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Effect of alkyl chain lengths on the assemblies of magnetic nanoparticles coated with multi-functional thiolactone-containing copolymer

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Abstract

This work presents the synthesis of magnetite nanoparticle (MNP) coated with poly(N,N-diethylaminoethyl methacrylate)-b-poly(N-isopropyl acrylamide-st-thiolactone acrylamide) (PDEAEMA-b-P(NIPAAm-st-TlaAm) copolymer and its use in controlled drug release and bio-conjugation. TlaAm units in the copolymer were ring-opened with various alkyl amines to form thiol groups (-SH), followed by thiol-ene coupling reactions with acrylamide-coated MNP and then quaternized to obtain cationic copolymer-MNP assemblies (the size < 200 nm/cluster). The use of alkyl amines having various chain lengths (e.g., 1-propylamine, 1-octylamine, or 1-dodecylamine) in the nucleophilic ring-opening reactions of the thiolactone rings affected their magnetic separation ability, water dispersibility, and release rate of doxorubicin model drug. In all cases, when increasing the temperature, they showed a thermo-responsive behavior as indicated by the decrease in hydrodynamic size and the accelerated drug release rate. These copolymer-MNP assemblies could be used as a novel platform with thermal-triggering controlled drug release and capability for adsorption with any negatively charged biomolecules.

MNP coated with multi-functional PDEAEMA-b-P(NIPAAm-st-TlaAm) copolymer and its proposed drug release

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References

  • Bischofberger I, Trappe V (2015) New aspects in the phase behaviour of poly-N-isopropyl acrylamide: systematic temperature dependent shrinking of PNiPAM assemblies well beyond the LCST. Sci Rep 5:15520–15529

    Article  Google Scholar 

  • Braunecker WA, Matyjaszewski K (2007) Controlled/living radical polymerization: features, developments, and perspectives. Prog Polym Sci 32:93–146

    Article  Google Scholar 

  • Chen J-T, Ahmed M, Liu Q, Narain R (2012) Synthesis of cationic magnetic nanoparticles and evaluation of their gene delivery efficacy in Hep G2 cells. J Biomed Mater Res A 100A:2342–2347

    Google Scholar 

  • Chen Y, Espeel P, Reinicke S, Du Prez FE, Stenzel MH (2014) Control of glycopolymer nanoparticle morphology by a one-pot, double modification procedure using thiolactones. Macromol Rapid Commun 35:1128–1134

    Article  Google Scholar 

  • Chen L, Zhang H, Li L, Yang Y, Liu X, Xu B (2015) Thermoresponsive hollow magnetic microspheres with hyperthermia and controlled release properties. J Appl Polym Sci 132:42617

    Google Scholar 

  • Du H, Wickramasinghe R, Qian X (2010) Effects of salt on the lower critical solution temperature of poly (N-isopropylacrylamide). J Phys Chem 114:16594–16604

    Article  Google Scholar 

  • Espeel P, Du Prez FE (2015) One-pot multi-step reactions based on thiolactone chemistry: a powerful synthetic tool in polymer science. Eur Polym J 6:247–272

    Article  Google Scholar 

  • Espeel P, Goethals F, Du Prez FE (2011) One-pot multistep reactions based on thiolactones: extending the realm of thiol-ene chemistry in polymer synthesis. J Am Chem Soc 133:1678–1681

    Article  Google Scholar 

  • Espeel P, Goethals F, Stamenovi MM, Petton L, Du Prez FE (2012) Double modular modification of thiolactone-containing polymers: towards polythiols and derived structures. Polym Chem 3:1007–1015

    Article  Google Scholar 

  • Gandhi A, Paul A, Sen OS, Sen KK (2015) Studies on thermoresponsive polymers: phase behaviour, drug delivery and biomedical applications. Asian J Pharm Sci 10:99–107

    Article  Google Scholar 

  • Hill MR, Carmean RN, Sumerlin BS (2015) Expanding the scope of RAFT polymerization: recent advances and new horizons. Macromolecules 48:5459–5469

    Article  Google Scholar 

  • Hu Y, Meng L, Niu L, Lu Q (2013) Highly cross-linked and biocompatible polyphosphazene-coated superparamagnetic Fe3O4 nanoparticles for magnetic resonance imaging. Langmuir 29:9156–9163

