{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,8]],"date-time":"2026-04-08T18:05:22Z","timestamp":1775671522646,"version":"3.50.1"},"reference-count":107,"publisher":"MDPI AG","issue":"14","license":[{"start":{"date-parts":[[2025,7,18]],"date-time":"2025-07-18T00:00:00Z","timestamp":1752796800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"name":"DST-SERB for the CRG","award":["CRG\/2022\/005673"],"award-info":[{"award-number":["CRG\/2022\/005673"]}]},{"name":"DST-SERB for the CRG","award":["UIDB\/50006\/2020"],"award-info":[{"award-number":["UIDB\/50006\/2020"]}]},{"name":"DST-SERB for the CRG","award":["UIDP\/50006\/2020"],"award-info":[{"award-number":["UIDP\/50006\/2020"]}]},{"name":"PTDC\/BTA-BTA\/0935\/2020 project","award":["CRG\/2022\/005673"],"award-info":[{"award-number":["CRG\/2022\/005673"]}]},{"name":"PTDC\/BTA-BTA\/0935\/2020 project","award":["UIDB\/50006\/2020"],"award-info":[{"award-number":["UIDB\/50006\/2020"]}]},{"name":"PTDC\/BTA-BTA\/0935\/2020 project","award":["UIDP\/50006\/2020"],"award-info":[{"award-number":["UIDP\/50006\/2020"]}]},{"name":"Associate Laboratory for Green Chemistry\u2014LAQV","award":["CRG\/2022\/005673"],"award-info":[{"award-number":["CRG\/2022\/005673"]}]},{"name":"Associate Laboratory for Green Chemistry\u2014LAQV","award":["UIDB\/50006\/2020"],"award-info":[{"award-number":["UIDB\/50006\/2020"]}]},{"name":"Associate Laboratory for Green Chemistry\u2014LAQV","award":["UIDP\/50006\/2020"],"award-info":[{"award-number":["UIDP\/50006\/2020"]}]},{"name":"Fundac\u00e3o para a Ci\u00eancia e a Tecnologia, MCTES (FCT\/MCTES)","award":["CRG\/2022\/005673"],"award-info":[{"award-number":["CRG\/2022\/005673"]}]},{"name":"Fundac\u00e3o para a Ci\u00eancia e a Tecnologia, MCTES (FCT\/MCTES)","award":["UIDB\/50006\/2020"],"award-info":[{"award-number":["UIDB\/50006\/2020"]}]},{"name":"Fundac\u00e3o para a Ci\u00eancia e a Tecnologia, MCTES (FCT\/MCTES)","award":["UIDP\/50006\/2020"],"award-info":[{"award-number":["UIDP\/50006\/2020"]}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>The nitrogen cycle (N-cycle) is a cornerstone of global biogeochemistry, regulating nitrogen availability and affecting atmospheric chemistry, agricultural productivity, and ecological balance. Central to this cycle is the reversible interplay between nitrate (NO3\u2212) and nitrite (NO2\u2212), mediated by molybdenum-dependent enzymes\u2014Nitrate reductases (NARs) and Nitrite oxidoreductases (NXRs). Despite catalyzing opposite reactions, these enzymes exhibit remarkable structural and mechanistic similarities. This review aims to elucidate the molecular underpinnings of nitrate reduction and nitrite oxidation by dissecting their enzymatic architectures, redox mechanisms, and evolutionary relationships. By focusing on recent structural, spectroscopic, and thermodynamic data, we explore how these two enzyme families represent \u201ctwo sides of the same coin\u201d in microbial nitrogen metabolism. Special emphasis is placed on the role of oxygen atom transfer (OAT) as a unifying mechanistic principle, the influence of environmental redox conditions, and the emerging evidence of bidirectional catalytic potential. Understanding this dynamic enzymatic interconversion provides insight into the flexibility and resilience of nitrogen-transforming pathways, with implications for environmental management, biotechnology, and synthetic biology.<\/jats:p>","DOI":"10.3390\/molecules30143023","type":"journal-article","created":{"date-parts":[[2025,7,18]],"date-time":"2025-07-18T12:09:53Z","timestamp":1752840593000},"page":"3023","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Nitrate\u2013Nitrite Interplay in the Nitrogen Biocycle"],"prefix":"10.3390","volume":"30","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0985-0031","authenticated-orcid":false,"given":"Biplab K.","family":"Maiti","sequence":"first","affiliation":[{"name":"Department of Chemistry, School of Sciences, Cluster University of Jammu, Jammu 180001, India"}]},{"given":"Isabel","family":"Moura","sequence":"additional","affiliation":[{"name":"LAQV, NOVA School of Sciences and Technology, Campus de Caparica, 2829-516 Caparica, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4726-2388","authenticated-orcid":false,"given":"Jos\u00e9 J. G.","family":"Moura","sequence":"additional","affiliation":[{"name":"LAQV, NOVA School of Sciences and Technology, Campus de Caparica, 2829-516 Caparica, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2025,7,18]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"401","DOI":"10.1038\/s41579-022-00687-z","article-title":"The Marine Nitrogen Cycle: New Developments and Global Change","volume":"20","author":"Hutchins","year":"2022","journal-title":"Nat. Rev. Microbiol."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"116959","DOI":"10.1016\/j.jenvman.2022.116959","article-title":"A Critical Review of the Central Role of Microbial Regulation in the Nitrogen Biogeochemical Process: New Insights for Controlling Groundwater Nitrogen Contamination","volume":"328","author":"Liu","year":"2023","journal-title":"J. Environ. 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