Skip to main content
SpringerLink
Log in

Synthesis and fluorescence studies of dual-responsive nanoparticles based on amphiphilic azobenzene-contained poly (monomethyl itaconate)

  • Original Paper
  • Published:
Journal of Polymer Research Aims and scope Submit manuscript

Abstract

Here photo- and pH-responsive behavior of polymer micelles formed by synthesized azo-modified poly (monomethyl itaconate)s (PMMI-Azo) with appropriate amounts of azobenzene side groups (DSAzo) were reported. The PMMI-Azo polymer with DSazo = 20 was used for the preparation of micelles using dialysis method. Self-assembly behavior of the PMMI-Azo was studied by transmission electron microscopy (TEM), fluorescence spectroscopy, dynamic light scattering (DLS) and UV–Vis spectrophotometry techniques. It was found that the PMMI-Azo polymers self-assembled into spherical micelles with core-shell structures. TEM images and DLS analysis of the PMMI-Azo-20 micelles showed regular spherical micelles which increased in size and polydispersity index after UV irradiation, caused by isomerization. It was also found that with increasing the polymer concentration, the fluorescence intensity decreased obviously which could be attributed to the interactions between the closely located pyrene and azobenzene in the micelles core. Experimental results suggested that the micellization-enhanced fluorescence was caused by a slowdown in the rate of the trans-to-cis photoisomerization. Furthermore, it was found that the fluorescence intensity of the aqueous micellar solutions was sensitive to stimulus such as pH change and UV light irradiation, as a result of alteration in aqueous micellar association. The results clearly indicated the role of UV irradiation and pH in the state of the polymer micellar association which is responsible for fluorescence intensity.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9

Similar content being viewed by others

References

  1. Mao J, Ji X, Bo S (2011) Synthesis and pH/temperature-responsive behavior of PLLA-b-PDMAEMA block polyelectrolytes prepared via ROP and ATRP. Macromol Chem Phys 212:744–752

    Article  CAS  Google Scholar 

  2. Wang F, Zhang D, Duan C, Jia L, Feng F, Liu Y, Wang Y, Hao L, Zhang Q (2011) Preparation and characterizations of a novel deoxycholic acid–O-carboxymethylated chitosan–folic acid conjugates and self-aggregates. Carbohyd Polym 84:1192–1200

    Article  CAS  Google Scholar 

  3. Tabatabaei Rezaei SJ, Nabid MR, Niknejad H, Entezami AA (2012) Folate-decorated thermoresponsive micelles based on star-shaped amphiphilic block copolymers for efficient intracellular release of anticancer drugs. Int J Pharm 437:70–79

    Article  Google Scholar 

  4. Yu B, Jiang X, Wang R, Yin J (2010) Multi stimuli responsive polymer nanoparticles on the basis of the amphiphilic azobenzene-contained hyperbranched poly(ether amine). Macromolecules 43:10457–10465

    Article  CAS  Google Scholar 

  5. Mura S, Nicolas J, Couvreur P (2013) Stimuli-responsive naocarriers for drug delivery. Nat Mater 12:991–10034

    Article  CAS  Google Scholar 

  6. Stuart MAC, Huck WTS, Genzer J, Muller M, Ober C, Stamm M, Shukhorukov GB, Szleifer I, Tsukruk VV, Urban M, Winnik F, Zauscher S, Luzinov I, Minko S (2010) Emerging applications of stimuli-responsive polymer materials. Nat Mater 9:101–113

    Article  Google Scholar 

  7. Karimi M, Sahandi Zangabad P, Ghasemi A, Hamblin MR (2015) Smart external stimulus-responsive nanocarriers for drug and gene delivery. Morgan & Claypool Publishers, San Rafael. doi:10.1088/978-1-6817-4202-1

  8. Gao GH, Park MJ, Li Y, Im GH, Kim JH, Kim HN, Lee JW, Jeon P, Bang OY, Lee JH, Lee DS (2012) The use of pH-sensitive positively charged polymeric micelles for protein delivery. Biomaterials 33:9157–9164