    Article  Google Scholar 

  • Huang L, Liu M, Mao L, Xu D, Wan Q, Zeng G, Shi Y, Wen Y, Zhang X, Wei Y (2017) Preparation and controlled drug delivery applications of mesoporous silica polymer nanocomposites through the visible light induced surface-initiated ATRP. Appl Surf Sci 412:571–577

    Article  Google Scholar 

  • Leung KCF, Lee S, Wong C, Chak C, Lai JMY, Zhu X, Wang YJ, Wang YXJ, Cheng CHK (2013) Nanoparticle–DNA–polymer composites for hepatocellular carcinoma cell labeling, sensing, and magnetic resonance imaging. Methods 64:315–321

    Article  Google Scholar 

  • Li Y, Zhang X, Cheng H, Kim G, Cheng S, Zhuo R (2006) Novel stimuli-responsive micelle self-assembled from Y-shaped P(U-Y-NIPAAm) copolymer for drug delivery. Biomacromolecules 7:2956–2960

    Article  Google Scholar 

  • Lim J, Yeap SP, Che HX, Low SC (2013) Characterization of magnetic nanoparticle by dynamic light scattering. Nanoscale Res Lett 8:381–394

    Article  Google Scholar 

  • Liu P, Luo Q, Guan Y, Zhang Y (2010) Drug release kinetics from monolayer films of glucose-sensitive microgel. Polymer 51:2668–2675

    Article  Google Scholar 

  • Lowe AB (2010) Thiol-ene “click” reactions and recent applications in polymer and materials synthesis. Polym Chem 1:17–36

    Article  Google Scholar 

  • Machida N, Inoue Y, Ishihara K (2014) Phospholipid polymer-coverd magnetic nanoparticles for tracking intracellular molecular reaction. Trans Mat Res Soc Japan 39:427–430

    Article  Google Scholar 

  • Maeda Y, Mochiduki H (2004) Hydration changes during thermosensitive association of a block copolymer consisting of LCST and UCST blocks. Macromol Rapid Commun 25:1330–1334

    Article  Google Scholar 

  • Mahmoud WE, Bronstein LM, Al-Hazmi F, Al-Noaiser F, Al-Ghamdi AA (2013) Development of Fe/Fe3O4 core-shell nanocubes as a promising magnetic resonance imaging contrast agent. Langmuir 29:13095–13101

    Article  Google Scholar 

  • Matyjaszewski K (2012) Atom transfer radical polymerization (ATRP): current status and future perspectives. Macromolecules 45:4015–4039

    Article  Google Scholar 

  • Meerod S, Rutnakornpituk B, Wichai U, Rutnakornpituk M (2015) Hydrophilic magnetic nanoclusters with thermo-responsive properties and their drug controlled release. J Magn Magn Mater 392:83–90

    Article  Google Scholar 

  • Mekkapat S, Thong-On B, Rutnakornpituk B, Wichai U, Rutnakornpituk M (2013) Magnetic core–bilayer shell complex of magnetite nanoparticle stabilized with mPEG–polyester amphiphilic block copolymer. J Nanopart Res 15:2051–2062

    Article  Google Scholar 

  • Moad G, Rizzardo E, Thang SH (2008) Radical addition fragmentation chemistry in polymer synthesis. Polymer 49:1079–1131

    Article  Google Scholar 

  • Patil SS, Wadgaonkar PP (2017) Temperature and pH dual stimuli responsive PCL-b-PNIPAAm block copolymer assemblies and the cargo release studies. J Polym Sci A Polym Chem 55:1383–1396

    Article  Google Scholar 

  • Prabha G, Raj V (2016) Preparation and characterization of polymer nanocomposites coated magnetic nanoparticles for drug delivery applications. J Magn Magn Mater 408:26–34

    Article  Google Scholar 

  • Qin S, Qin D, Ford WT, Resasco DE, Herrera JE (2004) Functionalization of single-walled carbon nanotubes with polystyrene via grafting to and grafting from methods. Macromolecules 37:752–757

    Article  Google Scholar 

  • Qu Y, Li J, Ren J, Leng J, Lin C, Shi D (2014) Enhanced magnetic fluid hyperthermia by micellar magnetic nanoclusters composed of MnxZn1-xFe2O4 nanoparticles for induced tumor cell apoptosis. ACS Appl Mater Interfaces 6:16867–16879

