Ion-Induced Polysaccharide Gelation: Peculiarities of Alginate Egg-Box Association with Different Divalent Cations
Structural aspects of polysaccharide hydrogels based on sodium alginate and divalent cations Ba<sup>2+</sup>, Ca<sup>2+</sup>, Sr<sup>2+</sup>, Cu<sup>2+</sup>, Zn<sup>2+</sup>, Ni<sup>2+</sup> and Mn<sup>2+</sup> wa...
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MDPI AG
2023-02-01
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| Series: | Polymers |
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| Online Access: | https://www.mdpi.com/2073-4360/15/5/1243 |
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| author | Anastasiya O. Makarova Svetlana R. Derkach Tahar Khair Mariia A. Kazantseva Yuriy F. Zuev Olga S. Zueva |
| author_facet | Anastasiya O. Makarova Svetlana R. Derkach Tahar Khair Mariia A. Kazantseva Yuriy F. Zuev Olga S. Zueva |
| author_sort | Anastasiya O. Makarova |
| collection | DOAJ |
| description | Structural aspects of polysaccharide hydrogels based on sodium alginate and divalent cations Ba<sup>2+</sup>, Ca<sup>2+</sup>, Sr<sup>2+</sup>, Cu<sup>2+</sup>, Zn<sup>2+</sup>, Ni<sup>2+</sup> and Mn<sup>2+</sup> was studied using data on hydrogel elemental composition and combinatorial analysis of the primary structure of alginate chains. It was shown that the elemental composition of hydrogels in the form of freezing dried microspheres gives information on the structure of junction zones in the polysaccharide hydrogel network, the degree of filling of egg-box cells by cations, the type and magnitude of the interaction of cations with alginate chains, the most preferred types of alginate egg-box cells for cation binding and the nature of alginate dimers binding in junction zones. It was ascertained that metal–alginate complexes have more complicated organization than was previously desired. It was revealed that in metal–alginate hydrogels, the number of cations of various metals per C12 block may be less than the limiting theoretical value equal to 1 for completely filled cells. In the case of alkaline earth metals and zinc, this number is equal to 0.3 for calcium, 0.6 for barium and zinc and 0.65–0.7 for strontium. We have determined that in the presence of transition metals copper, nickel and manganese, a structure similar to an egg-box is formed with completely filled cells. It was determined that in nickel–alginate and copper–alginate microspheres, the cross-linking of alginate chains and formation of ordered egg-box structures with completely filled cells are carried out by hydrated metal complexes with complicated composition. It was found that an additional characteristic of complex formation with manganese cations is the partial destruction of alginate chains. It has been established that the existence of unequal binding sites of metal ions with alginate chains can lead to the appearance of ordered secondary structures due to the physical sorption of metal ions and their compounds from the environment. It was shown that hydrogels based on calcium alginate are most promising for absorbent engineering in environmental and other modern technologies. |
| first_indexed | 2024-03-11T07:12:47Z |
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| institution | Directory Open Access Journal |
| issn | 2073-4360 |
| language | English |
| last_indexed | 2024-03-11T07:12:47Z |
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| series | Polymers |
| spelling | doaj.art-447a79d6dd8a4a87bdf273a37cede68e2023-11-17T08:28:07ZengMDPI AGPolymers2073-43602023-02-01155124310.3390/polym15051243Ion-Induced Polysaccharide Gelation: Peculiarities of Alginate Egg-Box Association with Different Divalent CationsAnastasiya O. Makarova0Svetlana R. Derkach1Tahar Khair2Mariia A. Kazantseva3Yuriy F. Zuev4Olga S. Zueva5Kazan Institute of Biochemistry and Biophysics, FRC Kazan Scientific Center of RAS, Lobachevsky St., 2/31, 420111 Kazan, RussiaInstitute of Natural Science and Technology, Murmansk State Technical University, Sportivnaya Str. 13, 183010 Murmansk, RussiaInstitute of Electric Power Engineering and Electronics, Kazan