{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T12:31:01Z","timestamp":1791981061063,"version":"4.4.0"},"reference-count":78,"publisher":"American Chemical Society (ACS)","issue":"8","license":[{"start":{"date-parts":[[2023,2,16]],"date-time":"2023-02-16T00:00:00Z","timestamp":1676505600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2023,2,16]],"date-time":"2023-02-16T00:00:00Z","timestamp":1676505600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2023,2,16]],"date-time":"2023-02-16T00:00:00Z","timestamp":1676505600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["42192500"],"award-info":[{"award-number":["42192500"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["42192503"],"award-info":[{"award-number":["42192503"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2023,2,28]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The dual roles of minerals in inhibiting and prolonging extracellular enzyme activity in soils and sediments are governed by enzyme adsorption to mineral surfaces. Oxygenation of mineral-bound Fe\u00ad(II) generates reactive oxygen species (ROS), yet it is unknown whether and how this process alters the activity and functional lifespan of extracellular enzymes. Here, the effect of mineral-bound Fe\u00ad(II) oxidation on the hydrolytic activity of a cellulose-degrading enzyme \u03b2-glucosidase (BG) was studied using two pre-reduced Fe-bearing clay minerals (nontronite and montmorillonite) and one pre-reduced iron oxide (magnetite) at pH 5 and 7. Under anoxic conditions, BG adsorption to mineral surfaces decreased its activity but prolonged its lifespan. Under oxic conditions, ROS was produced, with the amount of \u2022OH, the most abundant ROS, being positively correlated with the extent of structural Fe\u00ad(II) oxidation in reduced minerals. \u2022OH decreased BG activity and shortened its lifespan via conformational change and structural decomposition of BG. These results suggest that under oxic conditions, the ROS-induced inhibitory role of Fe\u00ad(II)-bearing minerals outweighed their adsorption-induced protective role in controlling enzyme activity. These results disclose a previously unknown mechanism of extracellular enzyme inactivation, which have pivotal implications for predicting the active enzyme pool in redox-oscillating environments.<\/jats:p>","DOI":"10.1021\/acs.est.2c09634","type":"journal-article","created":{"date-parts":[[2023,2,16]],"date-time":"2023-02-16T11:50:15Z","timestamp":1676548215000},"page":"3425-3433","source":"Crossref","is-referenced-by-count":86,"title":["Inhibition of Extracellular\nEnzyme Activity by Reactive\nOxygen Species upon Oxygenation of Reduced Iron-Bearing Minerals"],"prefix":"10.1021","volume":"57","author":[{"given":"Yizhi","family":"Sheng","sequence":"first","affiliation":[{"name":"China University of Geosciences , , ,","place":["Beijing, China, 100083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jinglong","family":"Hu","sequence":"additional","affiliation":[{"name":"China University of Geosciences , , ,","place":["Beijing, China, 100083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ravi","family":"Kukkadapu","sequence":"additional","affiliation":[{"name":"Pacific Northwest National Laboratory , , , ,","place":["Richland, Washington, United States, 99352"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Dongyi","family":"Guo","sequence":"additional","affiliation":[{"name":"China University of Geosciences , , ,","place":["Beijing, China, 100083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7766-3588","authenticated-orcid":true,"given":"Qiang","family":"Zeng","sequence":"additional","affiliation":[{"name":"China University of Geosciences , , ,","place":["Beijing, China, 100083"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7468-1350","authenticated-orcid":true,"given":"Hailiang","family":"Dong","sequence":"additional","affiliation":[{"name":"China University of Geosciences , , ,","place":["Beijing, China, 100083"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2023,2,16]]},"reference":[{"key":"2026081411135114200_cit1","doi-asserted-by":"publisher","first-page":"626","DOI":"10.1111\/j.1461-0248.2005.00756.x","article-title":"Cheaters,\ndiffusion and nutrients constrain decomposition by microbial enzymes\nin spatially structured environments","volume":"8","author":"Allison","year":"2005","journal-title":"Ecol.\nLett."