Enzymatic Formation of Supramolecular Hydrogels

Yang, Zhimou; Gu, Hongwei; Fu, D.; Gao, Ping; Lam, Jacqueline C.K.; Xu, Bin

doi:10.1002/adma.200690020

Cited by 459 publications

(110 citation statements)

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“…In their work, they use enzyme-catalyzed transformations of peptide-based gelators to control gelator assembly. 7,8,9,10 In our group, we also used enzymatic catalysis to control break-down kinetics of supramolecular gels. 11,12 Enzymes rank among the most active and efficient catalysts known.…”

Section: Timelinementioning

confidence: 99%

Catalysis of Supramolecular Hydrogelation

et al. 2016

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CONSPECTUSOne often thinks of catalysts as chemical tools to speed up a reaction, or to have a reaction run under more benign conditions. As such, catalysis has a role to play in the chemical industry and in lab scale synthesis that is not to be underestimated. Still, the role of catalysis in living systems (cells, organisms) is much more extensive, ranging from the formation and breakdown of small molecules and biopolymers, to controlling signal transduction cascades and feedback processes, motility and mechanical action. Such phenomena are only recently starting to receive attention in synthetic materials and chemical systems. 'Smart' soft materials could find many important applications ranging from personalized therapeutics to soft robotics, to name but a few. Until recently, approaches to controlling the properties of such materials were largely dominated by thermodynamics, for instance looking at phase behavior and interaction strength. However, kinetics play a large role in determining the behavior of such soft materials, for instance in the formation of kinetically trapped (metastable) states, or the dynamics of component exchange. As catalysts can change the rate of a chemical reaction, catalysis could be used to control the formation, dynamics and fate of supramolecular structures, when the molecules making up these structures contain chemical bonds whose formation or exchange are susceptible to catalysis. In this Account, we describe our efforts to use synthetic catalysts to control the properties of supramolecular hydrogels. Building on the concept of synthesizing the assembling molecule in the self-assembly medium from non-assembling precursors, we will introduce the use of catalysis to change the kinetics of assembler formation, and thereby the properties of the resulting material. In particular, we will focus on the synthesis of supramolecular hydrogels where the use of a catalyst provides access to gel materials with vastly different appearance and mechanical properties, or controls localized gel formation and the growth of gel objects. As such, catalysis will be applied to create molecular materials that exist outside of chemical equilibrium. In all, using catalysts to control the properties of soft materials constitutes a new avenue for catalysis, far beyond the traditional use in industrial and lab scale synthesis.

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Section: Timelinementioning

confidence: 99%

Catalysis of Supramolecular Hydrogelation

et al. 2016

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“…Indeed, enzymatically controlled self-assembly and disassembly underlies vital processes such as cell movement, intracellular transport and muscle contraction. In chemists' hands, the combination of biocatalysis and molecular self-assembly has recently emerged as a powerful new approach to make novel stimuli-responsive molecular materials [12][13][14][15][16][17] . We believe that catalytic control of self-assembly provides important new methodology beyond such triggering of material transitions.…”

mentioning

confidence: 99%

“…Although the traditional premise in selfassembly suggests that supramolecular material properties can be fully encoded into molecular building blocks, it is increasingly apparent that the chosen self-assembly pathway is central to the final structure and its material functionality. Biocatalytic control of self-assembly systems is a novel direction for laboratory-based self-assembly [12][13][14][15][16][17] , although it is omnipresent in the biological world. Indeed, enzymatically controlled self-assembly and disassembly underlies vital processes such as cell movement, intracellular transport and muscle contraction.…”

mentioning

confidence: 99%

Biocatalytic induction of supramolecular order

et al. 2010

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Supramolecular gels, which demonstrate tunable functionalities, have attracted much interest in a range of areas, including healthcare, environmental protection and energy-related technologies. Preparing these materials in a reliable manner is challenging, with an increased level of kinetic defects observed at higher self-assembly rates. Here, by combining biocatalysis and molecular self-assembly, we have shown the ability to more quickly access higher-ordered structures. By simply increasing enzyme concentration, supramolecular order expressed at molecular, nano-and micro-levels is dramatically enhanced, and, importantly, the gelator concentrations remain identical. Amphiphile molecules were prepared by attaching an aromatic moiety to a dipeptide backbone capped with a methyl ester. Their self-assembly was induced by an enzyme that hydrolysed the ester. Different enzyme concentrations altered the catalytic activity and size of the enzyme clusters, affecting their mobility. This allowed structurally diverse materials that represent local minima in the free energy landscape to be accessed based on a single gelator structure.M olecular self-assembly 1-7 can be controlled using a variety of stimuli, including chemical 8,9 and mechanical 10 triggers, as well as X-rays 11 . Although the traditional premise in selfassembly suggests that supramolecular material properties can be fully encoded into molecular building blocks, it is increasingly apparent that the chosen self-assembly pathway is central to the final structure and its material functionality. Biocatalytic control of self-assembly systems is a novel direction for laboratory-based self-assembly 12-17 , although it is omnipresent in the biological world. Indeed, enzymatically controlled self-assembly and disassembly underlies vital processes such as cell movement, intracellular transport and muscle contraction. In chemists' hands, the combination of biocatalysis and molecular self-assembly has recently emerged as a powerful new approach to make novel stimuli-responsive molecular materials [12][13][14][15][16][17] . We believe that catalytic control of self-assembly provides important new methodology beyond such triggering of material transitions. In particular, the combination of biological selectivity, localized action and operation under constant, physiological conditions provides a new methodology for bottomup nanofabrication of future soft materials and devices, allowing for unprecedented control of supramolecular order.Here, we focus on the control of supramolecular order with few defects. In principle, there are two possible approaches to defect reduction-either improving the fidelity of the self-assembly process (avoiding defects) or using fully reversible systems that operate under thermodynamic control (repairing defects). The latter approach is generally slow and only applicable to cases where the desired structure represents the global equilibrium state and where the system is fully reversible, that is, under thermodynamic control 16 . Many structure...

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“…Phosphatase triggered self-assembly was first reported by Xu et al 37,38 for fluorenyl functionalized phosphorylated tyrosine residues (Fmoc-pY). Since this early report, biocatalytically triggered self-assembly of aromatic peptide amphiphiles has developed into an active field, with examples studied in the context of biomedical, electronic and drug delivery applications, but so far it has not been associated with motility applications.…”

Section: -11mentioning

confidence: 99%

Nanopropulsion by Biocatalytic Self-Assembly

et al. 2014

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Enzymatic Formation of Supramolecular Hydrogels

Cited by 459 publications

References 0 publications

Catalysis of Supramolecular Hydrogelation

Catalysis of Supramolecular Hydrogelation

Biocatalytic induction of supramolecular order

Nanopropulsion by Biocatalytic Self-Assembly

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