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Preparation of Poly (N-Isopropylacrylamide) -Poly (2-Ethyl-2-Oxazoline) and Their Self-Assembly Properties with Dicarboxylic Acid

Year 2024, Volume: 11 Issue: 2, 813 - 824, 15.05.2024
https://doi.org/10.18596/jotcsa.1150117

Abstract

This study reports the synthesis of copolymers that contain thermally responsive polymers, namely poly(N-isopropylacrylamide) (PNIPAM) and poly(2-ethyl-2-oxazoline) (PEOX), as well as biodegradable side groups that are water-soluble and capable of hydrogen bonding. The assay aims to produce heat-responsive PNIPAM and PEOX polymers with di-carboxylic acid (DCA) controlled structuring of the resulting pH-sensitive nano-structured polymers. These will be used as a template in the synthesis of inorganic materials. The study demonstrated the impact of pH, salt concentration, and temperature on the polymer/DCA. This fragment describes the functional groups of the thermosensitive polymers PNIPAM and PEOX. These polymers have carboxylic acid functional groups at both ends, are water soluble, and are capable of hydrogen bonding. The structure of these polymers can be recognized with small molecules of DCA in an aqueous solution at different pH, salt concentrations, and temperatures with H-bonds. Additionally, these polymers can be used as templates to synthesize hollow silica polymers. The synthesized monomers and polymers were structurally characterized using Fourier transform infrared spectrophotometer (FT-IR). The resulting structured polymers were identified by scanning electron microscopy and atomic force microscopy (SEM, AFM). UV-VIS spectrophotometer and Differential Scanning Calorimetry (DSC) were used to determine the Lower Critical Solution temperature of the polymers.