},{"key":"2026081411135114200_cit2","doi-asserted-by":"publisher","first-page":"216","DOI":"10.1016\/j.soilbio.2012.11.009","article-title":"Soil enzymes in a changing environment:\nCurrent knowledge\nand future directions","volume":"58","author":"Burns","year":"2013","journal-title":"Soil Biol. 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Ecol."},{"key":"2026081411135114200_cit13","doi-asserted-by":"publisher","DOI":"10.1016\/j.scitotenv.2020.139744","article-title":"Meta-analysis of heavy\nmetal effects on soil enzyme activities","volume":"737","author":"Aponte","year":"2020","journal-title":"Sci.\nTotal Environ."},{"key":"2026081411135114200_cit14","doi-asserted-by":"publisher","first-page":"257","DOI":"10.1007\/s10311-014-0458-2","article-title":"Effects of\npesticides on soil enzymes: a review","volume":"12","author":"Riah","year":"2014","journal-title":"Environ.\nChem. 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Lett."},{"key":"2026081411135114200_cit18","doi-asserted-by":"publisher","first-page":"402","DOI":"10.1038\/s43017-021-00162-y","article-title":"Dynamic interactions at the mineral\u2013organic\nmatter interface","volume":"2","author":"Kleber","year":"2021","journal-title":"Nat. Rev. Earth Environ."},{"key":"2026081411135114200_cit19","doi-asserted-by":"publisher","first-page":"3018","DOI":"10.1021\/acs.est.8b05583","article-title":"Mineral surfaces as\nagents of environmental proteolysis:\nmechanisms and controls","volume":"53","author":"Chacon","year":"2019","journal-title":"Environ. Sci. Technol."},{"key":"2026081411135114200_cit20","doi-asserted-by":"publisher","first-page":"651","DOI":"10.1038\/nrmicro.2016.93","article-title":"Extracellular electron transfer mechanisms\nbetween microorganisms and minerals","volume":"14","author":"Shi","year":"2016","journal-title":"Nat. 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Lett."},{"key":"2026081411135114200_cit30","doi-asserted-by":"publisher","first-page":"88","DOI":"10.1016\/j.jhazmat.2017.01.040","article-title":"Degradation\nof 1, 4-dioxane by hydroxyl radicals produced from clay minerals","volume":"331","author":"Zeng","year":"2017","journal-title":"J. Hazard. Mater."},{"key":"2026081411135114200_cit31","doi-asserted-by":"publisher","first-page":"7639","DOI":"10.1021\/acs.est.7b00726","article-title":"Reduced iron-containing\nclay minerals as antibacterial\nagents","volume":"51","author":"Wang","year":"2017","journal-title":"Environ. Sci. Technol."},{"key":"2026081411135114200_cit32","doi-asserted-by":"publisher","first-page":"422","DOI":"10.1016\/j.gca.2017.12.025","article-title":"Mechanisms\nof electron transfer from structrual Fe\u00ad(II) in reduced nontronite\nto oxygen for production of hydroxyl radicals","volume":"223","author":"Yuan","year":"2018","journal-title":"Geochim. Cosmochim. Acta"},{"key":"2026081411135114200_cit33","doi-asserted-by":"publisher","DOI":"10.1016\/j.earscirev.2021.103525","article-title":"Fenton chemistry and\nreactive oxygen species in soil:\nAbiotic mechanisms of biotic processes, controls and consequences\nfor carbon and nutrient cycling","volume":"214","author":"Yu","year":"2021","journal-title":"Earth-Sci.\nRev."},{"key":"2026081411135114200_cit34","doi-asserted-by":"publisher","first-page":"5207","DOI":"10.1021\/acs.est.9b07185","article-title":"Mechanisms of enhanced\nantibacterial\nactivity by reduced chitosan-intercalated nontronite","volume":"54","author":"Xia","year":"2020","journal-title":"Environ. Sci. Technol."},{"key":"2026081411135114200_cit35","doi-asserted-by":"publisher","first-page":"15256","DOI":"10.1021\/acs.est.1c04367","article-title":"Antibacterial Mechanisms\nof Reduced Iron-Containing Smectite\u2013Illite Clay Minerals","volume":"55","author":"Guo","year":"2021","journal-title":"Environ. Sci. Technol."},{"key":"2026081411135114200_cit36","doi-asserted-by":"publisher","first-page":"1007","DOI":"10.1016\/j.scitotenv.2018.05.241","article-title":"Impact of Fe (II) oxidation in the presence of iron-reducing bacteria\non subsequent Fe (III) bio-reduction","volume":"639","author":"Chen","year":"2018","journal-title":"Sci. Total\nEnviron."},{"key":"2026081411135114200_cit37","doi-asserted-by":"publisher","first-page":"119","DOI":"10.1007\/s00775-003-0519-7","article-title":"Discovery\nof superoxide reductase: an historical perspective","volume":"9","author":"Nivie\u0300re","year":"2004","journal-title":"JBIC, J. Biol. Inorg. Chem."},{"key":"2026081411135114200_cit38","doi-asserted-by":"publisher","DOI":"10.1016\/j.scitotenv.2020.143397","article-title":"Contribution of the Fenton reaction\nand ligninolytic\nenzymes to soil organic matter mineralisation under anoxic conditions","volume":"760","author":"Merino","year":"2021","journal-title":"Sci. Total Environ."