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Synthesis, characterization, and evaluation of bioactivity of novel Fe(II) nano-complexes based on sucrose, glucose, and fructose

Abstract

Novel saccharide/Fe(II) complexes, sucrose/Fe(II) (1), glucose/Fe(II) (2), and fructose/Fe(II) (3) were synthesized. XRD, FTIR, NMR, TEM, XPS, UV–vis and DSC were applied for characterization. The amorphous complex is confirmed as nanoscale. It shows that the complex has ultraviolet absorption characteristics and high stability in acid and weak alkaline environments. The exothermic property at high temperature implies that it could be kept and used in normal environment. An analysis of in vitro bioactivity on apple dwarfing rootstock G. 935 reveals that complex 1 is able to provide iron for plantlets. Compared with EDTA/Fe(II), complex 1 has higher uptake efficiency and harmlessness in tissue culture. The above results suggest that the saccharide-based Fe(II) nano-complex could be applied for plant growth as iron source.

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References

  1. Abadía J, Álvarez-Fernandez A, Rombolá AD, Sanz M, Tagliavini M, Abadía A (2004) Technologies for the diagnosis and remediation of Fe deficiency. Soil Sci Plant Nutr 50:965–971. https://doi.org/10.1080/00380768.2004.10408562

    Article  Google Scholar 

  2. Allen KN, Lavie A, Petsko GA, Ringe D (1995) Design, synthesis, and characterization of a potent xylose isomerase inhibitor, D-threonohydroxamic acid, and high-resolution X-ray crystallographic structure of the enzyme-inhibitor complex. Biochemistry 34:3742–3749. https://doi.org/10.1021/bi00011a032

    Article  CAS  PubMed  Google Scholar 

  3. Álvarez-Fernández A, García-Marco S, Lucena JJ (2005) Evaluation of synthetic iron(III)-chelates (EDDHA/Fe3+, EDDHMA/Fe3+ and the novel EDDHSA/Fe3+) to correct iron chlorosis. Eur J Agron 22:119–130. https://doi.org/10.1016/j.eja.2004.02.001

    Article  CAS  Google Scholar 

  4. Araki K, Shiraishi S (1986) Catalytic action of iron and manganese ions in the photochemically-induced oxidation of d-fructose with atmospheric oxygen. Bull Gem Soc Jpn 59:229–234. https://doi.org/10.1246/bcsj.59.229

    Article  CAS  Google Scholar 

  5. Araki K, Sakuma M, Shiraishi S (1983) Photooxidation of d-fructose with iron (III) chloride under aerobic conditon. Chem Lett 12:665–666. https://doi.org/10.1246/cl.1983.665

    Article  Google Scholar 

  6. Bandwar RP, Giralt M, Hidalgo J, Rao CP (1996) Metal-saccharide chemistry and biology: saccharide complexes of zinc and their effect on metallothionein synthesis in mice. Carbohyd Res 284:73–84. https://doi.org/10.1016/0008-6215(96)00009-2

    Article  CAS  Google Scholar 

  7. Bera M, Patra A (2011) New dinuclear copper(II) and zinc(II) complexes for the investigation of sugar-metal ion interactions. Carbohyd Res 346:2075–2083. https://doi.org/10.1016/j.carres.2011.06.030

    Article  CAS  Google Scholar 

  8. Bin LM, Weng L, Bugter MH (2016) Effectiveness of FeEDDHA, FeEDDHMA, and FeHBED in preventing iron-deficiency chlorosis in soybean. J Agric Food Chem 64:8273–8281. https://doi.org/10.1021/acs.jafc.6b01382

    Article  CAS  PubMed  Google Scholar 

  9. Briat JF, Lobréaux S (1997) Iron transport and storage in plants. Trends Plant Sci 2:187–193. https://doi.org/10.1016/S1360-1385(97)01033-9

    Article  Google Scholar 

  10. Castillo A, Cabrera D, Rodríguez P, Zoppolo R, Robinson T (2015) In vitro micropropagation of CG41 apple rootstock. Acta Hort 1083:569–576. https://doi.org/10.17660/ActaHortic.2015.1083.76

    Article  Google Scholar 

  11. Chaney RL (1988) Plants can utilize iron form Fe-N, N′-di-(2-hydroxybenzoyl)-ethylenediamine-N, N′-diacetic acid, a ferric chelate with 106 greater formation constant than Fe-EDDHA. J Plant Nutr 11:1033–1050. https://doi.org/10.1080/01904168809363867

    Article  CAS  Google Scholar 

  12. Chaney RL, Brown JC, Tiffin LO (1972) Obligatory reduction of ferric chelates in iron uptake by soybeans. Plant Physiol 50:208–213. https://doi.org/10.1104/pp.50.2.208

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  13. Cieschi MT, Caballero-Molada M, Menéndez N, Naranjo MA, Lucena JJ (2017) Long-term effect of a leonardite iron humate improving Fe nutrition as revealed in silico, in vivo, and in field experiments. J Agric Food Chem 65:6554–6563. https://doi.org/10.1021/acs.jafc.7b01804