Project Number

BAP 2016-13

References

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  • 2. Wei M, Gao Y, Li X, Serpe MJ. Stimuli-responsive polymers and their applications. Polym Chem. 2017;8(1):127–43. Available from: URL
  • 3. Karimi M, Sahandi Zangabad P, Ghasemi A, Amiri M, Bahrami M, Malekzad H, et al. Temperature-responsive smart nanocarriers for delivery of therapeutic agents: applications and recent advances. ACS Appl Mater Interfaces. 2016;8(33):21107–33. Available from: URL 4. Li J, Kikuchi S, Sato S ichiro, Chen Y, Xu L, Song B, et al. Core-First Synthesis and Thermoresponsive Property of Three-, Four-, and Six-Arm Star-Shaped Poly (N, N-diethylacrylamide) s and Their Block Copolymers with Poly (N, N-dimethylacrylamide). Macromolecules. 2019;52(19):7207–17. Available from: URL
  • 5. Al-Zaidi AT, Al-Dokheily ME, Al-Atabi SH. Low critical solution temperatures and water swelling ratios of some new PNIPAAm copolymers synthesized by free radical polymerization. In: AIP Conference Proceedings. AIP Publishing LLC; 2020. p. 20176.
  • 6. Tseng W, Fang T, Chen C, Hsieh Y, Lai W. Upper Critical Solution Temperature‐Type Thermal Response of Soluble Multi‐l‐Arginyl‐Poly‐l‐Aspartic Acid (cyanophycin) Conjugated with Maltodextrin. J Polym Sci A Polym Chem. 2019;57(19):2048–55. Available from: URL
  • 7. Pasparakis G, Tsitsilianis C. LCST polymers: Thermoresponsive nanostructured assemblies towards bioapplications. Polymer, 2020; 211: 123146. Available from: URL
  • 8. Marsili L, Dal Bo M, Berti F, Toffoli G. Chitosan-Based Biocompatible Copolymers for Thermoresponsive Drug Delivery Systems: On the Development of a Standardization System. Pharmaceutics. 2021; 13(11): 1876. Available from: URL
  • 9. Kocak G, Tuncer C, Bütün V. Stimuli-Responsive Polymers Providing New Opportunities for Various Applications. Hacettepe J. Biol. & Chem., 2020; 48(5): 527-574. Available from: URL 10. Konefał R, Spěváček J, Černoch P. Thermoresponsive poly (2-oxazoline) homopolymers and copolymers in aqueous solutions studied by NMR spectroscopy and dynamic light scattering. Eur Polym J. 2018; 100: 241–52. Available from: URL
  • 11. Tang Q, Qian S, Chen W, Song X, Huang J. Preparation and characterization of temperature-responsive Ca–alginate/poly(N-isopropylacrylamide) hydrogel. Polym Int, 2023; 72: 252-262. Available from: URL
  • 12. Lusina A, Nazim T, Cegłowski M. Poly(2-oxazoline)s as Stimuli-Responsive Materials for Biomedical Applications: Recent Developments of Polish Scientists. Polymers. 2022; 14(19):4176. Available from: URL
  • 13. Mizusaki M, Endo T, Nakahata R, Morishima Y, Yusa S ichi. pH-induced association and dissociation of intermolecular complexes formed by hydrogen bonding between diblock copolymers. Polymers (Basel). 2017;9(8):367. Available from: URL
  • 14. Zhu YG, Wang Y, Shi Y, Wong JI, Yang HY. CoO nanoflowers woven by CNT network for high energy density flexible micro-supercapacitor. Nano Energy. 2014;3:46–54. Available from: URL
  • 15. Altıntaş Z, Adatoz EB, Ijaz A, Miko A, Demirel AL. Self-assembled poly (2-ethyl-2-oxazoline)/malonic acid hollow fibers in aqueous solutions. Eur Polym J. 2019;120:109222. Available from: URL 16. Kocak G, Tuncer C, Bütün V. pH-Responsive polymers. Polym Chem. 2017;8(1):144–76. Available from: URL
  • 17. Hendessi S, Güner PT, Miko A, Demirel AL. Hydrogen bonded multilayers of poly (2-ethyl-2-oxazoline) stabilized silver nanoparticles and tannic acid. Eur Polym J. 2017;88:666–78. Available from: URL
