.; Rathman, James F.; Axe, Frank U.; Crichlow, Charles A.; Foland, Lafayette D.; Scheuing, David R.; Wiersema, Richard J.; Zielske, Alfred G.

doi:10.1021/la00053a008

Cited by 257 publications

(280 citation statements)

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“…In the case of the ammoniocarboxylates (basic form VII in Figure 1), pK a values of 1.8, 3.3, 4.0 and 4.2 were reported for x, the number of methylene groups between the ionic sites, increasing from 1 to 4 [73]. This is due to the strong electron withdrawing effect of the ammonium group, which levels off for x  4, resulting in pK a values of about 4.5.…”

Section: Zwitterionic Moieties Realized In Polyzwitterions and Their mentioning

confidence: 96%

Structures and Synthesis of Zwitterionic Polymers

2014

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Abstract:The structures and synthesis of polyzwitterions ("polybetaines") are reviewed, emphasizing the literature of the past decade. Particular attention is given to the general challenges faced, and to successful strategies to obtain polymers with a true balance of permanent cationic and anionic groups, thus resulting in an overall zero charge. Also, the progress due to applying new methodologies from general polymer synthesis, such as controlled polymerization methods or the use of "click" chemical reactions is presented. Furthermore, the emerging topic of responsive ("smart") polyzwitterions is addressed. The considerations and critical discussions are illustrated by typical examples.

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Section: Zwitterionic Moieties Realized In Polyzwitterions and Their mentioning

confidence: 96%

Structures and Synthesis of Zwitterionic Polymers

2014

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“…73 Steric reasons facilitating, or hampering, respectively, intra-chain ion pairing were suggested as a possible explanation. Interestingly, in the case of the structurally closely related ammonioalkanoates, theoretical studies predict the maximum hydrophilicity of the zwitterionic group being for separation of the anionic and the cationic groups by 6-8 methylene groups, due to balancing the hydration and dehydration energies of the ionic and the spacer groups, respectively.…”

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confidence: 99%

Effect of the zwitterion structure on the thermo-responsive behaviour of poly(sulfobetaine methacrylates)

Hildebrand

Laschewsky

Päch³

et al. 2017

Polym. Chem.

135

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A series of new sulfobetaine methacrylates, including nitrogen-containing saturated heterocycles, was synthesised by systematically varying the substituents of the zwitterionic group. Radical polymerisation via the RAFT (reversible addition-fragmentation chain transfer) method in trifluoroethanol proceeded smoothly and was well controlled, yielding polymers with predictable molar masses. Molar mass analysis and control of the end-group fidelity were facilitated by end-group labeling with a fluorescent dye. The polymers showed distinct thermo-responsive behaviour of the UCST (upper critical solution temperature) type in an aqueous solution, which could not be simply correlated to their molecular structure via an incremental analysis of the hydrophilic and hydrophobic elements incorporated within them. Increasing the spacer length separating the ammonium and the sulfonate groups of the zwitterion moiety from three to four carbons increased the phase transition temperatures markedly, whereas increasing the length of the spacer separating the ammonium group and the carboxylate ester group on the backbone from two to three carbons provoked the opposite effect. Moreover, the phase transition temperatures of the analogous polyzwitterions decreased in the order dimethylammonio > morpholinio > piperidinio alkanesulfonates. In addition to the basic effect of the polymers' precise molecular structure, the concentration and the molar mass dependence of the phase transition temperatures were studied. Furthermore, we investigated the influence of added low molar mass salts on the aqueous-phase behaviour for sodium chloride and sodium bromide as well as sodium and ammonium sulfate. The strong effects evolved in a complex way with the salt concentration. The strength of these effects depended on the nature of the anion added, increasing in the order sulfate < chloride < bromide, thus following the empirical Hofmeister series. In contrast, no significant differences were observed when changing the cation, i.e. when adding sodium or ammonium sulfate.

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“…13). This result indicates that the gas-phase energy, which Comparison of critical micelle concentration (cmc; taken from [59]) and calculated solvation energy as a function of the number n of CH 2 groups of homologous betaines becomes lower as hmi decreases, is a major contributor to the final solvation energy. This result is most fascinating as one tends to ascribe effects on the solvation energy to structures in solution.…”

Section: Vagiprev)mentioning

confidence: 95%

“…9) [56]. Studies had established that 1) the distance between the carboxylato and the trimethylammonio groups increases linearly with an increase in the number of methylene groups [57] [58], and 2) a plot of log cmc (critical micelle concentration) and number of methylene groups in the zwitterionic head group of dodecylbetanes gives a parabolic relationship [59], with a maximum at n 4. Although the molecules are quite different, we consider the betaines as a model of the head group for the dodecyl betaines.…”

Section: Vagiprev)mentioning

confidence: 99%

Rationalizing the Solution Properties of Zwitterions by Means of Computational Chemistry

Gandour¹

2005

C&B

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This short review describes our computational studies of carnitine, acetylcarnitines, and betaines over the past two decades. Interspersed among the three computational studies--a molecular mechanics study of the conformer population of carnitine and acetylcarnitine, an AM1 study of the energetics of hydrolysis of acetylcarnitine, and an HF 6-31G* study of the solvation energies and structures of a homologous series of betaines--are brief overviews of our research in designing and testing new therapeutic agents for non-insulin dependent diabetes and for protection against sexually transmitted diseases. The three studies also show how computational chemistry has evolved during this time to enable an evaluation of the structure and energetics of zwitterions in aqueous solution.

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Effect of the intramolecular charge separation distance on the solution properties of betaines and sulfobetaines

Cited by 257 publications

References 0 publications

Structures and Synthesis of Zwitterionic Polymers

Structures and Synthesis of Zwitterionic Polymers

Effect of the zwitterion structure on the thermo-responsive behaviour of poly(sulfobetaine methacrylates)

Rationalizing the Solution Properties of Zwitterions by Means of Computational Chemistry

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