{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,17]],"date-time":"2026-04-17T04:01:03Z","timestamp":1776398463306,"version":"3.51.2"},"reference-count":41,"publisher":"MDPI AG","issue":"15","license":[{"start":{"date-parts":[[2019,8,1]],"date-time":"2019-08-01T00:00:00Z","timestamp":1564617600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100010661","name":"Horizon 2020","doi-asserted-by":"publisher","award":["MSCA-ITN-2016 n. 721613"],"award-info":[{"award-number":["MSCA-ITN-2016 n. 721613"]}],"id":[{"id":"10.13039\/100010661","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>A series of 2-nm gold nanoparticles passivated with different thiols all featuring at least one triazacyclonanone-Zn(II) complex and different flanking units (a second Zn(II) complex, a triethyleneoxymethyl derivative or a guanidinium of arginine of a peptide) were prepared and studied for their efficiency in the cleavage of the RNA-model substrate 2-hydroxypropyl-p-nitrophenyl phosphate. The source of catalysis for each of them was elucidated from the kinetic analysis (Michaelis\u2013Menten profiles, pH dependence and kinetic isotope effect). The data indicated that two different mechanisms were operative: One involving two Zn(II) complexes and the other one involving a single Zn(II) complex and a flanking guanidinium cation. The mechanism based on a dinuclear catalytic site appeared more efficient than the one based on the cooperativity between a metal complex and a guanidinium.<\/jats:p>","DOI":"10.3390\/molecules24152814","type":"journal-article","created":{"date-parts":[[2019,8,1]],"date-time":"2019-08-01T11:39:37Z","timestamp":1564659577000},"page":"2814","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":20,"title":["Factors Influencing the Activity of Nanozymes in the Cleavage of an RNA Model Substrate"],"prefix":"10.3390","volume":"24","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0048-6392","authenticated-orcid":false,"given":"Joanna","family":"Czescik","sequence":"first","affiliation":[{"name":"University of Padova, Department of Chemical Sciences, via Marzolo, 1 35131 Padova, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0661-9539","authenticated-orcid":false,"given":"Susanna","family":"Zamolo","sequence":"additional","affiliation":[{"name":"University of Bern, Department of Chemistry and Biochemistry, Freiestrasse 3, CH-3012 Bern, Switzerland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2098-8514","authenticated-orcid":false,"given":"Tamis","family":"Darbre","sequence":"additional","affiliation":[{"name":"University of Bern, Department of Chemistry and Biochemistry, Freiestrasse 3, CH-3012 Bern, Switzerland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Fabrizio","family":"Mancin","sequence":"additional","affiliation":[{"name":"University of Padova, Department of Chemical Sciences, via Marzolo, 1 35131 Padova, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6741-3374","authenticated-orcid":false,"given":"Paolo","family":"Scrimin","sequence":"additional","affiliation":[{"name":"University of Padova, Department of Chemical Sciences, via Marzolo, 1 35131 Padova, Italy"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2019,8,1]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"220","DOI":"10.1021\/ar500314j","article-title":"Catalytic Metal Ions and Enzymatic Processing of DNA and RNA","volume":"48","author":"Palermo","year":"2015","journal-title":"Accounts Chem. Res."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"5545","DOI":"10.1039\/c2cc30952a","article-title":"Progress in artificial metallonucleases","volume":"48","author":"Mancin","year":"2012","journal-title":"Chem. Commun."},{"key":"ref_3","first-page":"129","article-title":"Phosphate Ester Hydrolysis: The Path From Mechanistic Investigation to the Realization of Artificial Enzymes","volume":"51","author":"Martinez","year":"2017","journal-title":"Ad. Phys. Org. Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"645","DOI":"10.1146\/annurev-biochem-060409-093051","article-title":"Benchmark Reaction Rates, the Stability of Biological Molecules in Water, and the Evolution of Catalytic Power in Enzymes","volume":"80","author":"Wolfenden","year":"2011","journal-title":"Annu. Rev. Biochem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"1997","DOI":"10.1016\/j.ccr.2005.04.016","article-title":"Metal ion catalysis in acyl and phosphoryl transfer: Transition states as ligands","volume":"249","author":"Yatsimirsky","year":"2005","journal-title":"Coordin Chem. Rev."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"8246","DOI":"10.1002\/anie.201400335","article-title":"Catalytic Zinc Complexes for Phosphate Diester Hydrolysis","volume":"53","author":"Tirel","year":"2014","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"250","DOI":"10.1016\/j.cbpa.2008.01.012","article-title":"Roles of metal ions in nucleases","volume":"12","author":"Dupureur","year":"2008","journal-title":"Curr. Opin. Chem. Biol."