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The formation of NO from nitrate and nitrite<jats:italic>via<\/jats:italic>a reductive \u2018nitrate\u2013nitrite\u2013NO\u2019 pathway and resulting in vasodilation is now an established complementary route to traditional NOS\u2010derived vasodilation. Nitrate, found in our diet and abundant in mammalian tissues and circulation, is activated<jats:italic>via<\/jats:italic>reduction to nitrite predominantly by our commensal oral microbiome. The subsequent<jats:italic>in vivo<\/jats:italic>reduction of nitrite, a stable vascular reserve of NO, is facilitated by a number of haem\u2010containing and molybdenum\u2010cofactor proteins. NO generation from nitrite is enhanced during physiological and pathological hypoxia and in disease states involving ischaemia\u2013reperfusion injury. As such, modulation of these NO vascular repositories<jats:italic>via<\/jats:italic>exogenously supplied nitrite and nitrate has been evaluated as a therapeutic approach in a number of diseases. Ultimately, the chemical biology of nitrate and nitrite is governed by local concentrations, reaction equilibrium constants, and the generation of transient intermediates, with kinetic rate constants modulated at differing physiological pH values and oxygen tensions.<\/jats:p><\/jats:sec><jats:sec><jats:title>Linked Articles<\/jats:title><jats:p>This article is part of a themed section on Nitric Oxide 20 Years from the 1998 Nobel Prize. To view the other articles in this section visit<jats:ext-link xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"http:\/\/onlinelibrary.wiley.com\/doi\/10.1111\/bph.v176.2\/issuetoc\">http:\/\/onlinelibrary.wiley.com\/doi\/10.1111\/bph.v176.2\/issuetoc<\/jats:ext-link><\/jats:p><\/jats:sec>","DOI":"10.1111\/bph.14484","type":"journal-article","created":{"date-parts":[[2018,8,29]],"date-time":"2018-08-29T18:01:18Z","timestamp":1535565678000},"page":"228-245","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":139,"title":["Nitrite and nitrate chemical biology and signalling"],"prefix":"10.1111","volume":"176","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-5303-5758","authenticated-orcid":false,"given":"Anthony W","family":"DeMartino","sequence":"first","affiliation":[{"name":"Heart, Lung, Blood, and Vascular Medicine Institute University of Pittsburgh Pittsburgh PA 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