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Thermo-responsive self-folding feedstock with excellent shape memory programming

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Abstract

Shape memory polymers are smart materials that have the thermo-/chemo-responsive shape memory effect, can react to environmental stimuli, and exhibit excellent shape-fixity, shape-recovery and folding/unfolding effects. This type of shape memory polymer has shown great potential in the design and development of various drug delivery systems/devices. However, they have some intrinsic shortcomings, such as biodegradability, slow response rate, poor encapsulation ability of hydrophobic/hydrophilic drugs etc. These phenomenon sometimes limit their application in developing suitable drug delivery systems. In this study, we synthesized and characterized a poly(n-isopropyl acrylamide-4-acryloyloxy benzophenone) i.e., p(NIPAM-4ABP) based thermo-responsive self-folding shape-memory polymer with an excellent shape-memory behavior. The lower critical solution temperature of the synthesized p(NIPAM-4ABP) was determined using dynamic light scattering analysis to determine the effect of the addition of 4-ABP to the pNIPAM network. Fourier-transform infrared spectroscopy (FT-IR) was used to understand the reversibility of the shape-memory mechanism of the synthesized feedstock. A swelling study in different solvents was performed as a driving force to further encapsulate the drug molecules into p(NIPAM-4ABP) network. Finally, the shape memory behavior of this synthesized polymer was established via converted it into p(NIPAM-4ABP) feedstock to validate the excellent shape memory features.

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References

  • Ayar Z, Shafieian M, Mahmoodi N, Sabzevari O, Hassannejad Z (2021) A rechargeable drug delivery system based on pNIPAM hydrogel for the local release of curcumin. J Appl Polym Sci 138:51167

    Article  CAS  Google Scholar 

  • Bakó I, Pusztai L, Temleitner L (2017) Decreasing temperature enhances the formation of sixfold hydrogen bonded rings in water-rich water-methanol mixtures. Sci Rep 7:1–7

    Article  Google Scholar 

  • Biswal HS, Wategaonkar S (2009) Nature of the n−h··· s hydrogen bond. J Phys Chem A 113:12763–12773

    Article  CAS  PubMed  Google Scholar 

  • Dong Q, Luo C, Li N, Chi J, Zhang Q (2018) Temperature and recognition dual responsive poly (N-isopropylacrylamide) and poly (N, N-dimethylacrylamide) with adamantyl side group. Materials 11:473

    Article  PubMed  PubMed Central  Google Scholar 

  • Estabrook DA, Chapman JO, Yen S-T, Lin HH, Ng ET, Zhu L, van de Wouw HL, Campàs O, Sletten EM (2022) Macromolecular crowding as an intracellular stimulus for responsive nanomaterials. J Am Chem Soc 144(37):16792–16798

    Article  CAS  PubMed  Google Scholar 

  • Giguère PA (1984) Bifurcated hydrogen bonds in water. J Raman Spectrosc 15:354–359

    Article  Google Scholar 

  • Guan Y, Zhang Y (2011) PNIPAM microgels for biomedical applications: from dispersed particles to 3D assemblies. Soft Matter 7:6375–6384

    Article  CAS  Google Scholar 

  • Huang WM, Zhao Y, Wang CC, Purnawali H, Tang C, Zhang JL (2012) Thermo/chemo-responsive shape memory effect in polymers: a sketch of working mechanisms, fundamentals and optimization. J Polym Res 19(9):1–34

    Article  Google Scholar 

  • Jiang S, Liu F, Lerch A, Ionov L, Agarwal S (2015) Unusual and superfast temperature-triggered actuators. Adv Mater 27:4865–4870

    Article  CAS  PubMed  Google Scholar 

  • Jindal A, Vasudevan S (2020) Molecular conformation and hydrogen bond formation in liquid ethylene glycol. J Phys Chem B 124:9136–9143

    Article  CAS  PubMed  Google Scholar 

  • Jung Y, Marcus R (2007) On the theory of organic catalysis “on water.” J Am Chem Soc 129:5492–5502

    Article  CAS  PubMed  Google Scholar 

  • Khan A (2000) A liquid water model: Density variation from supercooled to superheated states, prediction of H–bonds, and temperature limits. J Phys Chem B 104:11268–11274

    Article  CAS  Google Scholar 

  • Kommi DN, Kumar D, Seth K, Chakraborti AK (2013) Protecting group-free concise synthesis of (RS)/(S)-lubeluzole. Org Lett 15:1158–1161

    Article  CAS  PubMed  Google Scholar 

  • Laurence C, Mansour S, Vuluga D, Planchat A, Legros J (2021) Hydrogen-bond acceptance of solvents: a 19F solvatomagnetic β1 database to replace solvatochromic and solvatovibrational scales. J Org Chem 86:4143–4158

    Article  CAS  PubMed  Google Scholar 

  • Lemanowicz M, Gierczycki A, Kuźnik W, Sancewicz R, Imiela P (2014) Determination of lower critical solution temperature of thermosensitive flocculants. Miner Eng 69:170–176

    Article  CAS  Google Scholar 

  • Li F, Zhu Y, You B, Zhao D, Ruan Q, Zeng Y, Ding C (2010) Smart hydrogels co-switched by hydrogen bonds and π–π stacking for continuously regulated controlled-release system. Adv Funct Mater 20:669–676

    Article  CAS  Google Scholar 

  • Mallamace D, Fazio E, Mallamace F, Corsaro C (2018) The role of hydrogen bonding in the folding/unfolding process of hydrated lysozyme: a review of recent NMR and FTIR results. Int J Mol Sci 19:3825