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"6165","DOI":"10.1002\/anie.200460649","article-title":"Nanozymes: Gold-nanoparticle-based transphosphorylation catalysts","volume":"43","author":"Manea","year":"2004","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Mancin, F., Prins, L., Pengo, P., Pasquato, L., Tecilla, P., and Scrimin, P. (2016). Hydrolytic Metallo-Nanozymes: From Micelles and Vesicles to Gold Nanoparticles. Molecules, 21.","DOI":"10.3390\/molecules21081014"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"15744","DOI":"10.1021\/ja801794t","article-title":"Phosphate Diester and DNA Hydrolysis by a Multivalent, Nanoparticle-Based Catalyst","volume":"130","author":"Bonomi","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"6982","DOI":"10.1021\/ja070980o","article-title":"Metallodendrimers as transphosphorylation catalysts","volume":"129","author":"Martin","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"2400","DOI":"10.1007\/s11051-014-2400-8","article-title":"Surface plasmon resonance promotion of homogeneous catalysis using a gold nanoparticle platform","volume":"16","author":"Knight","year":"2014","journal-title":"J. Nanopart Res."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"4826","DOI":"10.1002\/cctc.201801220","article-title":"An Unusual Two-Step Hydrolysis of Nerve Agents by a Nanozyme","volume":"10","author":"Khulbe","year":"2018","journal-title":"Chemcatchem"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"653","DOI":"10.1007\/s00775-009-0478-8","article-title":"Self-assembled gold nanocrystal micelles act as an excellent artificial nanozyme with ribonuclease activity","volume":"14","author":"Zhang","year":"2009","journal-title":"J. Biol. Inorg. Chem."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"72","DOI":"10.1016\/S0020-1693(01)00424-8","article-title":"Ligand effects on the phosphoesterase activity of Co(II) Schiff base complexes built on PAMAM dendrimers","volume":"317","author":"Zhang","year":"2001","journal-title":"Inorg. Chim. Acta"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"163","DOI":"10.1016\/j.ica.2013.11.008","article-title":"Zn(II) enhances nucleotide binding and dephosphorylation in the presence of a poly(ethylene imine) dendrimer","volume":"417","author":"Bazzicalupi","year":"2014","journal-title":"Inorg. Chim. Acta"},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"2622","DOI":"10.1039\/b926916a","article-title":"Phosphate diesters cleavage mediated by Ce(IV) complexes self-assembled on gold nanoparticles","volume":"8","author":"Bonomi","year":"2010","journal-title":"Org. Biomol. Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"485","DOI":"10.1021\/ar9500877","article-title":"Structure and Nuclease Activity of Simple Dinuclear Metal Complexes: Quantitative Dissection of the Role of Metal Ions","volume":"32","author":"Williams","year":"1999","journal-title":"Acc. Chem. Res."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"601","DOI":"10.1515\/pac-2014-1008","article-title":"Bio-inspired approaches to accelerating metal ion-promoted reactions: Enzyme-like rates for metal ion mediated phosphoryl and acyl transfer processes","volume":"87","author":"Brown","year":"2015","journal-title":"Pure Appl. Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"1158","DOI":"10.1021\/ja411969e","article-title":"Efficient phosphodiester cleaving nanozymes resulting from multivalency and local medium polarity control","volume":"136","author":"Mancin","year":"2014","journal-title":"J. Am. Chem. Soc."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"586","DOI":"10.1055\/s-1982-29870","article-title":"Phase-Transfer-Catalyzed Reactions of a-Haloalmides: Synthesis of a-Lactams","volume":"1982","author":"Scrimin","year":"1982","journal-title":"Synthesis"},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"14473","DOI":"10.1021\/ja406381b","article-title":"Catalysis by desolvation: The catalytic prowess of SAM-dependent halide-alkylating enzymes","volume":"135","author":"Lohman","year":"2013","journal-title":"J. Am. Chem Soc."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"13521","DOI":"10.1002\/anie.201708190","article-title":"Evolution of the Ligand Shell Morphology during Ligand Exchange Reactions on Gold Nanoparticles","volume":"56","author":"Luo","year":"2017","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"66001","DOI":"10.1209\/0295-5075\/119\/66001","article-title":"A review of molecular phase separation in binary self-assembled monolayers of thiols on gold surfaces","volume":"119","author":"Ong","year":"2017","journal-title":"Epl. Europhys. Lett."},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"1911","DOI":"10.1021\/acs.accounts.7b00165","article-title":"Characterization of Ligand Shell for Mixed-Ligand Coated Gold Nanoparticles","volume":"50","author":"Ong","year":"2017","journal-title":"Accounts Chem Res."