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Novel amphiphilic A2B2 type miktoarm star polymer with disulfide bonds based on PEG and PCL: micellization study

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Abstract

A diazidohydrin prepared from diglycidyl ether of ethylene glycol was used as a tetrafunctional core to prepare amphiphilic A2B2 type miktoarm star copolymer based on polyethylene glycol (PEG) and polycaprolactone (PCL). Presynthesized carboxyl-terminated poly (oxyethylene) hydrophilic arms having disulfide linkages as well as yne-terminated poly(oxy-1-oxohexamethylene) hydrophobic arms were connected to the core molecules via esterification and cycloaddition reactions, respectively. The structures obtained were verified by Fourier-transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopy techniques. The (PEG)2–(PCL)2 amphiphiles self-assemble to micelles at the critical micelle concentration (CMC) of 8.2 × 10–3 mg/mL. Interconnected masses of the nano-sized micelles were clearly distinguishable in the field emission-scanning electron microscopy (FE-SEM) image. Also, transmission electron microscopy (TEM) showed that the micelles were evenly distributed in aqueous solution as spherical particles with an average diameter of < 50 nm. Dynamic light scattering (DLS) measurements displayed a sharp unimodal distribution of micelles with an average hydrodynamic diameter of DH = 25 nm and a narrow polydispersity index of PDI = 0.55.

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References

  1. Pandey B, Patil NG, Bhosle GS et al (2018) Amphiphilic glycopolypeptide star copolymer-based cross-linked nanocarriers for targeted and dual-stimuli-responsive drug delivery. Bioconjug Chem 30:633–646

    Article  Google Scholar 

  2. Yu C, Wang L, Xu Z et al (2020) Smart micelles self-assembled from four-arm star polymers as potential drug carriers for pH-triggered DOX release. J Polym Res 27:1–10

    Article  Google Scholar 

  3. Mielańczyk A, Odrobińska J, Grządka S et al (2016) Miktoarm star copolymers from D-(−)-salicin core aggregated into dandelion-like structures as anticancer drug delivery systems: synthesis, self-assembly and drug release. Int J Pharm 515:515–526

    Article  PubMed  Google Scholar 

  4. Zhang S, Hou Y, Chen H et al (2018) Reduction-responsive amphiphilic star copolymers with long-chain hyperbranched poly (ε-caprolactone) core and disulfide bonds for trigger release of anticancer drugs. Eur Polymer J 108:364–372

    Article  CAS  Google Scholar 

  5. Long L, Zhao J, Li K et al (2016) Synthesis of star-branched PLA-b-PMPC copolymer micelles as long blood circulation vectors to enhance tumor-targeted delivery of hydrophobic drugs in vivo. Mater Chem Phys 180:184–194

    Article  CAS  Google Scholar 

  6. Ali I, Kareem F, Rahim S et al (2020) Architecture based selectivity of Amphiphilic block copolymers of poly (ethylene oxide) and poly (ε-caprolactone) for drug delivery. React Funct Polym 150:104553

    Article  CAS  Google Scholar 

  7. Huang Y, Yan J, Peng S et al (2020) pH/reduction dual-stimuli-responsive cross-linked micelles based on multi-functional amphiphilic star copolymer: synthesis and controlled anti-cancer drug release. Polymers 12:82

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  8. Lotocki V, Yazdani H, Zhang Q et al (2021) Miktoarm Star polymers with environment-selective ros/gsh responsive locations: from modular synthesis to tuned drug release through micellar partial corona shedding and/or core disassembly. Macromol Biosci 21:2000305

    Article  CAS  Google Scholar 

  9. Oliveira ASR, Mendonça Pv, Simões S et al (2021) Amphiphilic well-defined degradable star block copolymers by combination of ring-opening polymerization and atom transfer radical polymerization: synthesis and application as drug delivery carriers. J Polym Sci 59:211–229

    Article  CAS  Google Scholar 

  10. Vlassi E, Papagiannopoulos A, Pispas S (2021) Amphiphilic AxBy mikto-arm star copolymers with PLMA and POEGMA arms: self-assembly and drug encapsulation. J Polym Sci 59:775–786

    Article  CAS  Google Scholar 

  11. Alizadeh R, Ghaemy M (2015) pH-responsive ABC type miktoarm star terpolymers: synthesis via combination of click reaction and SET-LRP, characterization, self-assembly, and controlled drug release. Polymer 66:179–191

    Article  CAS  Google Scholar 

  12. Motamedi S, Massoumi B, Jaymand M, Hamishehkar H (2020) A dual stimuli-responsive star-shaped nanocarrier as de novo drug delivery system for chemotherapy of solid tumors. J Polym Res 27:1–12

    Article  Google Scholar 

  13. Huang Y, Tang Z, Peng S et al (2020) pH/redox/UV irradiation multi-stimuli responsive nanogels from star copolymer micelles and Fe3+ complexation for “on-demand” anticancer drug delivery. React Funct Polym 149:104532

    Article  CAS  Google Scholar 

  14. Zhang R, Wen L, Wu W et al (2019) Quantitative structure-property relationship for pH-triggered drug release performance of acid-responsive four/six-arms star polymeric micelles. Pharm Res 36:1–10

    Article  Google Scholar 

  15. Yuan W, Gao X, Pei E, Li Z (2018) Light-and pH-dually responsive dendrimer-star copolymer containing spiropyran groups: synthesis, self-assembly and controlled drug release. Polym Chem 9:3651–3661

    Article  CAS  Google Scholar 

  16. Shang Y, Zheng N, Wang Z (2019) Tetraphenylsilane-cored star-shaped polymer micelles with pH/redox dual response and active targeting function for drug-controlled release. Biomacromol 20:4602–4610