    Article  CAS  PubMed  Google Scholar 

  14. Enomoto Y, Hodoshima H, Shimada H, Shoji K, Yoshihara T, Goto F (2007) Long-distance signals positively regulate the expression of iron uptake genes in tobacco roots. Planta 227:81–89. https://doi.org/10.1007/s00425-007-0596-x

    Article  CAS  PubMed  Google Scholar 

  15. García-Marco S, Martínez N, Yunta F, Hernández-Apaolaza L, Lucena JJ (2006) Effectiveness of ethylenediamine-N(o-hydroxyphenylacetic)-N′(p-hydroxyphenylacetic) acid (o, p-EDDHA) to supply iron to plants. Plant Soil 279:31–40. https://doi.org/10.1007/s11104-005-8218-5

    Article  CAS  Google Scholar 

  16. Garrison W, Dale A, Saxena PK (2013) Improved shoot multiplication and development in hybrid hazelnut nodal cultures by ethylenediamine di-2-hydroxy-phenylacetic acid (Fe-EDDHA). Can J Plant Sci 93:511–521. https://doi.org/10.4141/cjps2012-218

    Article  CAS  Google Scholar 

  17. Giammanco GE, Sosnofsky CT, Ostrowski AD (2015) Light-responsive iron(III)-polysaccharide coordination hydrogels for controlled delivery. ACS Appl Mater Interfaces 7:3068–3076. https://doi.org/10.1021/am506772x

    Article  CAS  PubMed  Google Scholar 

  18. Grosvenor AP, Kobe BA, Biesinger BC, McIntyre NS (2004) Investigation of multiplet splitting of Fe 2p XPS spectra and bonding in iron compounds. Surf Interface Anal 36:1564–1574. https://doi.org/10.1002/sia.1984

    Article  CAS  Google Scholar 

  19. Hagstrom GR (1984) Current management practices for correcting iron deficiency in plants with emphasis on soil management. J Plant Nutr 7:23–46. https://doi.org/10.1080/01904168409363173

    Article  CAS  Google Scholar 

  20. Hu HJ, Xue JH, Wen XD, Li WH, Zhang C, Yang LM, Xu YZ, Zhao GZ, Bu XX, Liu KX, Chen JE, Wu JG (2013) Sugar-metal ion interactions: the complicated coordination structures of cesium ion with d-Ribose and myo-inositol. Inorg Chem 52:13132–13145. https://doi.org/10.1021/ic402027j

    Article  CAS  PubMed  Google Scholar 

  21. Hu B, Yu D, Huang K, Yu SJ (2015) Metal-ion interactions with sugars: crystal structure of bis(4-dehydro-l-arabinose) calcium methanol bishydrate. Chin J Struct Chem 34:764–770. https://doi.org/10.14102/j.cnki.0254-5861.2011-0517

    CAS  Article  Google Scholar 

  22. Jiang Y, Xue JH, Wen XD, Zhai YJ, Yang LM, Xu YZ, Zhao GZ, Kou K, Liu KX, Chen JE, Wu JG (2016) Sugar-metal ion interactions: the coordination behavior of cesium ion with lactose, d-arabinose and l-arabinose. J Mol Struct 1109:179–191. https://doi.org/10.1016/j.molstruc.2016.01.005

    Article  CAS  Google Scholar 

  23. Kane RC (2003) Intravenous iron replacement with sodium ferric gluconate complex in sucrose for iron deficiency anemia in adults. Curr Therapeutic Res 64:263–268. https://doi.org/10.1016/S0011-393X(03)00038-9

    Article  CAS  Google Scholar 

  24. Lu Y, Deng GC, Miao FM, Li ZM (2003) Sugar complexation with calcium ion. Crystal structure and FT-IR study of a hydrated calcium chloride complex of d-Ribose. J Inorg Biochem 96:487–492. https://doi.org/10.1016/S0162-0134(03)00251-4

    Article  CAS  PubMed  Google Scholar 

  25. Lucena JJ (2000) Effect of bicarbonate, nitrate and other environmental factors on iron deficiency chlorosis. A review. J Plant Nutr 23:1591–1606. https://doi.org/10.1080/01904160009382126

    Article  CAS  Google Scholar 

  26. Lucena JJ (2003) Fe chelates for remediation of Fe chlorosis in strategy I plants. J Plant Nutr 26:1969–1984. https://doi.org/10.1081/PLN-120024257

    Article  CAS  Google Scholar 

  27. McIntyre NS, Zetaruk DG (1977) X-ray photoelectron spectroscopic studies of iron oxides. Anal Chem 49:1521–1529. https://doi.org/10.1021/ac50019a016

    Article  CAS  Google Scholar 

  28. Molassiotis AN, Dimassi K, Therios I, Diamantidis G (2003) Fe-EDDHA promotes rooting of rootstock GF-677 (Prunus amygdalus × P. persica) explants in vitro. Biol Plant 47:141–144. https://doi.org/10.1023/A:1027309705022

