2024 (1) 6

https://doi.org/10.15407/polymerj.46.01.056

PYROLYSIS OF PLASTICIZED FILMS BASED ON SOY PROTEIN, DENATURED BY DIFFERENT SUBSTANCES

Tetiana Samoilenko* (ORCID: 0000-0002-3232-1621), Larysa Yashchenko (ORCID: 0000-0002-0736-8073), Nataliia Yarova (ORCID: 0000-0002-3347-8073), Volodymyr Bortnytskyi (ORCID: 0000-0003-4954-6533), Oleksandr Brovko (ORCID: 0000-0003-0238-1137)
Institute of Macromolecular Chemistry NAS of Ukraine, 48, Kharkivske highway, Kyiv, 02155, Ukraine,

*e-mail: s_t_f@ukr.net
Polym. J., 2024, 46, no. 1: 56-65.

Section: Structure and properties.

Language: Ukrainian.

Abstract:

Polymer films based on soy protein isolate (SPI) were obtained using the thermo-pressing method. Plasticizers and denaturing agents were added to ensure better the film-forming properties and reduce the fragility of the resulting materials. Glycerol, sorbitol and their mixture were used for plasticization, while solutions of alkali (potassium hydroxide), surfactants of natural origin (sodium coco sulfate) and reducing agent (sodium sulfite) were used for denaturation. By combining different types of plasticization and denaturation, a series of samples were obtained and compared with a sample based on raw soy protein. In addition to the obvious differences in the appearance of the films, the processes of their thermal degradation, studied by pyrolysis mass spectrometry, also differed significantly. In fact, unprocessed soy protein has the highest thermal stability with the temperature of the most intensive decomposition equal to 270 °С, which can decrease to 200 °С under the conditions of denaturation and plasticization. Despite the increase in the number of film components, the amount of volatile decomposition products decreases (from 86 to 32), as well as the molecular weight of the heaviest of them (from 169 to 74). This is a sign of a change in the mechanism of soy protein degradation due to denaturation and plasticization caused by transformations in its supramolecular structure, such as unfolding and extension of macrochains with increased availability of functional groups. The pyrolytic behavior of some protein samples plasticized with sorbitol is closest to that of untreated soy protein, which may indicate a lower plasticizing efficiency of sorbitol with longer molecules than glycerol. The interpretation of the recorded mass spectra of the volatile pyrolysis products showed that the thermal degradation of protein materials is dominated by processes such as decarboxylation, dehydration, deamination and decarbonylation, while in the presence of plasticizers the splitting of their own molecules also becomes dominant. The characteristic mass spectra of protein films denatured by surfactants also contain ionic fragments of relatively high molecular weight, probably derived from sodium coco sulfate molecules.

Key words: soy protein, pyrolysis mass-spectrometry, denaturation, plasticizer, thermal degradation.