    Article  CAS  Google Scholar 

  9. Moleaodorog Avin I, Ibanescu C, Hodorog-Rusu A, Peptu E, Doroftei F, Hurduc N (2011) Amphiphilic azopolymers capable to generate photo-sensitive micelles. Cent Eur J Chem 9(6):1117–1125

    Google Scholar 

  10. Wang G, Tong X, Zhao Y (2004) Preparation of azobenzene-containing amphiphilic diblock copolymers for light-responsive micellar aggregates. Macromolecules 37:8911–8917

    Article  CAS  Google Scholar 

  11. Jin Q, Luy C, Ji J, Agarwal S (2012) Design and proof of reversible micelle-to-vesicle multistimuli-responsive morphological regulations. J Polym Sci A Polym Chem 50:451–457

    Article  CAS  Google Scholar 

  12. Alvarez-Lorenzo C, Bromberg L, Concheiro A (2009) Light-sensitive intelligent drug delivery systems. Photochem Photobiol 85:848–860

    Article  CAS  Google Scholar 

  13. Fomina N, Sankaranarayanan J, Almutairi A (2012) Photochemical mechanism of light-triggered release from nanocarriers. Adv Drug Deliv Rev 64:1005–1020

    Article  CAS  Google Scholar 

  14. Goulet-Hanssens A, Barrett CJ (2013) Photo-control of niological systems with azobenzene polymers. J Polym Sci A Polym Chem 51:3058–3070

    Article  CAS  Google Scholar 

  15. Wang S, Shen Q, Hasnain Nawaz MH, Zhang w (2013) Photocontrolled reversible supramolecular assemblies of a diblock Azo-copolymer based on β-cyclodextrin–azo host–guest inclusion complexation. Polym Chem 4:215–2157

    CAS  Google Scholar 

  16. Lin S, Wang Y, Cai C, Xing Y, Lin J, Chen T, He X (2013) Tuning self-assembly and photo-responsive behavior of azobenzene-containing triblock copolymers by combining homopolymers. Nanotechnology 24:085602

    Article  Google Scholar 

  17. Gohy JF, Zhao Y (2013) Photo-responsive block copolymer micelles: design and behavior. Chem Soc Rev 42(17):7117–7129

    Article  CAS  Google Scholar 

  18. Saiz LM, Oyanguren PA, Galante MJ (2012) Polyurethane-epoxy based azopolymers: influence of chemical structure over photoinduced birefringence. React Funct Polym 72:478–485

    Article  CAS  Google Scholar 

  19. Forcen P, Oriol L, Sanchez C, Rodrigues FJ, Alcala R, Hvilsted S, Jankova K (2004) Methacrylic Azopolymers for holographic storage: a comparison among polymer types. Eur Polym J 43:3292–3300

    Article  Google Scholar 

  20. Ren H, Chen D, Shi Y, Yu H, Fu Z (2014) A carboxylic Azo monomer and its homopolymer: synthesis, self-organization and fluorescence behavior in solution. Polym Chem 6:270–277

    Article  Google Scholar 

  21. Li C, Lo C-W, Zhu D, Li C, Liu Y, Jiang H (2009) Synthesis of a photoresponsive liquid-crystalline polymer containing azobenzene. Macromol Rapid Commun 30:1928–1935

    Article  Google Scholar 

  22. Huang Y, Kang H, Li G, Wang C, Huang Y, Liu R (2013) Synthesis and photosensitivity of azobenzene functionalized hydroxypropyl cellulose. RCS Adv 3:15909–15916

    CAS  Google Scholar 

  23. Che P, He Y, Wang X (2005) Hyperbranched azo-polymers synthesized by azo-coupling reaction of an AB2 monomer and post polymerization modification. Macromolecules 38:8657–8663

