Artificial enzyme

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Schematic drawing of artificial phosphorylase

An artificial enzyme is a synthetic, organic molecule or ion that recreate some function of an enzyme. The area promises to deliver catalysis at rates and selectivity observed in many enzymes.


Enzyme catalysis of chemical reactions occur with high selectivity and rate. The substrate is activated in a small part of the enzyme's macromolecule called the active site. There, the binding of a substrate close to functional groups in the enzyme causes catalysis by so-called proximity effects. It is possible to create similar catalysts from small molecule by combining substrate-binding with catalytic functional groups. Classically artificial enzymes bind substrates using receptors such as cyclodextrin, crown ethers, and calixarene.[1][2]

Artificial enzymes based on amino acids or peptides as characteristic molecular moieties have expanded the field of artificial enzymes or enzyme mimics. For instance, scaffolded histidine residues mimics certain metalloproteins and -enzymes such as hemocyanin, tyrosinase, and catechol oxidase).[3]

Artificial enzymes have been designed from scratch via a computational strategy using Rosetta.[4] In December 2014, it was announced that active enzymes had been produced that were made from artificial molecules which do not occur anywhere in nature.[5] In 2017, a book chapter entitled "Artificial Enzymes: The Next Wave" was published.[1]


Nanozymes are nanomaterials with enzyme-like characteristics.[6][7] They have been widely explored for various applications, such as biosensing, bioimaging, tumor diagnosis and therapy, antibiofouling.[8][9][10][11][12]


In 1996 and 1997, Dugan et al. discovered the superoxide dismutase (SOD) mimicking activities of fullerene derivatives.[13][14]


In 2004, the term "nanozymes" was coined by Flavio Manea, Florence Bodar Houillon, Lucia Pasquato, and Paolo Scrimin.[15] In 2006, nanoceria (i.e., CeO2 nanoparticles) was used for preventing retinal degeneration induced by intracellular peroxides.[16][17] In 2007, Xiyun Yan and coworkers reported that ferromagnetic nanoparticles possessed intrinsic peroxidase-like activity.[18][19] In 2008, Hui Wei and Erkang Wang developed an iron oxide nanozyme based sensing platform for bioactive molecules (such as hydrogen peroxide and glucose).[20]