References

1. Song F., Tang D.L., Wang X.L., Wang Y.Z. Biodegradable soy protein isolate-based materials: a review. Biomacromolecules, 2011, 12, no. 10: 3369–3380. https://dx.doi.org/10.1021/bm200904x.
2. Cuq B., Gontard N., Guilbert S. Proteins as agricultural polymers for packaging production. Cereal Chem., 1998, 75: 1–9. https://doi.org/10.1094/CCHEM.1998.75.1.1
3. Kumar R., Choudhary V., Mishra S., Varma I.K., Mattiason B. Adhesives and plastics based on soy protein products. Ind. Crops Prod., 2002, 16: 155–172. https://doi.org/10.1016/S0926-6690(02)00007-9.
4. Zhong Z.K., Sun X.S. Thermal and mechanical properties and water absorption of sodium dodecyl sulfate-modified soy protein (11S). J. Appl. Polym. Sci., 2001, 81: 166–175. https://doi.org/10.1002/app.1426.
5. Wihodo M., Moraru C.I. Physical and chemical methods used to enhance the structure and mechanical properties of protein films: A review. J. Food Eng., 2013, 114, no. 3: 292–302. http://dx.doi.org/10.1016/j.jfoodeng.2012.08.021.
6. Liu P., Xu H., Zhao Y., Yang Y. Rheological properties of soy protein isolate solution for fibers and films. Food Hydrocoll., 2017, 64: 149–156. http://dx.doi.org/10.21577/0103-5053.20170090.
7. Zink J., Wyrobnik T., Prinz T., Schmid M. Physical, chemical and biochemical modifications of protein-based films and coatings: an extensive review. Int. J. Mol. Sci., 2016, 17: 1376. https://doi.org/10.3390/ijms17091376.
8. Wan V.C.-H., Kim M.S., Lee S.-Y. Water vapor permeability and mechanical properties of soy protein isolate edible films composed of different plasticizer combinations. J. Food Sci., 2005, 70, nо. 6: 387–391. https://doi.org/10.1111/j.1365-2621.2005.tb11443.x.
9. Brandenburg A.H., Weller C.L., Testin R.F. Edible films and coatings from soy proteins. J. Food Sci., 1993, 58: 1086 – 1089. https://doi.org/10.1111/j.1365-2621.1993.tb06120.x.
10. Schmidt V., Giacomelli C., Soldi V. Thermal stability of films formed by soy protein isolate–sodium dodecyl sulfate. Polym. Degrad. Stabil., 2005, 87: 25–31. https://doi.org/10.1016/j.polymdegradstab.2004.07.003.
11. Huang W., Sun X. Adhesive properties of soy proteins modified by sodium dodecyl sulfate and sodium dodecyl benzene sulfonate. J. Am. Oil Chem. Soc., 2000, 77, no. 7: 705–708. https://doi.org/10.1007/s11746-000-0113-6.
12. Du Y., Li S., Zhang Y. Treatments of protein for biopolymer production in view of processability and physical properties: a review. J. Appl. Polym. Sci., 2018, 133, no. 17: 43351–43364. https://doi.org/10.1002/app.43351.
13. Kim K.M., Marx D.B., Weller C.L., Hanna M.A. Influence of sorghum wax, glycerin, and sorbitol on physical properties of soy protein isolate films. J. Am. Oil Chem.Soc., 2003, 80: 71–76. https://doi.org/10.1007/s11746-003-0653-9.
14. Sothornvit R., Krochta J.M. Plasticizer effect on mechanical properties of β-lactoglobulin films. J. Food Eng., 2001, 50, no. 3: 149–155. https://doi.org/10.1016/S0260-8774(00)00237-5.
15. Ruan Q., Chen Y., Kong X., Hua Y. Analysis using fluorescence labeling and mass spectrometry of disulfide-mediated interactions of soy protein when heated. J. Agric. Food Chem., 2015, 63: 3524−3533. https://doi.org/10.1021/jf504519z.
16. Samoilenko T.F., Yashchenko L.M., Yarova N.V., Brovko O.O. Vplyv plastyfikatoriv na vtorynnu strukturu soievoho bilka. Materialy Vseukrainskoi naukovoi konferentsii: «Aktualni zadachi khimii: doslidzhennia ta perspektyvy»: Zhytomyr. Vydavets PP «Yevro-Volyn», 2022: 141–142.
17. Samoilenko T.F., Yashchenko L.M., Yarova N.V., Brovko O.O. Zmina konformatsii soievoho bilka, denaturovanoho natrii kokosulfatom, zalezhno vid skladu plastyfikatsiinoi systemy «hlitseryn/sorbit». Materialy Vseukrainskoi naukovoi konferentsii «Aktualni zadachi khimii: doslidzhennia ta perspektyvy»: Zhytomyr: PP «Yevro-Volyn», 2023: 232–233.
18. Wang Y., Cao X., Zhang L. Effects of cellulose whiskers on properties of soy protein thermoplastics. Macromol. Biosci, 2006, 6: 524–531. https://doi.org/10.1002/mabi.200600034.
19. Li X., Fan P., Zang M., Xing J. Rapid determination of oligopeptides and amino acids in soybean protein hydrolysates using high-resolution mass spectrometry. Phytochem. Anal., 2015, 26: 15–22. https://doi.org/10.1002/pca.2531.
20. Niu Q., Jinglan W., Congcong С., Zhanjun C., Yanan Z. , Wu W., Jian W., Yang P., Beibei Y., Guanyi C., Frederik R. Comparative study of different algae pyrolysis using photoionization mass spectrometry and gas chromatography/mass spectrometry. J. Anal. Appl. Pyrol., 2021, 155: 105068. https://doi.org/10.1016/j.jaap.2021.105068.
21. Li J., Yanan Z., Chengbiao W., Wei W., Zhengyi L., Yuanyu T., Peijie Z., Yingyun Q., Song Q. Golden seaweed tides from beach inundations as a valuable sustainable fuel resource: Fast pyrolysis characteristics, product distribution and pathway study on Sargassum horneri based on model compounds. Algal Res., 2020, 48: 101888. https://doi.org/10.1016/j.algal.2020.101888.
22. Ratcliff M.A., Medley E.E., Simmonds P.G. Pyrolysis of amino acids. Mechanistic considerations. J. Org. Chem., 1974, 39, no. 11: 1481–1490. https://doi.org/10.1021/jo00924a007.
23. Simmonds P.G., Medley E.E., Ratcliff M.A., Shulman G.P. Thermal decomposition of aliphatic monoamino-monocarboxylic acids. Anal. Chem., 1972, 44, no. 12: 2060–2066. https://doi.org/10.1021/ac60320a040.