    Article  Google Scholar 

  • Reinicke S, Espeel P, Stamenović MM, Du Prez FE (2013) One-pot double modification of P(NIPAAm): a tool for designing tailor-made multiresponsive polymers. ACS Macro Lett 2:539–543

    Article  Google Scholar 

  • Rodkate N, Rutnakornpituk M (2016) Multi-responsive magnetic microsphere of poly(N-isopropylacrylamide)/carboxymethylchitosan hydrogel for drug controlled release. Carbohydr Polym 151:251–259

    Article  Google Scholar 

  • Sahoo B, Devi KSP, Banerjee R, Maiti TK, Pramanik P, Dhara D (2013) Thermal and pH responsive polymer-tethered multifunctional magnetic nanoparticles for targeted delivery of anticancer drug. ACS Appl Mater Interfaces 5:3884–3893

    Article  Google Scholar 

  • Sciannamea V, Jérôme R, Detrembleur C (2008) In-situ nitroxide-mediated radical polymerization (NMP) processes: their understanding and optimization. Chem Rev 108:1104–1126

    Article  Google Scholar 

  • Singh LP, Srivastava SK, Mishra R, Ningthoujam RS (2014) Multifunctional hybrid nanomaterials from water dispersible CaF2:Eu3+, Mn2+ and Fe3O4 for luminescence and hyperthermia application. J Phys Chem C 118:18087–18096

    Article  Google Scholar 

  • Stamenovi MM, Espeel P, Van Camp V, Du Prez FE (2011) Norbornenyl-based RAFT agents for the preparation of functional polymers via thiol-ene chemistry. Macromolecules 44:5619–5630

    Article  Google Scholar 

  • Trongsatitkul T, Budhlall BM (2013) Microgels or microcapsules? Role of morphology on the release kinetics of thermoresponsive PNIPAm-co-PEGMa hydrogels. Polym Chem 4:1502–1516

    Article  Google Scholar 

  • Ulbrich K, Holá K, Šubr V, Bakandritsos A, Tuček J, Zbořil R (2016) Targeted drug delivery with polymers and magnetic nanoparticles: covalent and noncovalent approaches, release control, and clinical studies. Chem Rev 116:5338–5431

    Article  Google Scholar 

  • Wang B, Li B, Zhao B, Li CY (2008) Amphiphilic janus gold nanoparticles via combining “solid-state grafting-to” and “grafting-from” methods. J Am Chem Soc 130:11594–11595

    Article  Google Scholar 

  • Wang C, Xu H, Liang C, Liu Y, Li Z, Yang G, Cheng L, Li Y, Liu Z (2013) Iron oxide @ polypyrrole nanoparticles as a multifunctional drug carrier for remotely controlled cancer therapy with synergistic antitumor effect. ACS Nano 7:6782–6795

    Article  Google Scholar 

  • Willcock H, O’Reilly RK (2010) End group removal and modification of RAFT polymers. Polym Chem 1:149–157

    Article  Google Scholar 

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Acknowledgements

The authors acknowledge the Thailand Research Fund (TRF)(RSA5980002) for financial support. MR thanks the National Research Council of Thailand (NRCT) (R2561B086) for the supports. SP thanks The Royal Golden Jubilee PhD Program (PhD/0210/2556) for the scholarship.

Funding

This study was funded by The Thailand Research Fund (TRF) (RSA5980002), the National Research Council of Thailand (NRCT) (R2561B086), and the Royal Golden Jubilee PhD Program (PhD/0210/2556).

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Authors and Affiliations

  1. Department of Chemistry and Center of Excellence in Biomaterials, Faculty of Science, Naresuan University, Phitsanulok, 65000, Thailand

    Sujittra Paenkaew & Metha Rutnakornpituk

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  1. Sujittra Paenkaew
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  2. Metha Rutnakornpituk
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Correspondence to Metha Rutnakornpituk.

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Paenkaew, S., Rutnakornpituk, M. Effect of alkyl chain lengths on the assemblies of magnetic nanoparticles coated with multi-functional thiolactone-containing copolymer. J Nanopart Res 20, 193 (2018). https://doi.org/10.1007/s11051-018-4295-2

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