RESUMO
The fabrication of protected peptide-based hydrogels on electrode surfaces can be achieved by employing the electrochemical oxidation of hydroquinone to benzoquinone, liberating protons at the electrode-solution interface. The localised reduction in pH below the dipeptide gelator molecules pKa initiates the neutralisation, self-assembly and formation of self-supporting hydrogels exclusively at the electrode surface. Previous examples have been on a nanometre to millimetre scale, using deposition times ranging from seconds to minutes. However, the maximum size to which these materials can grow and their subsequent mechanical properties have not yet been investigated. Here, we report the fabrication of the largest reported di- and tri-peptide based hydrogels using this electrochemical method, employing deposition times of two to five hours. To overcome the oxidation of hydroquinone in air, the fabrication process was performed under an inert nitrogen atmosphere. We show that this approach can be used to form multilayer gels, with the mechanical properties of each layer determined by gelator composition. We also describe examples where gel-to-crystal transitions and syneresis occur within the material.
Assuntos
Hidrogéis , Hidroquinonas , Dipeptídeos , Oxirredução , PeptídeosRESUMO
In living systems, self-assembly processes are driven by the consumption of chemical fuels. Synthetic adaptation of living systems can be achieved by coupling of competing pathways that drive the assembly and disassembly, respectively, under the influence of chemical fuels. Here, a pH-responsive transient gel system is created by simultaneous incorporation of two triggers, of which one is responsible for the initiation of the self-assembly by increasing the pH and the second trigger drives the disassembly by reducing the pH. This method allows us to prepare transient gels with a high degree of control over the self-assembly lifetime as well as the mechanical properties of the transient gels.