In 2010 and 2011, graphene oxide with peroxidase-like activity was reported.[21][22] In 2012, recombinant human heavy-chain ferritin coated iron oxide nanoparticle with peroxidase-like activity was prepared and used for targeting and visualizing tumour tissues.[23] In 2012, vanadium pentoxide nanoparticles with vanadium haloperoxidase mimicking activities were used for preventing marine biofouling.[24] In 2014, it was demonstrated that carboxyfullerene could be used to treat neuroprotection postinjury in Parkinsonian nonhuman primates.[25] Peroxidase-like polyoxometalate derivatives were developed as functional anti-amyloid agents for Alzheimer’s disease.[26] V2O5 nanozymes with cytoprotective function was reported.[27] In 2015, a supramolecular regulation strategy was proposed to modulate the activity of gold-based nanozymes for imaging and therapeutic applications.[28][29] A nanozyme-strip for rapid local diagnosis of Ebola was developed.[30][31] Nanoceria nanozymes were used for DNA sensing.[32] An integrated nanozyme has been developed for real time monitoring the dynamic changes of cerebral glucose in living brains.[33][34] Cu(OH)2 nanozymes with peroxidase-like activities were reported.[35] Ionic FePt, Fe3O4, Pd, and CdSe NPs with peroxidase-like activities were reported.[36] A book entitled "Nanozymes: Next Wave of Artificial Enzymes" was published.[37] A book chapter entitled "Nanozymes" in the book of "Enzyme Engineering" was published (in Chinese).[38] Oxidase-like nanoceria has been used for developing self-regulated bioassays.[39] Multi-enzyme mimicking Prussian blue was developed for therapeutics.[40] Histidine was used to modulate iron oxide nanoparticles' peroxidase mimicking activities.[41] Gold nanoparticles' peroxidase mimicking activities were modulated via a supramolecular strategy for cascade reactions.[42] A molecular imprinting strategy was developed to improve the selectivity of Fe3O4 nanozymes with peroxidase-like activity.[43] A new strategy was developed to enhance the peroxidase mimicking activity of gold nanoparticles by using hot electrons.[44] Researchers have designed gold nanoparticles (AuNPs) based integrative nanozymes with both SERS and peroxidase mimicking activities for measuring glucose and lactate in living tissues.[45] Cytochrome c oxidase mimicking activity of Cu2O nanoparticles was modulated by receiving electrons from cytochrome c.[46] Fe3O4 NPs were combined with glucose oxidase for tumor therapeutics.[47] Manganese dioxide nanozymes have been used as cytoprotective shells.[48] Mn3O4 Nanozyme for Parkinson's Disease (cellular model) was reported.[49] Heparin elimination in live rats has been monitored with 2D MOF based peroxidase mimics and AG73 peptide.[50] Glucose oxidase and iron oxide nanozymes were encapsulated within multi-compartmental hydrogels for incompatible tandem reactions.[51] A cascade nanozyme biosensor was developed for detection of viable Enterobacter sakazakii.[52] An integrated nanozyme of GOx@ZIF-8(NiPd) was developed for tandem catalysis.[53] Charge-switchable nanozymes were developed.[54] Site-selective RNA splicing nanozyme was developed.[55] A nanozymes special issue in Progress in Biochemistry and Biophysics was published.[56] Mn3O4 nanozymes with ROS scavenging activities have been developed for in vivo anti-inflammation.[57] A concept entitled "A Step into the Future – Applications of Nanoparticle Enzyme Mimics" was proposed.[58] Facet-dependent oxidase and peroxidase-like activities of Pd nanoparticles were reported.[59] Au@Pt multibranched nanostructures as bifunctional nanozymes were developed.[60] Ferritin coated carbon nanozymes were developed for tumor catalytic therapy.[61] CuO nanozymes were developed to kill bacteria via a light-controlled manner.[62] Enzymatic activity of oxygenated CNT was studied.[63] Nanozymes were used to catalyze the oxidation of l-Tyrosine and l-Phenylalanine to dopachrome.[64] Nanozyme as an emerging alternative to natural enzyme for biosensing and immunoassay was summarized.[65] Standardized assay was proposed for peroxidase-like nanozymes.[66] Semiconductor QDs as nucleases for site-selective photoinduced cleavage of DNA[67]. 2D-MOF nanozyme-based sensor arrays was constructed for detecting phosphates and probing their enzymatic hydrolysis.[68] N-doped carbon nanomaterials as specific peroxidase mimics were reported.[69] Nanozyme sensor arrays were developed to detect analytes from small Molecules to proteins and cells.[70] Copper oxide nanozyme for Parkinson’s Disease was reported.[71] Exosome-like nanozyme vesicles for tumor Imaging was developed.[72] A comprehensive review on nanozymes was published by Chemical Society Reviews.[73] A progress report on nanozymes was published.[74] eg occupancy as an effective descriptor was developed for the catalytic activity of perovskite oxide-based peroxidase mimics.[75] A Chemical Reviews on nanozymes was published.[76] A single-atom strategy was used for developing nanozymes.[77][78][79] Nanozyme for metal-free bioinspired cascade photocatalysis was reported.[80]


Several conferences have focused on nanozymes. In 2015, a nanozyme workshop for was held at the 9th Asian Biophysics Associatation (ABA) Symposium.[81] In Pittcon 2016, a Networking entitled "Nanozymes in Analytical Chemistry and Beyond" was devoted to nanozymes.[82] An Xiangshan Science Conference was devoted to nanozyme research.[83][84] A scientific session was devoted to "Biomimetic Nanocatalysis" in 15th Chinese Biophysics Congress.[85] The "Nanozymes for Bioanalysis (Oral)" section was included in the 256th ACS National Meeting (2018 Fall, Boston).[86]

See also[edit]


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