  • 18. Oleszko-Torbus N, Utrata-Wesołek A, Bochenek M, Lipowska-Kur D, Dworak A, Wałach W. Thermal and crystalline properties of poly (2-oxazoline)s. Polym Chem. 2020;11(1):15–33. Available from: URL 19. Ohnsorg ML, Ting JM, Jones SD, Jung S, Bates FS, Reineke TM. Tuning PNIPAm self-assembly and thermoresponse: roles of hydrophobic end-groups and hydrophilic comonomer. Polym Chem. 2019;10(25):3469–79. Available from: URL
  • 20. Gandhi A, Paul A, Sen SO, Sen KK. Studies on thermoresponsive polymers: Phase behaviour, drug delivery and biomedical applications. Asian J Pharm Sci. 2015;10(2):99–107. Available from: URL
  • 21. Adams N, Schubert US. Poly (2-oxazolines) in biological and biomedical application contexts. Adv Drug Deliv Rev. 2007;59(15):1504–20. Available from: URL
  • 22. Gaertner FC, Luxenhofer R, Blechert B, Jordan R, Essler M. Synthesis, biodistribution and excretion of radiolabeled poly (2-alkyl-2-oxazoline) s. Journal of Controlled Release. 2007;119(3):291–300. Available from: URL
  • 23. Dutta K, De S. Smart responsive materials for water purification: an overview. J Mater Chem A Mater. 2017;5(42):22095–112. Available from: URL
  • 24. Zou H, Wu Q, Li Q, Wang C, Zhou L, Hou XH, et al. Thermo-and redox-responsive dumbbell-shaped copolymers: from structure design to the LCST–UCST transition. Polym Chem. 2020;11(4):830–42. Available from: URL
  • 25. Chen JJ, Ahmad AL, Ooi BS. Poly (N-isopropylacrylamide-co-acrylic acid) hydrogels for copper ion adsorption: Equilibrium isotherms, kinetic and thermodynamic studies. J Environ Chem Eng. 2013;1(3):339–48. Available from: URL
  • 26. Wang J, Sutti A, Lin T, Wang X. Thermo-responsive PNIPAM hydrogel nanofibres photocrosslinked by azido-POSS. In: Fiber Society Spring 2013 Technical Conference. Fiber Society; 2013. Available from: URL
  • 27. Li G, Song S, Zhang T, Qi M, Liu J. pH-sensitive polyelectrolyte complex micelles assembled from CS-g-PNIPAM and ALG-gP (NIPAM-co-NVP) for drug delivery. Int J Biol Macromol. 2013;62:203–10. Available from: URL
  • 28. Lai H, Wang Z, Wu P. Structural evolution in a biphasic system: poly (N-isopropylacrylamide) transfer from water to hydrophobic ionic liquid. RSC Adv. 2012;2(31):11850–7. Available from: URL
  • 29. Saad A, Mills R, Wan H, Mottaleb MA, Ormsbee L, Bhattacharyya D. Thermo-responsive adsorption-desorption of perfluoroorganics from water using PNIPAm hydrogels and pore functionalized membranes. J Memb Sci. 2020;599:117821. Available from: URL
  • 30. Rusen L, Dinca V, Mustaciosu C, Icriverzi M, Sima LE, Bonciu A, et al. Smart Thermoresponsive Surfaces Based on pNIPAm Coatings and Laser Method for Biological Applications. Modern Technologies for Creating the Thin-film Systems and Coatings. 2017;10. Available from: URL
  • 31. Mourdikoudis S, Pallares RM, Thanh NTK. Characterization techniques for nanoparticles: comparison and complementarity upon studying nanoparticle properties. Nanoscale. 2018;10(27):12871–934. Available from: URL
  • 32. Niranjanmurthi L, Park C, Lim KT. Synthesis and characterization of graphene oxide/poly (2-ethyl-2-oxazoline) composites. Molecular Crystals and Liquid Crystals. 2012;564(1):206–12. Available from: URL 33. Minkova LI, Miteva T, Sek D, Kaczmarczyk B, Magagnini PL, Paci M, et al. Reactive blending of a functionalized polyethylene with a semiflexible liquid crystalline copolyester. J Appl Polym Sci. 1996;62(10):1613–25. Available from: URL
  • 34. Kuo SW. Hydrogen bonding in polymeric materials. John Wiley & Sons; 2018. Available from: URL
Year 2024, Volume: 11 Issue: 2, 813 - 824, 15.05.2024
https://doi.org/10.18596/jotcsa.1150117