},{"key":"2026081411135114200_cit39","doi-asserted-by":"publisher","first-page":"2804","DOI":"10.1111\/gcb.12229","article-title":"Iron oxidation stimulates\norganic matter decomposition\nin humid tropical forest soils","volume":"19","author":"Hall","year":"2013","journal-title":"Global Change\nBiol."},{"key":"2026081411135114200_cit40","doi-asserted-by":"publisher","first-page":"69","DOI":"10.1007\/s10533-005-2053-x","article-title":"Ferrous iron stimulates phenol oxidase activity and organic matter\ndecomposition in waterlogged wetlands","volume":"76","author":"Van\nBodegom","year":"2005","journal-title":"Biogeochemistry"},{"key":"2026081411135114200_cit41","doi-asserted-by":"publisher","first-page":"7671","DOI":"10.1021\/acs.est.7b06439","article-title":"Proteomics approach\nto trace site-specific damage in\naquatic extracellular enzymes during photoinactivation","volume":"52","author":"Egli","year":"2018","journal-title":"Environ. Sci. Technol."},{"key":"2026081411135114200_cit42","doi-asserted-by":"publisher","first-page":"14403","DOI":"10.1021\/acs.est.0c04696","article-title":"Inactivation and site-specific oxidation\nof aquatic extracellular bacterial leucine aminopeptidase by singlet\noxygen","volume":"54","author":"Egli","year":"2020","journal-title":"Environ. Sci. Technol."},{"key":"2026081411135114200_cit43","doi-asserted-by":"publisher","first-page":"322","DOI":"10.1016\/j.ecolind.2011.06.031","article-title":"\u03b2-Glucosidase kinetic parameters as indicators of soil quality\nunder conventional and organic cropping systems applying two analytical\napproaches","volume":"13","author":"Moscatelli","year":"2012","journal-title":"Ecol. Indic."},{"key":"2026081411135114200_cit44","doi-asserted-by":"publisher","first-page":"101","DOI":"10.1016\/j.soilbio.2018.01.020","article-title":"Differential\ncapacity of kaolinite and birnessite to protect surface associated\nproteins against thermal degradation","volume":"119","author":"Chacon","year":"2018","journal-title":"Soil Biol.\nBiochem."},{"key":"2026081411135114200_cit45","doi-asserted-by":"publisher","first-page":"1537","DOI":"10.1016\/S0038-0717(97)00231-9","article-title":"Biochemistry,\nThe effect of copper on the activity of cellulase and \u03b2-glucosidase\nin the presence of montmorillonite or Al-montmorillonite","volume":"30","author":"Geiger","year":"1998","journal-title":"Soil Biol. Biochem."},{"key":"2026081411135114200_cit46","doi-asserted-by":"publisher","first-page":"157","DOI":"10.1016\/S0929-1393(02)00020-3","article-title":"beta-glucosidase activity\nin pasture soils","volume":"20","author":"Turner","year":"2002","journal-title":"Appl. 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Biochem."},{"key":"2026081411135114200_cit53","doi-asserted-by":"publisher","first-page":"331","DOI":"10.1023\/B:AECO.0000007044.52801.6b","article-title":"Extracellular enzyme-clay mineral\ncomplexes: Enzyme\nadsorption, alteration of enzyme activity, and protection from photodegradation","volume":"37","author":"Tietjen","year":"2003","journal-title":"Aquat. Ecol."},{"key":"2026081411135114200_cit54","doi-asserted-by":"publisher","first-page":"1194","DOI":"10.1016\/j.scitotenv.2019.05.479","article-title":"Temperature sensitivity\nof mineral-enzyme\ninteractions on the hydrolysis of cellobiose and indican by beta-glucosidase","volume":"686","author":"Yang","year":"2019","journal-title":"Sci. Total Environ."},{"key":"2026081411135114200_cit55","doi-asserted-by":"publisher","DOI":"10.1016\/j.colsurfb.2020.111115","article-title":"Adsorption\nkinetics, conformational change, and enzymatic activity of beta-glucosidase\non hematite (alpha-Fe2O3) surfaces","volume":"193","author":"Zang","year":"2020","journal-title":"Colloids Surf., B"},{"key":"2026081411135114200_cit56","doi-asserted-by":"publisher","first-page":"240","DOI":"10.1016\/j.soilbio.2017.12.020","article-title":"Cross-laboratory\ncomparison of fluorimetric\nmicroplate and colorimetric bench-scale soil enzyme assays","volume":"121","author":"Dick","year":"2018","journal-title":"Soil Biol. Biochem."},{"key":"2026081411135114200_cit57","doi-asserted-by":"publisher","first-page":"S125","DOI":"10.2136\/sssaj2013.08.0349nafsc","article-title":"Regional\nassessment of soil microbial\nfunctional diversity of Douglas-fir forests","volume":"78","author":"McGinnis","year":"2014","journal-title":"Soil Sci. Soc. Am. 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