NMR spectroscopy of Cu(II) complexes with acrylamide and sodium acrylate copolymer and ω-amino acids

  • Dmitry L. Kudryavsky Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieninhradskaja Street, Minsk 220006, Belarus https://orcid.org/0000-0002-0993-5721
  • Elena K. Fomina Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieninhradskaja Street, Minsk 220006, Belarus https://orcid.org/0000-0002-3895-274X
  • Lyudmila Yu. Tychinskaya Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, 13 Surhanava Street, Minsk 220072, Belarus
  • Evgeny D. Skakovsky Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, 13 Surhanava Street, Minsk 220072, Belarus https://orcid.org/0000-0003-0804-1010
  • Svetlana E. Bogushevich Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, 5 Akademika Kuprevicha Street, 2 building, Minsk 220141, Belarus https://orcid.org/0000-0003-0587-6960
DOI: https://doi.org/10.33581/2520-257X-2021-1-85-98

Abstract

Macromolecular complexes of acrylamide and sodium acrylate copolymer with microelements, including Cu(II), may form at preparation of crop protection and stimulation compositions, where the copolymer serves as an adhesive, water-retaining and film-forming agent. Preparations for crop production may also contain amino acids that protect plants under stressful conditions (cold, dry, etc.). Carboxylic groups of copolymer, carboxylic and amino groups of amino acids may be involved in mixed Cu(II) ions complexes formation. Number of methylene groups separating carboxylic and amino group of amino acids affects its ability to form a stable chelate cycle and, therefore, ligand composition of mixed Cu(II) ions complexes with acrylamide and sodium acrylate copolymer and amino acid. This work is aimed at determining the ligand composition of mixed macromolecular Cu(II) ion complexes with acrylamide and sodium acrylate copolymer and ω-amino acids (β-alanine, γ-aminobutyric acid, ε-aminocaproic acid). 13C and 1H NMR spectroscopy was used to clarify complexes composition. A complex where carboxylic groups of amino acids are ligands has been found to form in aqueous solutions of Cu(II) ions and ω-amino acid (β-alanine, γ-aminobutyric acid, ε-aminocaproic acid) at molar ratio of Cu(II) ions – amino acid equal to 1 : 6. A chelate complex where both carboxylic and amino groups of β-alanine are involved in coordination has been discovered to form in the solution containing Cu(II) ions, β-alanine, as well as acrylamide and sodium acrylate copolymer at molar ratio of Cu(II) – β-alanine – copolymer COO− equal to 1 : 6 : 30. Carboxylic groups of copolymer participate in complex formation as well. Carboxylic groups of both amino acids and the copolymer have been shown to participate in complex formation in aqueous solutions containing Cu(II) ions, either γ-aminobutyric or ε-aminokaproic acid and also acrylamide and sodium acrylate copolymer.

Author Biographies

Dmitry L. Kudryavsky, Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieninhradskaja Street, Minsk 220006, Belarus

junior researcher at the laboratory of structural and chemical modification of polymers

Elena K. Fomina, Research Institute for Physical Chemical Problems, Belarusian State University, 14 Lieninhradskaja Street, Minsk 220006, Belarus

PhD (chemistry); leading researcher at the laboratory of structural and chemical modification of polymers

Lyudmila Yu. Tychinskaya, Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, 13 Surhanava Street, Minsk 220072, Belarus

PhD (chemistry); leading researcher of the laboratory of physicochemical research methods

Evgeny D. Skakovsky, Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, 13 Surhanava Street, Minsk 220072, Belarus

PhD (chemistry), docent; leading researcher at the laboratory of physical and chemical research methods

Svetlana E. Bogushevich, Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, 5 Akademika Kuprevicha Street, 2 building, Minsk 220141, Belarus

PhD (chemistry); leading researcher of the laboratory of physicochemical research methods