Abstract

Supporting Institution

İnönü Üniversitesi

Project Number

BAP 2016-13

References

  • 1. Pino-Ramos VH, Ramos-Ballesteros A, López-Saucedo F, López-Barriguete JE, Varca GHC, Bucio E. Radiation grafting for the functionalization and development of smart polymeric materials. In: Applications of Radiation Chemistry in the Fields of Industry, Biotechnology and Environment. Springer; 2017. p. 67–94.
  • 2. Wei M, Gao Y, Li X, Serpe MJ. Stimuli-responsive polymers and their applications. Polym Chem. 2017;8(1):127–43. Available from: URL
  • 3. Karimi M, Sahandi Zangabad P, Ghasemi A, Amiri M, Bahrami M, Malekzad H, et al. Temperature-responsive smart nanocarriers for delivery of therapeutic agents: applications and recent advances. ACS Appl Mater Interfaces. 2016;8(33):21107–33. Available from: URL 4. Li J, Kikuchi S, Sato S ichiro, Chen Y, Xu L, Song B, et al. Core-First Synthesis and Thermoresponsive Property of Three-, Four-, and Six-Arm Star-Shaped Poly (N, N-diethylacrylamide) s and Their Block Copolymers with Poly (N, N-dimethylacrylamide). Macromolecules. 2019;52(19):7207–17. Available from: URL
  • 5. Al-Zaidi AT, Al-Dokheily ME, Al-Atabi SH. Low critical solution temperatures and water swelling ratios of some new PNIPAAm copolymers synthesized by free radical polymerization. In: AIP Conference Proceedings. AIP Publishing LLC; 2020. p. 20176.
  • 6. Tseng W, Fang T, Chen C, Hsieh Y, Lai W. Upper Critical Solution Temperature‐Type Thermal Response of Soluble Multi‐l‐Arginyl‐Poly‐l‐Aspartic Acid (cyanophycin) Conjugated with Maltodextrin. J Polym Sci A Polym Chem. 2019;57(19):2048–55. Available from: URL
  • 7. Pasparakis G, Tsitsilianis C. LCST polymers: Thermoresponsive nanostructured assemblies towards bioapplications. Polymer, 2020; 211: 123146. Available from: URL
  • 8. Marsili L, Dal Bo M, Berti F, Toffoli G. Chitosan-Based Biocompatible Copolymers for Thermoresponsive Drug Delivery Systems: On the Development of a Standardization System. Pharmaceutics. 2021; 13(11): 1876. Available from: URL
  • 9. Kocak G, Tuncer C, Bütün V. Stimuli-Responsive Polymers Providing New Opportunities for Various Applications. Hacettepe J. Biol. & Chem., 2020; 48(5): 527-574. Available from: URL 10. Konefał R, Spěváček J, Černoch P. Thermoresponsive poly (2-oxazoline) homopolymers and copolymers in aqueous solutions studied by NMR spectroscopy and dynamic light scattering. Eur Polym J. 2018; 100: 241–52. Available from: URL
  • 11. Tang Q, Qian S, Chen W, Song X, Huang J. Preparation and characterization of temperature-responsive Ca–alginate/poly(N-isopropylacrylamide) hydrogel. Polym Int, 2023; 72: 252-262. Available from: URL
  • 12. Lusina A, Nazim T, Cegłowski M. Poly(2-oxazoline)s as Stimuli-Responsive Materials for Biomedical Applications: Recent Developments of Polish Scientists. Polymers. 2022; 14(19):4176. Available from: URL
  • 13. Mizusaki M, Endo T, Nakahata R, Morishima Y, Yusa S ichi. pH-induced association and dissociation of intermolecular complexes formed by hydrogen bonding between diblock copolymers. Polymers (Basel). 2017;9(8):367. Available from: URL
  • 14. Zhu YG, Wang Y, Shi Y, Wong JI, Yang HY. CoO nanoflowers woven by CNT network for high energy density flexible micro-supercapacitor. Nano Energy. 2014;3:46–54. Available from: URL
  • 15. Altıntaş Z, Adatoz EB, Ijaz A, Miko A, Demirel AL. Self-assembled poly (2-ethyl-2-oxazoline)/malonic acid hollow fibers in aqueous solutions. Eur Polym J. 2019;120:109222. Available from: URL 16. Kocak G, Tuncer C, Bütün V. pH-Responsive polymers. Polym Chem. 2017;8(1):144–76. Available from: URL
  • 17. Hendessi S, Güner PT, Miko A, Demirel AL. Hydrogen bonded multilayers of poly (2-ethyl-2-oxazoline) stabilized silver nanoparticles and tannic acid. Eur Polym J. 2017;88:666–78. Available from: URL