    Article  CAS  Google Scholar 

  17. Buwalda S, al Samad A, el Jundi A et al (2018) Stabilization of poly (ethylene glycol)-poly (ε-caprolactone) star block copolymer micelles via aromatic groups for improved drug delivery properties. J Colloid Interface Sci 514:468–478

    Article  CAS  PubMed  Google Scholar 

  18. Yoon K, Kang HC, Li L et al (2015) Amphiphilic poly (ethylene glycol)-poly (ε-caprolactone) AB 2 miktoarm copolymers for self-assembled nanocarrier systems: synthesis, characterization, and effects of morphology on antitumor activity. Polym Chem 6:531–542

    Article  CAS  Google Scholar 

  19. Feng Z, Zhi-Ming W, Ya-Fei H et al (2014) Synthesis, self-assembly, and drug release behavior of star-shaped poly (ε-caprolactone)-b-poly (ethylene oxide) block copolymer with porphyrin core. J Appl Polym Sci. https://doi.org/10.1002/app.40996

    Article  PubMed  PubMed Central  Google Scholar 

  20. Khoee S, Hashemi A, Molavipordanjani S (2018) Synthesis and characterization of IUdR loaded PEG/PCL/PEG polymersome in mixed DCM/DMF solvent: experimental and molecular dynamics insights into the role of solvent composition and star architecture in drug dispersion and diffusion. Eur J Pharm Sci 114:1–12

    Article  CAS  PubMed  Google Scholar 

  21. Zhang Y, Luo S, Liang Y et al (2018) Synthesis, characterization, and property of biodegradable PEG-PCL-PLA terpolymers with miktoarm star and triblock architectures as drug carriers. J Biomater Appl 32:1139–1152

    Article  CAS  PubMed  Google Scholar 

  22. Gou P, Zhu W, Xu N, Shen Z (2009) Synthesis, self-assembly and drug-loading capacity of well-defined drug-conjugated amphiphilic A2B2 type miktoarm star copolymers based on poly (ε-caprolactone) and poly (ethylene glycol). J Polym Sci, Part A: Polym Chem 47:6962–6976

    Article  CAS  Google Scholar 

  23. Shi C, Guo X, Qu Q et al (2014) Actively targeted delivery of anticancer drug to tumor cells by redox-responsive star-shaped micelles. Biomaterials 35:8711–8722

    Article  CAS  PubMed  Google Scholar 

  24. Fan X, Wang X, Cao M et al (2017) “Y”-shape armed amphiphilic star-like copolymers: design, synthesis and dual-responsive unimolecular micelle formation for controlled drug delivery. Polym Chem 8:5611–5620

    Article  CAS  Google Scholar 

  25. Yang H, Zhao X, Zhang X et al (2018) Optimization of bioreducible micelles self-assembled from amphiphilic hyperbranched block copolymers for drug delivery. J Polym Sci, Part A: Polym Chem 56:1383–1394

    Article  CAS  Google Scholar 

  26. Kim Y, Uthaman S, Nurunnabi M et al (2018) Synthesis and characterization of bioreducible cationic biarm polymer for efficient gene delivery. Int J Biol Macromol 110:366–374

    Article  CAS  PubMed  Google Scholar 

  27. Zhao F, Yin H, Zhang Z, Li J (2013) Folic acid modified cationic γ-cyclodextrin-oligoethylenimine star polymer with bioreducible disulfide linker for efficient targeted gene delivery. Biomacromol 14:476–484

    Article  CAS  Google Scholar 

  28. Zhang S, Guo N, Wan G et al (2019) pH and redox dual-responsive nanoparticles based on disulfide-containing poly (β-amino ester) for combining chemotherapy and COX-2 inhibitor to overcome drug resistance in breast cancer. J Nanobiotechnol 17:1–17

    Article  Google Scholar 

  29. Lee YS, Kim HJ, Yang DH, Chun HJ (2019) Preparation and anticancer activity evaluation of self-assembled paclitaxel conjugated MPEG-PCL micelles on 4T1 cells. J Ind Eng Chem 71:369–377

    Article  CAS  Google Scholar 

  30. Chakraborty T, Chakraborty I, Ghosh S (2011) The methods of determination of critical micellar concentrations of the amphiphilic systems in aqueous medium. Arab J Chem 4:265–270

    Article  CAS  Google Scholar 

  31. Zhou C, Hou C, Wang L et al (2021) Synthesis and micellar property of amphiphilic brush-arm star copolymers via living ROMP. Polymer 229:123951

    Article  CAS  Google Scholar 

  32. Tasdelen MA (2011) Poly (epsilon-caprolactone)/clay nanocomposites via “click” chemistry. Eur Polymer J 47:937–941

    Article  CAS  Google Scholar 

  33. Lotocki V, Kakkar A (2020) Miktoarm Star Polymers: branched architectures in drug delivery. Pharmaceutics 12:827

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  34. Yong HW, Kakkar A (2021) Nanoengineering branched star polymer-based formulations: scope, strategies, and advances. Macromol Biosci 21(8):2100105

    Article  CAS  Google Scholar 

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Acknowledgements

The authors wish to express their gratitude to the School of Chemistry and Research Council of Damghan University for financial support of this research.

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Correspondence to Hossein Behniafar.

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Rezaei, A., Behniafar, H. Novel amphiphilic A2B2 type miktoarm star polymer with disulfide bonds based on PEG and PCL: micellization study. Polym. Bull. 80, 10249–10261 (2023). https://doi.org/10.1007/s00289-022-04564-w

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