Effect of crosslinking agent type on the properties of PVA-Sodium Alginate-Nanocellulose pad obtained by electrospinning

Document Type : Complete scientific research article

Authors

1 PhD student in Wood and Paper Engineering, Gorgan University of Agricultural Sciences and Natural Resources, Gorgan, Iran.

2 Associate Prof., Department of Paper Science and Engineering, Gorgan University of Agricultural Sciences and Natural Resources, Gorgan, Iran

3 Associate Professor of Natural Resources Engineering - Wood and Paper Science and Technology, Biorefinery Department, Faculty of New Technologies and Aerospace Engineering, Shahid Beheshti University, Zirab Campus, Iran

4 Department of Paper Science and Engineering, Faculty of Wood and Paper Engineering, University of Agricultural Sciences and Natural Resources, Gorgan, Iran.

5 , Department of Paper Science and Engineering, Faculty of Wood and Paper Engineering, University of Agricultural Sciences and Natural Resources, Gorgan, Iran.

6 Department of Nanobiotechnology, Faculty of Biotechnology, Specialized University of New Technologies, Amol, Iran.

Abstract

Background and Objectives: In recent years, the use of electrospun pads with cross-linking agents has attracted significant attention due to their improved mechanical and biological properties. These pads have great potential for applications in tissue engineering and the repair of damaged tissues. In this study, the effects of different cross-linking agents, including calcium chloride, citric acid, glutaraldehyde, and zinc chloride, on the mechanical properties of electrospun polyvinyl alcohol (PVA), sodium alginate (NaAlg), and cellulose nanofibers (CNF) pads were investigated.
Materials and Methods: To prepare the electrospun pads, process variables were first optimized. Then, a combination of PVA, NaAlg, and CNF solution was prepared and added to it different amounts of cross-linking agents at different levels. The electrospinning of these solutions was carried out under optimal conditions and the Tensile Strength of the pads were measured. To evaluate the functional groups and morphology of the pads, Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR) and Scanning Electron Microscopy (SEM) analyses were performed. Response surface methodology (RSM) was used through central composite design (CCD) to investigate the effect of experimental variables. Data analysis was also performed using Design Expert 12 software.
Results: The analysis of obtained results using the Response Surface Methodology (RSM) showed that the addition of crosslinking agents significantly increased the tensile strength of the electrospun pads. The electrospun pads containing calcium chloride and glutaraldehyde exhibited an increase in tensile strength by 77 % and 40 %, respectively. Also, Citric acid and zinc chloride increased the tensile strength of the pads by up to 29 % compared to the control sample.
SEM images indicated that the crosslinking agent calcium chloride caused the fibers to come closer and increase the number of connections. ATR-FTIR results indicated changes and the creation of new functional groups, which were observed in the stretching vibration regions of O-H and C=O bonds. Furthermore, ATR-FTIR analysis showed that in the presence of calcium chloride, the interaction of calcium ions with hydroxyl and carboxyl groups in the polymers led to the formation of hydrogen bonds and new linkages.
Conclusion: The use of cross-linking agents of calcium chloride and Glutaraldehyde effectively improved the mechanical and structural properties of the PVA-NaAlg-NFC electrospun pads. Overall, the results of this study showed that the appropriate selection of cross-linking agent can lead to the preparation of electrospun pads with high strength to be used as a substrate for various research applications. Also, this research can be a guide for the development of advanced and innovative materials in the field of tissue engineering and other biological and medical applications.