  • 18. Oleszko-Torbus N, Utrata-Wesołek A, Bochenek M, Lipowska-Kur D, Dworak A, Wałach W. Thermal and crystalline properties of poly (2-oxazoline)s. Polym Chem. 2020;11(1):15–33. Available from: URL 19. Ohnsorg ML, Ting JM, Jones SD, Jung S, Bates FS, Reineke TM. Tuning PNIPAm self-assembly and thermoresponse: roles of hydrophobic end-groups and hydrophilic comonomer. Polym Chem. 2019;10(25):3469–79. Available from: URL
  • 20. Gandhi A, Paul A, Sen SO, Sen KK. Studies on thermoresponsive polymers: Phase behaviour, drug delivery and biomedical applications. Asian J Pharm Sci. 2015;10(2):99–107. Available from: URL
  • 21. Adams N, Schubert US. Poly (2-oxazolines) in biological and biomedical application contexts. Adv Drug Deliv Rev. 2007;59(15):1504–20. Available from: URL
  • 22. Gaertner FC, Luxenhofer R, Blechert B, Jordan R, Essler M. Synthesis, biodistribution and excretion of radiolabeled poly (2-alkyl-2-oxazoline) s. Journal of Controlled Release. 2007;119(3):291–300. Available from: URL
  • 23. Dutta K, De S. Smart responsive materials for water purification: an overview. J Mater Chem A Mater. 2017;5(42):22095–112. Available from: URL
  • 24. Zou H, Wu Q, Li Q, Wang C, Zhou L, Hou XH, et al. Thermo-and redox-responsive dumbbell-shaped copolymers: from structure design to the LCST–UCST transition. Polym Chem. 2020;11(4):830–42. Available from: URL
  • 25. Chen JJ, Ahmad AL, Ooi BS. Poly (N-isopropylacrylamide-co-acrylic acid) hydrogels for copper ion adsorption: Equilibrium isotherms, kinetic and thermodynamic studies. J Environ Chem Eng. 2013;1(3):339–48. Available from: URL
  • 26. Wang J, Sutti A, Lin T, Wang X. Thermo-responsive PNIPAM hydrogel nanofibres photocrosslinked by azido-POSS. In: Fiber Society Spring 2013 Technical Conference. Fiber Society; 2013. Available from: URL
  • 27. Li G, Song S, Zhang T, Qi M, Liu J. pH-sensitive polyelectrolyte complex micelles assembled from CS-g-PNIPAM and ALG-gP (NIPAM-co-NVP) for drug delivery. Int J Biol Macromol. 2013;62:203–10. Available from: URL
  • 28. Lai H, Wang Z, Wu P. Structural evolution in a biphasic system: poly (N-isopropylacrylamide) transfer from water to hydrophobic ionic liquid. RSC Adv. 2012;2(31):11850–7. Available from: URL
  • 29. Saad A, Mills R, Wan H, Mottaleb MA, Ormsbee L, Bhattacharyya D. Thermo-responsive adsorption-desorption of perfluoroorganics from water using PNIPAm hydrogels and pore functionalized membranes. J Memb Sci. 2020;599:117821. Available from: URL
  • 30. Rusen L, Dinca V, Mustaciosu C, Icriverzi M, Sima LE, Bonciu A, et al. Smart Thermoresponsive Surfaces Based on pNIPAm Coatings and Laser Method for Biological Applications. Modern Technologies for Creating the Thin-film Systems and Coatings. 2017;10. Available from: URL
  • 31. Mourdikoudis S, Pallares RM, Thanh NTK. Characterization techniques for nanoparticles: comparison and complementarity upon studying nanoparticle properties. Nanoscale. 2018;10(27):12871–934. Available from: URL
  • 32. Niranjanmurthi L, Park C, Lim KT. Synthesis and characterization of graphene oxide/poly (2-ethyl-2-oxazoline) composites. Molecular Crystals and Liquid Crystals. 2012;564(1):206–12. Available from: URL 33. Minkova LI, Miteva T, Sek D, Kaczmarczyk B, Magagnini PL, Paci M, et al. Reactive blending of a functionalized polyethylene with a semiflexible liquid crystalline copolyester. J Appl Polym Sci. 1996;62(10):1613–25. Available from: URL
  • 34. Kuo SW. Hydrogen bonding in polymeric materials. John Wiley & Sons; 2018. Available from: URL
There are 29 citations in total.

Details

Primary Language English
Subjects Polymer Science and Technologies
Journal Section RESEARCH ARTICLES
Authors

Perihan Yilmaz Erdogan 0000-0002-1375-603X

Fatma Bilge Emre 0000-0002-2972-5596

Turgay Seçkin 0000-0001-8483-7366

Project Number BAP 2016-13
Publication Date May 15, 2024
Submission Date November 25, 2022
Acceptance Date February 5, 2024
Published in Issue Year 2024 Volume: 11 Issue: 2

Cite

Vancouver Yilmaz Erdogan P, Emre FB, Seçkin T. Preparation of Poly (N-Isopropylacrylamide) -Poly (2-Ethyl-2-Oxazoline) and Their Self-Assembly Properties with Dicarboxylic Acid. JOTCSA. 2024;11(2):813-24.