References

  1. Wöhrle D, Pomogailo AD. Metal complexes and metals in macromolecules: synthesis, structure and properties. Weinheim: Wiley-VCH Verlag GmbH & Co. KGaA; 2003. 685 p. DOI: 10.1002/9783527610778.
  2. Li W, Zhao H, Teasdale PR, John R, Zhang S. Synthesis and characterisation of a polyacrylamide – polyacrylic acid copolymer hydrogel for environmental analysis of Cu and Cd. Reactive and Functional Polymers. 2002;52(1):31–41. DOI: 10.1016/S1381-5148(02)00055-X.
  3. Xie J, Liu X, Liang J. Absorbency and adsorption of poly(acrylic acid-co-acrylamide) hydrogel. Journal of Applied Polymer Science. 2007;106(3):1606–1613. DOI: 10.1002/app.26666.
  4. Çavus S, Gürdag G, Sözgen K, Gürkaynak M. The preparation and characterization of poly(acrylic acid-co-methacrylamide) gel and its use in the non‐competitive heavy metal removal. Polymers for Advanced Technologies. 2009;20(3, special issue):165–172. DOI: 10.1002/pat.1248.
  5. Thomas A, Gaillard N, Favero C. Some key features to consider when studying acrylamide-based polymers for chemical enhanced oil recovery. Oil & Gas Science and Technology – Revue IFP Energies nouvelles. 2012;67(6):887−902. DOI: 10.2516/ogst2012065.
  6. Sojka RE, Bjorneberg DL, Entry JA, Lentz RD, Orts WJ. Polyacrylamide in agriculture and environmental land management. Advances in Agronomy. 2007;92:75–162. DOI: 10.1016/S0065-2113(04)92002-0.
  7. Fomina EK, Krul’ LP, Grinyuk EV. [Phase state of aqueous solutions of acrylamide-sodium acrylate copolymers in the presence of copper, zinc, and manganese ions]. Zhurnal prikladnoi khimii. 2015:88(9):1359–1363. Russian.
  8. Fomina EK, Grinyuk EV, Butovskaya GV, Krul’ LP. [Macromolecular complexes of microelements with acrylamide and sodium acrylate copolymer]. Sviridov readings. 2017;13:294–314. Russian.
  9. Tsivion Y, inventor; Tsivion Y, assignee. Plant feed solutions comprising nutritive metals. United Kingdom patent GB 2411896A. 2005 September 14.
  10. López-Rayo S, Nadal P, Lucena JJ. Novel chelating agents for iron, manganese, zinc, and copper mixed fertilisation in high pH soil-less cultures. Journal of the Science of Food and Agriculture. 2016;96(4):1111–1120. DOI: 10.1002/jsfa.7183.
  11. Popko M, Michalak I, Wilk R, Gramza M, Chojnacka K, Górecki H. Effect of the new plant growth biostimulants based on amino acids on yield and grain quality of winter wheat. Molecules. 2018:23(2):470. DOI: 10.3390/molecules23020470.
  12. Ertani A, Cavani L, Pizzeghello D, Brandellero E, Altissimo A, Ciavatta C, et al. Biostimulant activity of two protein hydrolyzates in the growth and nitrogen metabolism of maize seedlings. Journal of Plant Nutrition and Soil Science. 2009;172(2):237–244. DOI: 10.1002/jpln.200800174.
  13. Beck W. Metal complexes of biologically important ligands, CLXXII [1]. Metal ions and metal complexes as protective groups of amino acids and peptides – reactions at coordinated amino acids. Zeitschrift für Naturforschung B: A Journal of Chemical Sciences. 2014;64(11–12):1221–1245. DOI: 10.1515/znb-2009-11-1202.
  14. Kudryavsky DL, Fomina EK, Butovskaya GV, Grinyuk EV, Tychinskaya LYu, Skakovsky ED. Macromolecular mixed complexes of copper(II) with glycine and copolymer of acrylamide and sodium acrylate. Polymer Materials and Technologies. 2019;5(4): 21–32. DOI: 10.32864/polymmattech-2019-5-4-21-32. Russian.
  15. Wu G. Amino acids: biochemistry and nutrition. Boca Raton: CRC Press, 2013. 503 p. DOI: 10.1201/b14661.
  16. Ihs A, Liedberg B, Uvdal K, Törnkvist C, Bodö P, Lundström I. Infrared and photoelectron spectroscopy of amino acids on copper: Glycine, L-alanine and β-alanine. Journal of Colloid and Interface Science. 1990;140(1):192–206. DOI: 10.1016/0021-9797(90)90335-l.
  17. Krul’ LP, Shakhno AV, Grinyuk EV, Skakovskii ED, Tychinskaya LY, Gospodarev DA, et al. [Interaction of carboxylated polyacrylamide with chromium(III) acetate: 13C NMR study of mechanism]. Zhurnal obshchei khimii. 2013;83(11):1829–1834. Russian.
  18. Fomina EK, Krul’ LP, Butovskaya GV, Grinyuk EV, Shakhno AV, Skakovskii ED, et al. Structure determination of the macromolecular complexes of microelements with acrylamide and sodium acrylate copolymers by 13C NMR spectroscopy. Proceedings of the National Academy of Sciences of Belarus. Chemical series. 2016;4:80–90. Russian.
  19. Krul’ LP, Nareiko EI, Krakodeev DV, Grinyuk EV, Rybak AS, Skakovskii ED, et al. [13C NMR study of the structure of products formed in base hydrolysis of nitron D polyacrylonitrile fiber]. Zhurnal prikladnoi khimii. 2003:76(6):1006–1008. Russian.
  20. Kitayama T, Hatada K. NMR Spectroscopy of Polymers. Berlin: Springer; 2004. 228 p.
  21. Martell AE, Hancock RD. Metal complexes in aqueous solutions. Berlin: Springer; 1996. 254 p.
Published
2021-04-12
Keywords: acrylamide and sodium acrylate copolymer, amino acids, macromolecular metal complexes, mixed complexes, Cu(II) ions, aqueous solutions
How to Cite
Kudryavsky, D. L., Fomina, E. K., Tychinskaya, L. Y., Skakovsky, E. D., & Bogushevich, S. E. (2021). NMR spectroscopy of Cu(II) complexes with acrylamide and sodium acrylate copolymer and ω-amino acids. Journal of the Belarusian State University. Chemistry, 1, 85-98. https://doi.org/10.33581/2520-257X-2021-1-85-98
Issue
No 1 (2021): Journal of the Belarusian State University. Chemistry
Section
Original Articles

Copyright (c) 2021 Journal of the Belarusian State University. Chemistry

Creative Commons License

This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.

The authors who are published in this journal agree to the following:

  1. The authors retain copyright on the work and provide the journal with the right of first publication of the work on condition of license Creative Commons Attribution-NonCommercial. 4.0 International (CC BY-NC 4.0).
  2. The authors retain the right to enter into certain contractual agreements relating to the non-exclusive distribution of the published version of the work (e.g. post it on the institutional repository, publication in the book), with the reference to its original publication in this journal.
  3. The authors have the right to post their work on the Internet (e.g. on the institutional store or personal website) prior to and during the review process, conducted by the journal, as this may lead to a productive discussion and a large number of references to this work. (See The Effect of Open Access.)