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Photocleavable amphiphilic diblock copolymer micelles bearing a nitrobenzene block

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Abstract

Amphiphilic diblock copolymers containing photocleavable nitrobenzene acrylate groups were synthesized by the reversible addition-fragmentation chain transfer (RAFT) method. The diblock copolymer (NBMA)14-b-(GLBT)47 consisted of nitrobenzyl methacrylate as a hydrophobic block and carboxy methyl betaine, industrially known as “GLBT,” as a hydrophilic, zwitterionic block. The diblock copolymer was self-assembled into the micelles of 30–40 nm hydrodynamic radii in aqueous buffer solution of various pHs. The diblock copolymer showed non-surface activity in alkaline and acidic buffers but remained surface active at a neutral buffer (pH 7). On exposure to UV irradiation of 360 nm light, polymeric micelles were dissociated due to cleavage of the acrylate bond leaving the block as a hydrophilic acid group. Significant change in surface activity at pH 7 was observed after UV irradiation and the copolymer tended to be less surface active. Encapsulation of a model drug was shown using Nile red, a fluorescence probe, and light-stimulated release of the hydrophobic molecule was demonstrated. Our focus is to develop a photoresponsive nano-carrier utilizing the above system.

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References

  1. Yan B, Tong X, Ayotte P, Zhao Y (2011) Light-responsive block copolymer vesicles based on a photo-softening effect. Soft Matter 7:10001–10009

    Article  CAS  Google Scholar 

  2. Torchilin VP (2007) Micellar nanocarriers: pharmaceutical perspectives. Pharm Res 24:1–16

    Article  CAS  Google Scholar 

  3. Klaikherd A, Nagamani C, Thayumanavan S (2009) Multi-stimuli sensitive amphiphilic block copolymer assemblies. J Am Chem Soc 131:4830–4838

    Article  CAS  Google Scholar 

  4. Pichot C (2004) Surface-functionalized latexes for biotechnological applications. Curr Opin Colloid Interface Sci 9:213–221

    Article  CAS  Google Scholar 

  5. Ko NR, Oh JK (2014) Glutathione-triggered disassembly of dual disulfide located degradable nanocarriers of polylactide-based block copolymers for rapid drug release. Biomacromolecules 15:3180–3189

    Article  CAS  Google Scholar 

  6. Wu W-C, Chen C-Y, Lee W-Y, Chen W-C (2015) Stimuli-responsive conjugated rod-coil block copolymers: synthesis, morphology, and applications. Polymer 65:A1–A16

    Article  CAS  Google Scholar 

  7. Miller T, Breyer S, van Colen G, Mier W, Haberkorn U, et al. (2013) Premature drug release of polymeric micelles and its effects on tumor targeting. Int J Pharm 445:117–124

    Article  CAS  Google Scholar 

  8. Wei H, Zhuo R-X, Zhang X-Z (2013) Design and development of polymeric micelles with cleavable links for intracellular drug delivery. Prog Polym Sci 38:503–535

    Article  CAS  Google Scholar 

  9. Lau CH, Li P, Li F, Chung T-S, Paul DR (2013) Reverse-selective polymeric membranes for gas separations. Prog Polym Sci 38:740–766

    Article  CAS  Google Scholar 

  10. Rahikkala A, Aseyev V, Tenhu H, Kauppinen EI, Raula J (2015) Thermoresponsive nanoparticles of self-assembled block copolymers as potential carriers for drug delivery and diagnostics. Biomacromolecules 16(9):2750–2756. doi:10.1021/acs.biomac.5b00690

    Article  CAS  Google Scholar 

  11. Delcea M, Möhwald H, Skirtach AG (2011) Stimuli-responsive LbL capsules and nanoshells for drug delivery. Adv Drug Deliv Rev 63:730–747

    Article  CAS  Google Scholar 

  12. Mura S, Nicolas J, Couvreur P (2013) Stimuli-responsive nanocarriers for drug delivery. Nat Mater 12:991–1003

    Article  CAS  Google Scholar 

  13. Cao J, Huang S, Chen Y, Li S, Li X, et al. (2013) Near-infrared light-triggered micelles for fast controlled drug release in deep tissue. Biomaterials 34:6272–6283

    Article  CAS  Google Scholar 

  14. Chen Z, Wang X, Zhang L, He L (2014) Vesicles from the self-assembly of coil–rod–coil triblock copolymers in selective solvents. Polymer 55:2921–2927

    Article  CAS  Google Scholar 

  15. Cui J, Han Y, Jiang W (2014) Asymmetric vesicle constructed by AB/CB diblock copolymer mixture and its behavior: A Monte Carlo Study. Langmuir 30:9219–9227

