{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T01:47:46Z","timestamp":1791251266875,"version":"4.1.0"},"reference-count":46,"publisher":"Wiley","issue":"10","license":[{"start":{"date-parts":[[2008,4,17]],"date-time":"2008-04-17T00:00:00Z","timestamp":1208390400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Rapid Comm Mass Spectrometry"],"published-print":{"date-parts":[[2008,5,30]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    Nicotianamine (NA) is considered as a key element in plant metal homeostasis. This non\u2010proteinogenic amino acid has an optimal structure for chelation of metal ions, with six functional groups that allow octahedral coordination. The ability to chelate metals by NA is largely dependent on the pK of the resulting complex and the pH of the solution, with most metals being chelated at neutral or basic pH values.\n                    <jats:italic>In silico<\/jats:italic>\n                    calculations using pKa and pK values have predicted the occurrence of metal\u2010NA complexes in plant fluids, but the use of soft ionization techniques (e.g. electrospray), together with high\u2010resolution mass spectrometers (e.g. time\u2010of\u2010flight mass detector), can offer direct and metal\u2010specific information on the speciation of NA in solution. We have used direct infusion electrospray ionization mass spectrometry (time\u2010of\u2010flight) ESI\u2010MS(TOF) to study the complexation of Mn, Fe(II), Fe(III), Ni, Cu by NA. The pH dependence of the metal\u2010NA complexes in ESI\u2010MS was compared to that predicted\n                    <jats:italic>in silico<\/jats:italic>\n                    . Possible exchange reactions that may occur between Fe\u2010NA and other metal micronutrients as Zn and Cu, as well as between Fe\u2010NA and citrate, another possible Fe ligand candidate in plants, were studied at pH 5.5 and 7.5, values typical of the plant xylem and phloem saps. Metal\u2010NA complexes were generally observed in the ESI\u2010MS experiments at a pH value approximately 1\u20132 units lower than that predicted\n                    <jats:italic>in silico<\/jats:italic>\n                    , and this difference could be only partially explained by the estimated error, approximately 0.3 pH units, associated with measuring pH in organic solvent\u2010containing solutions. Iron\u2010NA complexes are less likely to participate in ligand\u2010 and metal\u2010exchange reactions at pH 7.5 than at pH 5.5. Results support that NA may be the ligand chelating Fe at pH values usually found in phloem sap, whereas in the xylem sap NA is not likely to be involved in Fe transport, conversely to what occurs with other metals such as Cu and Ni. Some considerations that need to be addressed when studying metal complexes in plant compartments by ESI\u2010MS are also discussed. Copyright \u00a9 2008 John Wiley &amp; Sons, Ltd.\n                  <\/jats:p>","DOI":"10.1002\/rcm.3523","type":"journal-article","created":{"date-parts":[[2008,4,17]],"date-time":"2008-04-17T12:49:05Z","timestamp":1208436545000},"page":"1553-1562","source":"Crossref","is-referenced-by-count":125,"title":["Formation of metal\u2010nicotianamine complexes as affected by pH, ligand exchange with citrate and metal exchange. A study by electrospray ionization time\u2010of\u2010flight mass