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 1.Keirouz, A., Wang, Z., Reddy, V. S., Nagy, Z. K., Vass, P., Buzgo, M., Ramakrishna, S., & Radacsi, N. (2023). The history of electrospinning: past, present, and future developments. Advanced Materials Technologies. 8 (11), 2201723.
2.Ji, D., Lin, Y., Guo, X., Ramasubramanian, B., Wang, R., Radacsi, N., & Ramakrishna, S. (2024). Electrospinning of nanofibres. Nature Reviews Methods Primers. 4 (1), 1.
3.Borban, B., Gohain, M.B., Yadav, D., Karki, S., & Ingole, P.G. (2023). Nano-Electrospun Membranes: Green Solutions for Diverse Industrial Needs. J. of Hazardous Materials Advances, 100373.
4.Mhetre, H., Kanse, Y., & Chendake, Y. (2023). Influence of Electrospinning Voltage on the Diameter and Properties of 1-dimensional Zinc Oxide Nanofiber. ES Materials & Manufacturing. 20, 838.
5.Aneem, T. H., Firdous, S. O., Anjum, A., Wong, S. Y., Li, X., & Arafat, M. T. (2024). Enhanced wound healing of ciprofloxacin incorporated PVA/alginate/ PAA electrospun nanofibers with antibacterial effects and controlled drug release. Materials Today Communications. 38, 107950.
6.Rufato, K. B., Veregue, F. R., de Paula Medeiro, R., Francisco, C. B., Souza, P. R., Popat, K. C., & Martins, A. F. (2023). Electrospinning of poly (vinyl alcohol) and poly (vinyl alcohol)/tannin solutions: A critical viewpoint about cross-linking. Materials Today Communications. 35, 106271.
7.Sharma, R., Malviya, R., Singh, S., & Prajapati, B. (2023). A critical review on classified excipient sodium-alginate-based hydrogels: Modification, characterization, and application in soft tissue engineering. Gels. 9 (5), pp. 430.
8.Wang, H., Kong, L., & Ziegler, G. R. (2019). Fabrication of starch-nanocellulose composite fibers by electrospinning. Food Hydrocolloids, 90, 90-98.
9.Pasaoglu, M. E., & Koyuncu, I. (2021). Substitution of petroleum-based polymeric materials used in the electrospinning process with nanocellulose: A review and future outlook. Chemosphere. 269, 128710.
10.Yan, J., Bai, T., Yue, Y., Cheng, W., Bai, L., Wang, D., ... & Han, G. (2022). Nanostructured superior oil-adsorbent nanofiber composites using one-step electrospinning of polyvinylidene fluoride/ nanocellulose. Composites Science and Technology. 224, 109490.
11.Afra, S., Samadi, A., Asadi, P., Bordbar, M., Iloukhani, M., Rai, A., & Aghajanpour, M. (2024). Chitosan crosslinkers and their functionality in 3D bioprinting to produce chitosan-based bioinks. Inorganic Chemistry Communications. 112842.
12.Lim, D.J. (2022). Cross-linking agents for electrospinning-based bone tissue engineering. International J. of Molecular Sciences. 23 (10), 5444.
13.Ehrmann, A. (2021). Non-toxic crosslinking of electrospun gelatin nanofibers for tissue engineering and biomedicine-a review. Polymers. 13, 1973. 22p.
14.Nataraj, D., Reddy, R., & Reddy, N. (2020). Crosslinking electrospun poly (vinyl) alcohol fibers with citric acid
to impart aqueous stability for medical applications. European Polymer J.124, 109484.
15.Zhan, F., Yan, X., Li, J., Sheng, F., & Li, B. (2021). Encapsulation of tangeretin in PVA/PAA crosslinking electrospun fibers by emulsion-electrospinning: Morphology characterization, slow-release, and antioxidant activity assessment. Food Chemistry. 337, 127763.
16.Ge, H., & Wang, M. (2023). Raman Spectrum of the Li2SO4-MgSO4-H2O System: Excess Spectrum and Hydration Shell Spectrum. Molecules. 28, 7356. 13p.
17.Sarker, M., Izadifar, M., Schreyer, D., & Chen, X. (2018). Influence of ionic crosslinkers (Ca2+/Ba2+/Zn2+) on the mechanical and biological properties of 3D Bioplotted Hydrogel Pads. J. of Biomaterials Science, Polymer Edition. 29 (10), 1126-1154.
18.Kumar, A., Lee, Y., Kim, D., Rao, K. M., Kim, J., Park, S., ... & Han, S. S. (2017). Effect of crosslinking functionality on microstructure, mechanical properties, and in vitro cytocompatibility of cellulose nanocrystals reinforced poly (vinyl alcohol)/sodium alginate hybrid pads. International J. of Biological Macromolecules. 95, 962-973.
19.Doustdar, F., Olad, A., & Ghorbani, M. (2022). Effect of glutaraldehyde and calcium chloride as different crosslinking agents on the characteristics of chitosan/cellulose nanocrystals scaffold. International J. of Biological Macromolecules. 208, 912-924.
20.Kidane, S. W. (2021). Application of response surface methodology in food process modeling and optimization. In Response surface methodology in engineering science. IntechOpen.
21.Zangeneh, N., Azizian, A., Lye, L., & Popescu, R. (2002). Application of response surface methodology in numerical geotechnical analysis. In Proc. 55th Canadian Society for Geotechnical Conference, Hamilton. 8p.