},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"9316","DOI":"10.1021\/acsnano.6b03931","article-title":"Patchy and Janus Nanoparticles by Self-Organization of Mixtures of Fluorinated and Hydrogenated Alkanethiolates on the Surface of a Gold Core","volume":"10","author":"Marson","year":"2016","journal-title":"ACS Nano"},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"7200","DOI":"10.1021\/ja211030y","article-title":"Lanthanide-based NMR: A tool to investigate component distribution in mixed-monolayer-protected nanoparticles","volume":"134","author":"Guarino","year":"2012","journal-title":"J. Am. Chem. Soc."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"1523","DOI":"10.1039\/C1CC14726A","article-title":"Mapping the nanoparticle-coating monolayer with NMR pseudocontact shifts","volume":"48","author":"Guarino","year":"2011","journal-title":"Chem. Commun."},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"1540","DOI":"10.1002\/anie.200903924","article-title":"Thiol\u2013Ene Click Chemistry","volume":"49","author":"Hoyle","year":"2010","journal-title":"Angew. Chem. Int. Ed."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"4120","DOI":"10.1021\/la703558y","article-title":"Expeditious Synthesis of Water-Soluble, Monolayer-Protected Gold Nanoparticles of Controlled Size and Monolayer Composition","volume":"24","author":"Manea","year":"2008","journal-title":"Langmuir"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"4879","DOI":"10.1002\/chem.201002590","article-title":"Catalytic self-assembled monolayers on Au nanoparticles: The source of catalysis of a transphosphorylation reaction","volume":"17","author":"Zaupa","year":"2011","journal-title":"Chemistry."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"4728","DOI":"10.1021\/acs.joc.6b00644","article-title":"Upper Rim Bifunctional cone-Calix[4]arenes Based on a Ligated Metal Ion and a Guanidinium Unit as DNAase and RNAase Mimics","volume":"81","author":"Salvio","year":"2016","journal-title":"J. Org. Chem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"5887","DOI":"10.1021\/acs.joc.5b00965","article-title":"Ribonuclease Activity of an Artificial Catalyst that Combines a Ligated Cu(II) Ion and a Guanidinium Group at the Upper Rim of a cone-Calix[4]arene Platform","volume":"80","author":"Salvio","year":"2015","journal-title":"J. Org. Chem."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"2104","DOI":"10.1002\/anie.201309747","article-title":"Zn2+-regulated self-sorting and mixing of phosphates and carboxylates on the surface of functionalized gold nanoparticles","volume":"53","author":"Pezzato","year":"2014","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"5375","DOI":"10.1002\/ejoc.201800300","article-title":"Distance between Metal Centres Affects Catalytic Efficiency of Dinuclear CoIII Complexes in the Hydrolysis of a Phosphate Diester","volume":"2018","author":"Bencze","year":"2018","journal-title":"Eur J. Org. Chem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"2948","DOI":"10.1021\/ja9638770","article-title":"Highly Efficient Phosphate Diester Transesterification by a Calix[4 ]arene-Based Dinuclear Zinc(II) Catalyst","volume":"119","author":"Molenveld","year":"1997","journal-title":"J. Am. Chem. Soc."},{"key":"ref_37","doi-asserted-by":"crossref","first-page":"18","DOI":"10.1021\/jo00080a006","article-title":"Leaving group effect in the cleavage of picolinate esters catalyzed by hydroxy-functionalized metallomicelles","volume":"59","author":"Scrimin","year":"1994","journal-title":"J. Org. Chem."},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"92","DOI":"10.1016\/j.chempr.2017.05.016","article-title":"Nanoparticle-Based Receptors Mimic Protein-Ligand Recognition","volume":"3","author":"Riccardi","year":"2017","journal-title":"Chem."},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"6538","DOI":"10.1073\/pnas.0609144104","article-title":"A cationic host displaying positive cooperativity in water","volume":"104","author":"Hughes","year":"2007","journal-title":"Proc. Natl. Acad. Sci. USA"},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"9878","DOI":"10.1021\/ja046894v","article-title":"Guanidinium Groups Act as General-Acid Catalysts in Phosphoryl Transfer Reactions: A Two-Proton Inventory on a Model System","volume":"126","author":"Piatek","year":"2004","journal-title":"J. Am. Chem. Soc."},{"key":"ref_41","doi-asserted-by":"crossref","first-page":"7056","DOI":"10.1002\/anie.200602532","article-title":"Efficient phosphodiester binding and cleavage by a Zn(II) complex combining hydrogen-bonding interactions and double Lewis acid activation","volume":"45","author":"Feng","year":"2006","journal-title":"Angew. Chem. Int. Ed. Engl."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/24\/15\/2814\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T13:12:26Z","timestamp":1760188346000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/24\/15\/2814"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2019,8,1]]},"references-count":41,"journal-issue":{"issue":"15","published-online":{"date-parts":[[2019,8]]}},"alternative-id":["molecules24152814"],"URL":"https:\/\/doi.org\/10.3390\/molecules24152814","relation":{},"ISSN":["1420-3049"],"issn-type":[{"value":"1420-3049","type":"electronic"}],"subject":[],"published":{"date-parts":[[2019,8,1]]}}}