State Power Engineering University, Krasnoselskaya St. 51, 420066 Kazan, RussiaKazan Institute of Biochemistry and Biophysics, FRC Kazan Scientific Center of RAS, Lobachevsky St., 2/31, 420111 Kazan, RussiaKazan Institute of Biochemistry and Biophysics, FRC Kazan Scientific Center of RAS, Lobachevsky St., 2/31, 420111 Kazan, RussiaInstitute of Electric Power Engineering and Electronics, Kazan State Power Engineering University, Krasnoselskaya St. 51, 420066 Kazan, RussiaStructural aspects of polysaccharide hydrogels based on sodium alginate and divalent cations Ba<sup>2+</sup>, Ca<sup>2+</sup>, Sr<sup>2+</sup>, Cu<sup>2+</sup>, Zn<sup>2+</sup>, Ni<sup>2+</sup> and Mn<sup>2+</sup> was studied using data on hydrogel elemental composition and combinatorial analysis of the primary structure of alginate chains. It was shown that the elemental composition of hydrogels in the form of freezing dried microspheres gives information on the structure of junction zones in the polysaccharide hydrogel network, the degree of filling of egg-box cells by cations, the type and magnitude of the interaction of cations with alginate chains, the most preferred types of alginate egg-box cells for cation binding and the nature of alginate dimers binding in junction zones. It was ascertained that metal–alginate complexes have more complicated organization than was previously desired. It was revealed that in metal–alginate hydrogels, the number of cations of various metals per C12 block may be less than the limiting theoretical value equal to 1 for completely filled cells. In the case of alkaline earth metals and zinc, this number is equal to 0.3 for calcium, 0.6 for barium and zinc and 0.65–0.7 for strontium. We have determined that in the presence of transition metals copper, nickel and manganese, a structure similar to an egg-box is formed with completely filled cells. It was determined that in nickel–alginate and copper–alginate microspheres, the cross-linking of alginate chains and formation of ordered egg-box structures with completely filled cells are carried out by hydrated metal complexes with complicated composition. It was found that an additional characteristic of complex formation with manganese cations is the partial destruction of alginate chains. It has been established that the existence of unequal binding sites of metal ions with alginate chains can lead to the appearance of ordered secondary structures due to the physical sorption of metal ions and their compounds from the environment. It was shown that hydrogels based on calcium alginate are most promising for absorbent engineering in environmental and other modern technologies.https://www.mdpi.com/2073-4360/15/5/1243sodium alginatedivalent metal cationshydrogelmetal sorptionassociation structure |
| spellingShingle | Anastasiya O. Makarova Svetlana R. Derkach Tahar Khair Mariia A. Kazantseva Yuriy F. Zuev Olga S. Zueva Ion-Induced Polysaccharide Gelation: Peculiarities of Alginate Egg-Box Association with Different Divalent Cations Polymers sodium alginate divalent metal cations hydrogel metal sorption association structure |
| title | Ion-Induced Polysaccharide Gelation: Peculiarities of Alginate Egg-Box Association with Different Divalent Cations |
| title_full | Ion-Induced Polysaccharide Gelation: Peculiarities of Alginate Egg-Box Association with Different Divalent Cations |
| title_fullStr | Ion-Induced Polysaccharide Gelation: Peculiarities of Alginate Egg-Box Association with Different Divalent Cations |
| title_full_unstemmed | Ion-Induced Polysaccharide Gelation: Peculiarities of Alginate Egg-Box Association with Different Divalent Cations |
| title_short | Ion-Induced Polysaccharide Gelation: Peculiarities of Alginate Egg-Box Association with Different Divalent Cations |
| title_sort | ion induced polysaccharide gelation peculiarities of alginate egg box association with different divalent cations |
| topic | sodium alginate divalent metal cations hydrogel metal sorption association structure |
| url | https://www.mdpi.com/2073-4360/15/5/1243 |
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