Biocatalytic Self-Assembly Using Reversible and Irreversible Enzyme Immobilization

Abstract

Biocatalytic control of molecular self-assembly provides an effective approach for developing smart biomaterials, allowing versatile enzyme-mediated tuning of material structure and properties as well as enabling biomedical applications. We functionalized surfaces with bioinspired polydopamine and polyphenol coatings to study the effects of enzyme surface localization and surface release on the self-assembly process. We show how these coatings could be conveniently used to release enzymes for bulk gelation as well as to irreversibly immobilize enzymes for localizing the self-assembly to the surface. The results provide insights to the mode of action of biocatalytic self-assembly relevant to nanofabrication and enzyme-responsive materials.

Surface‐Assisted Self‐Assembly Strategies Leading to Supramolecular Hydrogels

“…Recently, Ulijn showed the effect of the anchoring strength of an enzyme on a surface on the self‐assembly process . Using again thermolysin and the system Fmoc‐T‐OH/F‐NH 2 (T=threonine, F‐NH 2 =phenylalanine with a carboxamide group at C‐terminal position), forming the hydrogelator Fmoc‐TF‐NH 2 in situ, they showed that when the enzyme is not covalently fixed on the substrate and if the rinsing is not strong enough to remove the weakly adsorbed enzymes, the self‐assembly leads to gelation in the bulk but in the proximity of the surface because the enzyme desorbs from the surface.…”

Surface‐Assisted Self‐Assembly of a Hydrogel by Proton Diffusion

“…Electrochemical production of protons using patterned electrodes was also used by Payne to gain spatial control on the self‐assembly of Fmoc protected amino acids . Others, such as van Esch and Eelkema, could control fiber formation and orientation by a pH gradient, further resorting to surface‐confined acidic catalysis, while Ulijn paved the way of surface‐confined enzyme catalysis, further developed by Vigier‐Carrière et al together with Jierry . Recently, controlled proton diffusion in a microfluidic device was utilized to study the kinetics of gelation of a pH responsive benzene‐1,3,5‐tricarboxamide (BTA) .…”

Oberflächenunterstützte Selbstorganisationsstrategien für supramolekulare Hydrogele

“…In einer neueren Studie demonstrierte Ulijn den Einfluss, den die Stärke der Verankerung eines Enzyms auf einer Oberfläche auf den Selbstorganisationsprozess hat . Erneut Thermolysin wurde zusammen mit Fmoc‐T‐OH/F‐NH 2 (T=Threonin, F‐NH 2 =Phenylalanin mit einer Carboxamidgruppe in C‐terminaler Position) eingesetzt, um den Hydrogelator Fmoc‐TF‐NH 2 in situ zu bilden.…”