Photothermally switchable peptide nanostructures towards modulating catalytic hydrolase activity

Singh, Ashmeet; Joseph, Jojo P.; Gupta, Deepika; Miglani, Chirag; Mavlankar, Nimisha A.; Pal, Asish

doi:10.1039/d1nr03655f

Cited by 32 publications

(31 citation statements)

References 43 publications

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“…The RADA16H, RADA16H 2 , and RADA16H 3 catalyzed the hydrolysis of pNPA with a constant Km on the order of 3 × 10 -3 M, with k cat values of 2.43 × 10 -3 s −1 -4.87 × 10 -3 s −1 (Supplementary Table S2). The catalytical efficiencies (k cat / K m ) of RADA16H, RADA16H 2 , and RADA16H 3 were on the same order of most of the previously reported artificial peptide-based enzymes for pNPA hydrolysis (Singh et al, 2015;Zhang et al, 2017;Huang et al, 2020;Liu et al, 2020;Hamley 2021;Singh et al, 2021). However, it is 40-240 times slower than the histidine-containing amyloid-forming peptides, such as IHIHIQI, IHIHIQI and IHIHIYI, which include a Zn 2+ in their catalytic center (Rufo et al, 2014;Al-Garawi et al, 2017;Song et al, 2018).…”

Section: Hydrolysis Kinetic Study Of the Peptide Nanofiberssupporting

confidence: 76%

“…The common features of the peptide assemblies share some of the characteristics of enzymes and suggest that these peptides are a promising framework to mimic natural enzymes and provide a backbone of active sites ( Zozulia et al, 2018 ; Liu et al, 2020 ; Han et al, 2021 ). Compared to the natural enzymes, these peptide assemblies are much more robust and stable over a broad range of pH and temperature and can be readily synthesized ( Singh et al, 2021 ; Dowari et al, 2022 ). Histidine has been frequently found in active center of proteases and other hydrolytic enzymes as its imidazole side chain is capable of serving as a hydrogen bond donor or acceptor ( Sharma et al, 2016 ).…”

Section: Introductionmentioning

confidence: 99%

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An artificial self-assembling peptide with carboxylesterase activity and substrate specificity restricted to short-chain acid p-nitrophenyl esters

et al. 2022

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Natural enzymes possess remarkable catalytic activity and high substrate specificity. Many efforts have been dedicated to construct artificial enzymes with high catalytic activity. However, how to mimic the exquisite substrate specificity of a natural enzyme remains challenging because of the complexity of the enzyme structure. Here, we report artificial carboxylesterases that are specific for short chain fatty acids and were constructed via peptide self-assembly. These artificial systems have esterase-like activity rather than lipase-like activity towards p-nitrophenyl esters. The designer peptides self-assembled into nanofibers with strong β-sheet character. The extending histidine units and the hydrophobic edge of the fibrillar structure collectively form the active center of the artificial esterase. These artificial esterases show substrate specificity for short-chain acids esters. Moreover, 1-isopropoxy-4-nitrobenzene could function as a competitive inhibitor of hydrolysis of p-nitrophenyl acetate for an artificial esterase.

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Section: Hydrolysis Kinetic Study Of the Peptide Nanofiberssupporting

confidence: 76%

Section: Introductionmentioning

confidence: 99%

An artificial self-assembling peptide with carboxylesterase activity and substrate specificity restricted to short-chain acid p-nitrophenyl esters

et al. 2022

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“…Light mediated [2 + 2] cyclodimerization in coumarin, anthracene and cinnamate moieties endows excellent dynamic and reversible photoresponsive systems. 14 , 14 g Incorporation of these moieties into the polymeric chain is an interesting approach to design photoresponsive self-healing materials for smart coating applications. However, this requires judicious optimization of a number of critical parameters such as low viscosity, ease of processing, good control over the molecular weight, crosslinking ability, flexibility vs. rigidity, architectural control, tacticity in a multiphase, compartmentalized network.…”

Section: Introductionmentioning

confidence: 99%

Modulation of flexo-rigid balance in photoresponsive thymine grafted copolymers towards designing smart healable coating

Miglani¹,

Joseph²,

Gupta³

et al. 2021

RSC Adv.

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“…However, a repeated annealing of the nanofibers rendered the formation of thermodynamically stable twisted bundle morphology (Figures 1D and S2G,H) similar to our previous report. 42,46 We monitored such a pathway-driven self-assembly process of trans-1 in water using UV−vis and CD spectroscopy analyses.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Photochemically Sequestered Off-Pathway Dormant States of Peptide Amphiphiles for Predictive On-Demand Piezoresponsive Nanostructures

Gupta¹,

Bhatt²,

Gupta³

et al. 2022

Chem. Mater.

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Supramolecular assemblies are essential for specific biological functions and mandate precise control over the mesoscopic scale for higher functional efficiency. Such well-defined biomimetic self-organization can be accessed through kinetically controlled nonequilibrium transformations rather than the typical downhill thermodynamically driven processes. Recently, spatiotemporal control for the living supramolecular polymerization has rendered a paradigm shift toward designing complex multicomponent supramolecular active materials; however, directing the active monomer toward predictive kinetically trapped materials still remains a considerable challenge as this necessitates circumventing spontaneous nucleation of the monomers during the self-assembly process. Herein, we demonstrate dual strategies (chemical and photo) to sequester the active peptide self-assembling motifs in dormant states that, upon judicious activation, engage in controlled seeded supramolecular polymerization in aqueous milieu for the first time. Amyloid-inspired peptide 1 with a pendant azobenzene moiety demonstrates the formation of on-pathway metastable nanoparticles by the interplay of solvent and temperature that could be transformed into kinetically controlled nanofibers and thermodynamically controlled twisted bundles. Further, using coupled equilibrium such as the host−guest inclusion complex with cyclodextrin or photoisomerization with UV light leads to the formation of two distinct offpathway metastable states that retard the spontaneous supramolecular polymerization. A judicious manipulation of the free-energy landscapes in tandem with suitable chemical and photostimuli renders the activation of the dormant states for the peptide selfassembly through a seeded growth strategy. Finally, such photochemical sequestration of self-assembly pathways results in on−off piezoresponsive peptide nanostructures. In summary, we demonstrated for the first time the nonequilibrium peptide self-assembly coupled with dormant metastable states to allow access to an interesting repertoire of structural diversities and attenuated piezoresponse control in supramolecular peptide nanostructures.

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Photothermally switchable peptide nanostructures towards modulating catalytic hydrolase activity

Abstract: Enzymes are the most efficient catalysts in nature that possess an impressive range of catalytic activities albeit limited by the stability in adverse condition. Functional peptides have emerged as alternative...

Cited by 32 publications

References 43 publications

An artificial self-assembling peptide with carboxylesterase activity and substrate specificity restricted to short-chain acid p-nitrophenyl esters

An artificial self-assembling peptide with carboxylesterase activity and substrate specificity restricted to short-chain acid p-nitrophenyl esters

Modulation of flexo-rigid balance in photoresponsive thymine grafted copolymers towards designing smart healable coating

Photochemically Sequestered Off-Pathway Dormant States of Peptide Amphiphiles for Predictive On-Demand Piezoresponsive Nanostructures

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