The controlled electrochemical
deposition of hydrogels
from low-molecular
weight hydrogelators (LMWHGs) allows for the defined formation of
thin films on electrodes. Here, the deposition of fibrillar networks
consisting of N,N′,N″-tris(4-carboxyphenylene)-1,3,5-benzenetricarboxamide
(BTA) onto ultraflat gold electrodes has been studied. This process,
also termed electrogelation, is based on a local change in the pH
due to electrolysis of water at the electrode. The protonation of
the BTA sodium salt leads to self-assembly into supramolecular fibrillar
structures mainly via hydrogen bonding of the uncharged molecules.
The resulting hydrogel film was characterized in terms of its thickness
by atomic force microscopy (AFM). Two different AFM-based techniques
have been used: ex situ imaging of dried films and in situ nanoindentation of the hydrated hydrogel films.
The deposition process was studied as a function of gelator concentration,
applied potential, and gelation time. These parameters allow control
of the film thickness to a high degree of accuracy within a few tenths
of nanometers. Film formation takes place in a few seconds at moderate
applied potentials, which is beneficial for biomedical applications.
The results obtained for the BTA presented here can be transferred
to any type of pH-responsive LMWHG and many reversibly formed hydrogel
films.