    Article  CAS  Google Scholar 

  24. Schumers JM, Fustin CA, Gohy JF (2010) Light-responsive block copolymers. Macromol Rapid Commun 15 31(18):1588–607

    Article  CAS  Google Scholar 

  25. Jochum FD, Theato P (2010) Thermo- and light responsive micellation of azobenzene containing block copolymers. Chem Commun 28 46(36):6717–6719

    Article  CAS  Google Scholar 

  26. Bagheri M, Pourmoazzen Z, Entezami AA (2013) Synthesis, characterization and liquid crystalline behavior of poly(monomethyl itaconate)s with new pendant cholesterol moieties. Iran Polym J 22:303–311

    Article  CAS  Google Scholar 

  27. Pourmoazzen Z, Bagheri M, Entezami AA (2014) Cholesteryl-modified poly(monomethyl itaconate)s micelles as nano-carriers for pH-responsive drug delivery. Polym J 46:806–812

    Article  CAS  Google Scholar 

  28. Pourmoazzen Z, Bagheri M, Entezami AA, Kushki KN (2013) pH-responsive micelles composed of poly(ethylene glycol) and cholesterol-modified poly(monomethyl itaconate) as a nanocarrier for controlled and targeted release of piroxicam. J Polym Res 20:295–306

    Article  Google Scholar 

  29. Bagheri M, Pourmoazzen Z, Entezami AA (2013) pH-responsive nanosized-micelles based on poly(monomethylitaconate)-co-poly(dimethylaminoethyl methacrylate) and cholesterol side chains effect on pH change-induced release of piroxicam. J Polym Res 20:231–241

    Article  Google Scholar 

  30. Gargallo L, Radic D, Yazdani-Pedram M, Horta M (1989) Properties of polyelectrolytes: poly(monomethyl itaconate). Conformational and viscometric behavior in dilute solution. Eur Polym J 25:1059–1063

    Article  CAS  Google Scholar 

  31. Stewart D, Imrie CT (1996) Synthesis and characterization of spin-labelled and spin-probed side-chain liquid crystal polymers. Polymer 37(15):3419–3425

    Article  CAS  Google Scholar 

  32. Filip D, Macocinschi D (2014) Aggregation behavior β-cyclodextrine-based side-chain azo amphiphilic polyurethane. J Mater Sci 49:3451–3460

    Article  CAS  Google Scholar 

  33. Bo O, Zhao Y (2007) Fluorescence from an azobenzene-containing diblock copolymer micelle in solution. Langmuir 23:5746–5751

    Article  CAS  Google Scholar 

  34. Tsuda K, Dol GC, Gensch T, Hofkens J, Latterini L, Weener JW, Meijer EW, De Schryver FC (2000) Fluorescence from azobenzene functionalized poly (propylene imine) dendrimers in self-assembled supramolecular structures. J Am Chem Soc 122:3445–3452

Download references

Acknowledgments

The authors would like to thank the Vice Chancellor of Research of Azarbaijan Shahid Madani University for financially supporting this research. The authors’ warm thanks are also extended to Mr. Hossein Masaledan for his useful help.

Author information

Authors and Affiliations

  1. Chemistry Department, Science Faculty, Azarbaijan Shahid Madani University, P.O. Box: 53714-161, 5375171379, Tabriz, Iran

    Akram Golshan Hosseini, Massoumeh Bagheri & Rahim Mohammad-Rezaei

Authors
  1. Akram Golshan Hosseini
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Massoumeh Bagheri
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Rahim Mohammad-Rezaei
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Massoumeh Bagheri.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Hosseini, A.G., Bagheri, M. & Mohammad-Rezaei, R. Synthesis and fluorescence studies of dual-responsive nanoparticles based on amphiphilic azobenzene-contained poly (monomethyl itaconate). J Polym Res 23, 161 (2016). https://doi.org/10.1007/s10965-016-1061-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s10965-016-1061-y

Keywords

Search

Navigation