spectrometry"],"prefix":"10.1002","volume":"22","author":[{"given":"Rub\u00e9n","family":"Rell\u00e1n\u2010\u00c1lvarez","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Javier","family":"Abad\u00eda","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ana","family":"\u00c1lvarez\u2010Fern\u00e1ndez","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2008,4,17]]},"reference":[{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1093\/jexbot\/53.366.1"},{"key":"e_1_2_7_3_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)96769-3"},{"key":"e_1_2_7_4_2","doi-asserted-by":"publisher","DOI":"10.1104\/pp.119.3.1107"},{"key":"e_1_2_7_5_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF01955293"},{"key":"e_1_2_7_6_2","doi-asserted-by":"publisher","DOI":"10.1111\/j.1399-3054.1993.tb01367.x"},{"key":"e_1_2_7_7_2","doi-asserted-by":"publisher","DOI":"10.1039\/C39890000647"},{"key":"e_1_2_7_8_2","doi-asserted-by":"publisher","DOI":"10.1007\/s00425\u2010002\u20100920\u20104"},{"key":"e_1_2_7_9_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF00188095"},{"key":"e_1_2_7_10_2","doi-asserted-by":"publisher","DOI":"10.1080\/01904169209364428"},{"key":"e_1_2_7_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0176-1617(11)80226-9"},{"key":"e_1_2_7_12_2","doi-asserted-by":"publisher","DOI":"10.1104\/pp.111.2.533"},{"key":"e_1_2_7_13_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF01287417"},{"key":"e_1_2_7_14_2","doi-asserted-by":"publisher","DOI":"10.1105\/tpc.010256"},{"key":"e_1_2_7_15_2","doi-asserted-by":"publisher","DOI":"10.1007\/BF00008061"},{"key":"e_1_2_7_16_2","doi-asserted-by":"publisher","DOI":"10.1104\/pp.41.3.510"},{"key":"e_1_2_7_17_2","doi-asserted-by":"publisher","DOI":"10.1104\/pp.124.2.873"},{"key":"e_1_2_7_18_2","doi-asserted-by":"publisher","DOI":"10.1104\/pp.107.097162"},{"key":"e_1_2_7_19_2","doi-asserted-by":"publisher","DOI":"10.1034\/j.1399-3054.1999.106112.x"},{"key":"e_1_2_7_20_2","doi-asserted-by":"publisher","DOI":"10.1074\/jbc.M201896200"},{"key":"e_1_2_7_21_2","doi-asserted-by":"publisher","DOI":"10.1104\/pp.87.1.167"},{"key":"e_1_2_7_22_2","doi-asserted-by":"publisher","DOI":"10.1046\/j.1432-1327.1999.00717.x"},{"key":"e_1_2_7_23_2","doi-asserted-by":"publisher","DOI":"10.1104\/pp.119.2.471"},{"key":"e_1_2_7_24_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.96.12.7098"},{"key":"e_1_2_7_25_2","doi-asserted-by":"publisher","DOI":"10.1111\/j.1365\u2010313X.2004.02146.x"},{"key":"e_1_2_7_26_2","doi-asserted-by":"publisher","DOI":"10.1104\/pp.103.037572"},{"key":"e_1_2_7_27_2","doi-asserted-by":"publisher","DOI":"10.1093\/pcp\/pci081"},{"key":"e_1_2_7_28_2","doi-asserted-by":"publisher","DOI":"10.1093\/jxb\/47.1.41"},{"key":"e_1_2_7_29_2","doi-asserted-by":"publisher","DOI":"10.1021\/ac020704m"},{"key":"e_1_2_7_30_2","doi-asserted-by":"publisher","DOI":"10.1046\/j.1365\u2010313X.2003.01960.x"},{"key":"e_1_2_7_31_2","doi-asserted-by":"publisher","DOI":"10.1093\/pcp\/pci196"},{"key":"e_1_2_7_32_2","doi-asserted-by":"publisher","DOI":"10.1111\/j.1365-3040.2005.01273.x"},{"key":"e_1_2_7_33_2","doi-asserted-by":"publisher","DOI":"10.1007\/s11248\u2010005\u20107159\u20103"},{"key":"e_1_2_7_34_2","doi-asserted-by":"publisher","DOI":"10.1111\/j.1469\u20108137.2004.01209.x"},{"key":"e_1_2_7_35_2","doi-asserted-by":"publisher","DOI":"10.1039\/b602689c"},{"key":"e_1_2_7_36_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.chroma.2006.09.060"},{"key":"e_1_2_7_37_2","doi-asserted-by":"publisher","DOI":"10.1002\/rcm.2402"},{"key":"e_1_2_7_38_2","volume-title":"Critical 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