    Article  PubMed  PubMed Central  Google Scholar 

  • Martinez MV, Molina M, Barbero CA (2018) Poly (N-isopropylacrylamide) cross-linked gels as intrinsic amphiphilic materials: swelling properties used to build novel interphases. J Phys Chem B 122:9038–9048

    Article  CAS  PubMed  Google Scholar 

  • Merline JD, Reghunadhan NC, Ninan K (2008) Synthesis, characterization, curing and shape memory properties of epoxy-polyether system. J Macromol Sci a 45:312–322

    Article  CAS  Google Scholar 

  • Shun L (2021) Studies on 4D printing thermo-responsive PNIPAM-based materials (Doctoral dissertation), The University of Akron, Akron

  • Stoychev G, Puretskiy N, Ionov L (2011) Self-folding all-polymer thermoresponsive microcapsules. Soft Matter 7:3277–3279

    Article  CAS  Google Scholar 

  • Sun L, Huang WM, Ding Z, Zhao Y, Wang CC, Purnawali H, Tang C (2012) Stimulus-responsive shape memory materials: a review. Mater Des 1(33):577–640

    Article  Google Scholar 

  • Takamuku T, Saisho K, Nozawa S, Yamaguchi T (2005) X-ray diffraction studies on methanol–water, ethanol–water, and 2-propanol–water mixtures at low temperatures. J Mol Liq 119:133–146

    Article  CAS  Google Scholar 

  • Takei YG, Aoki T, Sanui K, Ogata N, Okano T, Sakurai Y (1993) Temperature-responsive bioconjugates. 2. Molecular design for temperature-modulated bioseparations. Bioconjug Chem 4:341–346

    Article  CAS  PubMed  Google Scholar 

  • Vikulina AS, Feoktistova NA, Balabushevich NG, von Klitzing R, Volodkin D (2020) Cooling-triggered release from mesoporous poly (n-isopropylacrylamide) microgels at physiological conditions. ACS Appl Mater Interfaces 12:57401–57409

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • Vilotijevic I, Jamison TF (2007) Epoxide-opening cascades promoted by water. Science 317:1189–1192

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • Yoshida R, Kaneko YO, Sakai K, Okano T, Sakurai Y, Bae Y, Kim S (1994) Positive thermosensitive pulsatile drug release using negative thermosensitive hydrogels. J Control Release 32:97–102

    Article  CAS  Google Scholar 

  • Young RE, Graf J, Miserocchi I, Van Horn RM, Gordon MB, Anderson CR, Sefcik LS (2019) Optimizing the alignment of thermoresponsive poly (N-isopropyl acrylamide) electrospun nanofibers for tissue engineering applications: a factorial design of experiments approach. PLoS ONE 14:e0219254

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  • Zakharchenko S, Puretskiy N, Stoychev G, Stamm M, Ionov L (2010) Temperature controlled encapsulation and release using partially biodegradable thermo-magneto-sensitive self-rolling tubes. Soft Matter 6:2633–2636

    Article  CAS  Google Scholar 

  • Zavgorodnya O, Kozlovskaya V, Liang X, Kothalawala N, Catledge SA, Dass A, Kharlampieva E (2014) Temperature-responsive properties of poly (N-vinylcaprolactam) multilayer hydrogels in the presence of Hofmeister anions. Mater Res Express 1:035039

    Article  CAS  Google Scholar 

  • Zhang JL, Huang WM, Lu HB (2014) Thermo-/chemo-responsive shape memory/change effect in a hydrogel and its composites. Mater Des 1(53):1077–1088

    Article  Google Scholar 

  • Zhang H, Zhang L, You J, Zhang N, Yu L, Zhao H, Qian H-J, Lu Z-Y (2021) Controlling the chain folding for the synthesis of single-chain polymer nanoparticles using thermoresponsive polymers. CCS Chem 3:2143–2154

    Article  CAS  Google Scholar 

  • Zhao Z, Li Z, Xia Q, Bajalis E, Xi H, Lin Y (2008) Swelling/deswelling kinetics of PNIPAAm hydrogels synthesized by microwave irradiation. Chem Eng J 142:263–270

    Article  CAS  Google Scholar 

  • Zhou S, Zheng X, Yu X, Wang J, Weng J, Li X, Feng B, Yin M (2007) Hydrogen bonding interaction of poly (D, L-lactide)/hydroxyapatite nanocomposites. Chem Mater 19:247–253

    Article  CAS  Google Scholar 

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Acknowledgements

S.B. sincerely acknowledges the award support received from the SERB, Ministry of Science and Technology, Government of India, through SERB-SIRE fellowship vide Award No: SIR/2022/000111.

Funding

This study was funded through the Science and Engineering Research Board (SERB)-International Research Experience (SIRE) 2022–23 fellowship for the project titled “Responsive Self-folding Feedstock for Pharmaceutical 4D Printing Applications” vide Award No: SIR/2022/000111 supported by the SERB, Ministry of Science and Technology, Government of India, New Delhi.

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Correspondence to Kapileswar Seth or Subham Banerjee.

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Suryavanshi, P., Kawre, S., Maniruzzaman, M. et al. Thermo-responsive self-folding feedstock with excellent shape memory programming. Chem. Pap. 77, 3145–3154 (2023). https://doi.org/10.1007/s11696-023-02693-8

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