    Article  CAS  Google Scholar 

  16. Jiménez ZA, Yoshida R (2015) Temperature driven self-assembly of a zwitterionic block copolymer that exhibits triple thermoresponsivity and pH sensitivity. Macromolecules 48:4599–4606

    Article  Google Scholar 

  17. Robertson JD, Patikarnmonthon DN, Joseph AS, Battaglia G (2014) Block copolymer micelles and vesicles for drug delivery. Engineering polymer systems for improved drug delivery. John Wiley & Sons, Inc. Honoken, New Jersey, pp. 163–188

    Book  Google Scholar 

  18. Chuanoi S, Kishimura A, Dong W-F, Anraku Y, Yamasaki Y, et al. (2014) Structural factors directing nanosized polyion complex vesicles (Nano-PICsomes) to form a pair of block aniomer/homo catiomers: studies on the aniomer segment length and the catiomer side-chain structure. Polym J 46:130–135

    Article  CAS  Google Scholar 

  19. Huang X, Sevimli SI, Bulmus V (2013) pH-labile sheddable block copolymers by RAFT polymerization: synthesis and potential use as siRNA conjugates. Eur Polym J 49:2895–2905

    Article  CAS  Google Scholar 

  20. Yang Y, Pan D, Luo K, Li L, Gu Z (2013) Biodegradable and amphiphilic block copolymer–doxorubicin conjugate as polymeric nanoscale drug delivery vehicle for breast cancer therapy. Biomaterials 34:8430–8443

    Article  CAS  Google Scholar 

  21. Rizis G, van de Ven TGM, Eisenberg A (2014) “Raft” formation by two-dimensional self-assembly of block copolymer rod micelles in aqueous solution. Angew Chem Int Ed 53:9000–9003

    Article  CAS  Google Scholar 

  22. Moad G, Chong YK, Postma A, Rizzardo E, Thang SH (2005) Advances in RAFT polymerization: the synthesis of polymers with defined end-groups. Polymer 46:8458–8468

    Article  CAS  Google Scholar 

  23. Lowe AB, McCormick CL (2007) Reversible addition–fragmentation chain transfer (RAFT) radical polymerization and the synthesis of water-soluble (co)polymers under homogeneous conditions in organic and aqueous media. Prog Polym Sci 32:283–351

    Article  CAS  Google Scholar 

  24. Yan Q, Han D, Zhao Y (2013) Main-chain photoresponsive polymers with controlled location of light-cleavable units: from synthetic strategies to structural engineering. Polym Chem 4:5026–5037

    Article  CAS  Google Scholar 

  25. Cui J, Campo AD (2014) Photo-responsive polymers: properties, synthesis and application. In: M.R. A, J.S. R (eds) Smart polymers and their applications. Woodhead Publisher, Cambridge, pp. 93–133

    Chapter  Google Scholar 

  26. Shrivastava S, Matsuoka H (2014) Photoresponsive block copolymer: synthesis, characterization, and surface activity control. Langmuir 30:3957–3966

    Article  CAS  Google Scholar 

  27. Jiang J, Tong X, Morris D, Zhao Y (2006) Toward photocontrolled release using light-dissociable block copolymer micelles. Macromolecules 39:4633–4640

    Article  CAS  Google Scholar 

  28. Bertrand O, Schumers J-M, Kuppan C, Marchand-Brynaert J, Fustin C-A, et al. (2011) Photo-induced micellization of block copolymers bearing 4,5-dimethoxy-2-nitrobenzyl side groups. Soft Matter 7:6891–6896

    Article  CAS  Google Scholar 

  29. Jiang G, Jiang T, Chen H, Li L, Liu Y, et al. (2015) Preparation of multi-responsive micelles for controlled release of insulin. Colloid Polym Sci 293:209–215

    Article  CAS  Google Scholar 

  30. Mitsukami Y, Donovan MS, Lowe AB, McCormick CL (2001) Water-soluble polymers. 81. direct synthesis of hydrophilic styrenic-based homopolymers and block copolymers in aqueous solution via RAFT. Macromolecules 34:2248–2256

    Article  CAS  Google Scholar 

  31. Matsuoka H, Maeda S, Kaewsaiha P, Matsumoto K (2004) Micellization of non-surface-active diblock copolymers in water. special characteristics of poly(styrene)-block-poly(styrenesulfonate). Langmuir 20:7412–7421

    Article  CAS  Google Scholar 

  32. Chu B (1991) Laser light scattering, basic principles and practice. Academic Press, Boston

    Google Scholar 

  33. Han D, Tong X, Zhao Y (2011) Fast photodegradable block copolymer micelles for burst release. Macromolecules 44:437–439