    Article  CAS  Google Scholar 

  29. Mouhtaridou GN, Sotiropoulos TE, Dimassi KN, Therios IN (2004) Effects of boron on growth, and chlorophyll and mineral contents of shoots of the apple rootstock MM 106 cultured in vitro. Biol Plantarum 48:617–619. https://doi.org/10.1023/B:BIOP.0000047169.13304.67

    Article  CAS  Google Scholar 

  30. Osório J, Osório ML, Correia PJ, de Varennes A, Pestana M (2014) Chlorophyll fluorescence imaging as a tool to understand the impact of iron deficiency and resupply on photosynthetic performance of strawberry plants. Sci Hortic 165:148–155. https://doi.org/10.1016/j.scienta.2013.10.042

    Article  CAS  Google Scholar 

  31. Riley RG, Zachara JM (1992) Chemical contaminants on DOE lands and selection of contaminant mixtures for subsurface science research. United States. https://doi.org/10.2172/10147081. https://www.osti.gov/servlets/purl/10147081

  32. Robinson NJ, Procter CM, Connolly EL, Guerinot ML (1999) A ferric-chelate reductase for iron uptake from soils. Nature 397:694–697. https://doi.org/10.1038/17800

    Article  CAS  PubMed  Google Scholar 

  33. Santi S, Schmidt W (2009) Dissecting iron deficiency-induced proton extrusion in Arabidopsis roots. New Phytol 183:1072–1084. https://doi.org/10.1111/j.1469-8137.2009.02908.x

    Article  CAS  Google Scholar 

  34. Shenker M, Chen Y (2005) Increasing iron availability to crops: fertilizers, organo-fertilizers, and biological approaches. Soil Sci Plant Nutr 51:1–17. https://doi.org/10.1111/j.1747-0765.2005.tb00001.x

    Article  CAS  Google Scholar 

  35. Somsook E, Hinsin D, Buakhrong P, Teanchai R, Mophan N, Pohmakotr M, Shiowatana J (2005) Interactions between iron(III) and sucrose, dextran, or starch in complexes. Carbohyd Polym 61:281–287. https://doi.org/10.1016/j.carbpol.2005.04.019

    Article  CAS  Google Scholar 

  36. Sotiropoulos TE (2007) Effect of NaCl and CaCl2 on growth and contents of minerals, chlorophyll, proline and sugars in the apple rootstock M 4 cultured in vitro. Biol Plant 51:177–180. https://doi.org/10.1007/s10535-007-0035-7

    Article  CAS  Google Scholar 

  37. Sotiropoulos TE, Mouhtaridou GN, Thomidis T, Tsirakoglou V, Dimassi KN, Therios IN (2005) Effects of different N-sources on growth, nutritional status, chlorophyll content, and photosynthetic parameters of shoots of the apple rootstock MM 106 cultured in vitro. Biol Plant 49:297–299. https://doi.org/10.1007/s10535-005-7299-6

    Article  Google Scholar 

  38. Sotiropoulos TE, Molassiotis A, Almaliotis D, Mouhtaridou G, Dimassi K, Therios I, Diamantidis G (2006) Growth, nutritional status, chlorophyll content, and antioxidant responses of the apple rootstock MM 111 shoots cultured under high boron concentrations in vitro. J Plant Nut 29:575–583. https://doi.org/10.1080/01904160500526956

    Article  CAS  Google Scholar 

  39. Thomas P, Mythili JB, Shivashankara KS (2000) Effects of photo-oxidative loss of FeNa2EDTA and of higher iron supply on chlorophyll content, growth and propagation rate in triploid watermelon cultures. Cell Dev Biol Plant 36:537–542. https://doi.org/10.1007/s11627-000-0096-1

    Article  CAS  Google Scholar 

  40. Willett AI, Rittmann BE (2003) Slow complexation kinetics for ferric iron and EDTA complexes make EDTA non-biodegradable. Biodegradation 14:105–121. https://doi.org/10.1023/A:1024074329955

    Article  CAS  PubMed  Google Scholar 

  41. Yunta F, García-Marco S, Lucena JJ, Gómez-Gallego M, Alcaraz R, Sierra MA (2003) Chelating agents related to ethylenediamine bis(2-hydroxyphenyl) acetic acid (EDDHA): synthesis, characterization, and equilibrium studies of the free ligands and their Mg2+, Ca2+, Cu2+, and Fe3+ chelates. Inorg Chem 42:5412–5421. https://doi.org/10.1021/ic034333j

    Article  CAS  PubMed  Google Scholar 

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Correspondence to Qin-Ping Wei.

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Yang, YZ., Li, MJ., Zhou, BB. et al. Synthesis, characterization, and evaluation of bioactivity of novel Fe(II) nano-complexes based on sucrose, glucose, and fructose. Chem. Pap. 73, 321–329 (2019). https://doi.org/10.1007/s11696-018-0582-8

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Keywords

  • Fe(II) complex
  • Saccharide-based ligand
  • Nano-complex
  • Stability
  • Iron supply