Salt-induced control of supramolecular order in biocatalytic hydrogelation

Sangita Roy, Nadeem Javid, Jan Sefcik, Peter J. Halling, Rein V. Ulijn

Research output: Contribution to journalArticlepeer-review

50 Citations (Scopus)


Biocatalytic action and specific ion effects are both known to have dramatic effects on molecular self-assembly and hydrogelation. In this paper, we demonstrate that these effects are highly cooperative. Biocatalytic hydrogelation of Fmoc peptides in the presence of salts combines kinetic (through enzymatic catalysis) and thermodynamic (specific ion and protein templating) contributions when applied in combination. Spectroscopic data (obtained by fluorescence spectroscopy and circular dichroism) revealed that hydrophobic interactions are greatly affected, giving rise to differential chiral organization and supramolecular structure formation. The kinetic effects of catalytic action could be removed from the system by applying a heat/cool cycle, giving insight into the thermodynamic influence of both protein and salt on these systems and showing that the effects of catalysis, templating, and salts are cooperative. The variable molecular interactions are expressed as variable material properties, such as thermal stability and mechanical strength of the final gel-phase material. To gain more insight into the role of the enzyme, beyond catalysis, in the underlying mechanism, static light scattering is performed, which indicates the different mode of aggregation of the enzyme molecules in the presence of different salts in aqueous solution that may play a role to direct the assembly via templating. Overall, the results show that the combination of specific salts and enzymatic hydrogelation can give rise to complex self-assembly behaviors that may be exploited to tune hydrogel properties.

Original languageEnglish
Pages (from-to)16664-16670
Number of pages7
Issue number48
Early online date1 Nov 2012
Publication statusPublished - 4 Dec 2012


  • salt-induced control
  • supramolecular order
  • biocatalytic hydrogelation


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