    Article  CAS  Google Scholar 

  34. Wan X, Liu T, Liu S (2011) Synthesis of amphiphilic tadpole-shaped linear-cyclic diblock copolymers via ring-opening polymerization directly initiating from cyclic precursors and their application as drug nanocarriers. Biomacromolecules 12:1146–1154

    Article  CAS  Google Scholar 

  35. Ghosh A, Yusa SI, Matsuoka H, Saruwatari Y (2011) Non-surface activity and micellization behavior of cationic amphiphilic block copolymer synthesized by reversible addition-fragmentation chain transfer process. Langmuir 27:9237–9244

    Article  CAS  Google Scholar 

  36. Kaewsaiha P, Matsumoto K, Matsuoka H (2005) Non-surface activity and micellization of ionic amphiphilic diblock copolymers in water. Hydrophobic chain length dependence and salt effect on surface activity and the critical micelle concentration. Langmuir 21:9938–9945

    Article  CAS  Google Scholar 

  37. Matsuoka H, Chen H, Matsumoto K (2012) Molecular weight dependence of non-surface activity for ionic amphiphilic diblock copolymers. Soft Matter 8:9140–9146

    Article  CAS  Google Scholar 

  38. Matsuoka H, Hachisuka M, Uda K, Onishi T, Ozoe S (2012) Why ionic amphiphilic block copolymer can be non-surface active comparison of homopolymer, block and random copolymers of poly(styrenesulfonate). Chem Lett 41:1063–1065

    Article  CAS  Google Scholar 

  39. Matsuoka H, Fujita S, Ghosh A, Nakayama S, Yamakawa Y, et al. (2013) Nanostructure of cationic polymer brush at the air/water interface. MATEC Web of Conferences (EDP Sciences publisher) 4: 04001p04001-p04004.

  40. Kalyanasundaram K, Thomas JK (1977) Environmental effects on vibronic band intensities in pyrene monomer fluorescence and their application in studies of micellar systems. J Am Chem Soc 99:2039–2044

    Article  CAS  Google Scholar 

  41. Dey J, Shrivastava S (2012) Can molecules with an anionic head and a poly(ethylene glycol) methyl ether tail self-assemble in water? A surface tension, fluorescence probe, light scattering, and transmission electron microscopic investigation. Soft Matter 8:1305–1308

    Article  CAS  Google Scholar 

  42. Sutthasupa S, Shiotsuki M, Matsuoka H, Masuda T, Sanda F (2010) Ring-opening metathesis block copolymerization of amino acid functionalized norbornene monomers. Effects of Solvent and pH on Micelle Formation Macromolecules 43:1815–1822

    CAS  Google Scholar 

  43. Matsuoka H, Onishi T, Ghosh A (2014) pH-responsive non-surface-active/surface-active transition of weakly ionic amphiphilic diblock copolymers. Colloid Polym Sci 292:797–806

    Article  CAS  Google Scholar 

  44. Faust BC, Allen JM (1993) Aqueous-phase photochemical formation of hydroxyl radical in authentic cloudwaters and fogwaters. Environmental Science & Technology 27:1221–1224

    Article  CAS  Google Scholar 

Download references

Acknowledgments

We thank Dr. Yoshiyuki Saruwatari, Osaka Organic Chemical Industry Ltd., for kindly supplying the GLBT monomer. This work was supported by a grant-in-aid for Scientific Research on Innovative Areas “Molecular Soft-Interface Science” (20106006) from the Ministry of Education, Culture, Sports, Science and Technology of Japan, to which our sincere gratitude is due.

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  1. Saurabh Shrivastava

    Present address: Alpha Assembly Solution, Alpha India Research Centre, Bangalore, 50022, India

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  1. Department of Polymer Chemistry, Kyoto University, Kyoto, 615-8510, Japan

    Saurabh Shrivastava & Hideki Matsuoka

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  1. Saurabh Shrivastava
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  2. Hideki Matsuoka
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Correspondence to Hideki Matsuoka.

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Electronic supplementary material

Synthesis scheme and characterization of monomer (IR and NMR spectrum); polymer structure at different pHs, and variation in hydrodynamic radius of polymer micelles with irradiation time are available free of charge via the Internet.

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Shrivastava, S., Matsuoka, H. Photocleavable amphiphilic diblock copolymer micelles bearing a nitrobenzene block. Colloid Polym Sci 294, 879–887 (2016). https://doi.org/10.1007/s00396-016-3839-1

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  • DOI: https://doi.org/10.1007/s00396-016-3839-1

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