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Nano Research 2017, 10(2): 704-717 https://doi.org/10.1007/s12274-016-1330-4
Research Article | Issue | Published: 23 November 2016

General synthesis of high-performing magneto-conjugated polymer core–shell nanoparticles for multifunctional theranostics

Show Author's Information Hao Yan1,2,3,  Lingyun Zhao1,2,  Wenting Shang4,  Zhongqun Liu1,2,  Wensheng Xie1,2,  Cai Qiang1,2,  Zhiyuan Xiong2,  Ranran Zhang1,2,  Baohua Li3,  Xiaodan Sun1,2( ),  Feiyu Kang1,3( )
State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China
Key Laboratory of Advanced Materials of Ministry of Education of China, Tsinghua University, Beijing 100084, China
Engineering Laboratory for Functionalized Carbon Materials, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055, China
Key Laboratory of Molecular Imaging, Institute of Automation, Chinese Academy of Sciences, Beijing 100190, China
Keywords:
iron oxide, polypyrrole, photothermal, magnetic, hyperthermal, poly(3, 4-, ethylenedioxythiophene): poly(4-styrenesulfonate) (PEDOT: PSS)
Cite this article:
Yan H, Zhao L, Shang W, et al. General synthesis of high-performing magneto-conjugated polymer core–shell nanoparticles for multifunctional theranostics. Nano Research, 2017, 10(2): 704-717. https://doi.org/10.1007/s12274-016-1330-4
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Abstract Full text Electronic supplementary material About this article

Recently, increasing attention has been paid to magneto-conjugated polymer core–shell nanoparticles (NPs) as theranostic platforms. However, the utilization of surfactants and extra oxidizing agents with potential toxicity in synthesis, the lack of general methods for the controlled synthesis of various kinds of magnetic NP (MNP)@conjugated polymer NPs, and the difficulty of obtaining balanced magneto-optical properties have greatly limited the applications of magneto-conjugated polymers in theranostics. We developed an in situ surface polymerization method free of extra surfactants and oxidizing agents to synthesize MNP@polypyrrole (PPy) NPs with balanced, prominent magneto-optical properties. MNP@PPy NPs with an adjustable size, different shapes, and a controlled shell thickness were obtained using this method. The method was extended to synthesize other MNP-conjugated polymer core–shell NPs, such as MNP@polyaniline and MNP@poly(3, 4-ethylenedioxythiophene): poly(4- styrenesulfonate) (PEDOT: PSS). We discuss the formation mechanism of the proposed method according to our experimental results. Finally, using the optical and magnetic properties of the obtained MNP@PEDOT: PSS NPs, in vivo multimodal imaging-guided hyperthermia was induced in mice, achieving an excellent tumor-ablation therapeutic effect. Our work is beneficial for extending the application of MNP-conjugated polymer core–shell NPs in the biomedical field.


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Electronic supplementary material
About this article

General synthesis of high-performing magneto-conjugated polymer core–shell nanoparticles for multifunctional theranostics

Show Author's information Hao Yan1,2,3, Lingyun Zhao1,2, Wenting Shang4, Zhongqun Liu1,2, Wensheng Xie1,2, Cai Qiang1,2, Zhiyuan Xiong2, Ranran Zhang1,2, Baohua Li3, Xiaodan Sun1,2( ), Feiyu Kang1,3( )
State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China
Key Laboratory of Advanced Materials of Ministry of Education of China, Tsinghua University, Beijing 100084, China
Engineering Laboratory for Functionalized Carbon Materials, Graduate School at Shenzhen, Tsinghua University, Shenzhen 518055, China
Key Laboratory of Molecular Imaging, Institute of Automation, Chinese Academy of Sciences, Beijing 100190, China

Abstract

Recently, increasing attention has been paid to magneto-conjugated polymer core–shell nanoparticles (NPs) as theranostic platforms. However, the utilization of surfactants and extra oxidizing agents with potential toxicity in synthesis, the lack of general methods for the controlled synthesis of various kinds of magnetic NP (MNP)@conjugated polymer NPs, and the difficulty of obtaining balanced magneto-optical properties have greatly limited the applications of magneto-conjugated polymers in theranostics. We developed an in situ surface polymerization method free of extra surfactants and oxidizing agents to synthesize MNP@polypyrrole (PPy) NPs with balanced, prominent magneto-optical properties. MNP@PPy NPs with an adjustable size, different shapes, and a controlled shell thickness were obtained using this method. The method was extended to synthesize other MNP-conjugated polymer core–shell NPs, such as MNP@polyaniline and MNP@poly(3, 4-ethylenedioxythiophene): poly(4- styrenesulfonate) (PEDOT: PSS). We discuss the formation mechanism of the proposed method according to our experimental results. Finally, using the optical and magnetic properties of the obtained MNP@PEDOT: PSS NPs, in vivo multimodal imaging-guided hyperthermia was induced in mice, achieving an excellent tumor-ablation therapeutic effect. Our work is beneficial for extending the application of MNP-conjugated polymer core–shell NPs in the biomedical field.

Keywords: iron oxide, polypyrrole, photothermal, magnetic, hyperthermal, poly(3, 4-, ethylenedioxythiophene): poly(4-styrenesulfonate) (PEDOT: PSS)

References(45)

1

Siegel, R. L.; Miller, K. D.; Jemal, A. Cancer statistics, 2015. CA Cancer J. Clin. 2015, 65, 5–29.
DOI Google Scholar
2

Chen, X. Y.; Gambhlr, S. S.; Cheon, J. Theranostic nano­medicine. Acc. Chem. Res. 2011, 44, 841.
DOI Google Scholar
3

Deveza, L.; Choi, J.; Yang, F. Therapeutic angiogenesis for treating cardiovascular diseases. Theranostics 2012, 2, 801–814.
DOI Google Scholar
4

Muthu, M. S.; Leong, D. T.; Mei, L.; Feng, S. S. Nanotheranostics—Application and further development of nanomedicine strategies for advanced theranostics. Theranostics 2014, 4, 660–677.
DOI Google Scholar
5

Song, X. R.; Wang, X. Y.; Yu, S. X.; Cao, J. B.; Li, S. H.; Li, J.; Liu, G.; Yang, H. H.; Chen, X. Y. Co9Se8 nanoplates as a new theranostic platform for photoacoustic/magnetic resonance dual-modal-imaging-guided chemo-photothermal combination therapy. Adv. Mater. 2015, 27, 3285–3291.
DOI Google Scholar
6

Li, J. W.; Arnal, B.; Wei, C. W.; Shang, J.; Nguyen, T.-M.; O'Donnell, M.; Gao, X. H. Magneto-optical nanoparticles for cyclic magnetomotive photoacoustic imaging. ACS Nano 2015, 9, 1964–1976.
DOI Google Scholar
7

Yu, J.; Yang, C.; Li, J. D. S.; Ding, Y. C.; Zhang, L.; Yousaf, M. Z.; Lin, J.; Pang, R.; Wei, L. B.; Xu, L. L. et al. Multifunctional Fe5C2 nanoparticles: A targeted theranostic platform for magnetic resonance imaging and photoacoustic tomography-guided photothermal therapy. Adv. Mater. 2014, 26, 4114–4120.
DOI Google Scholar
8

Yu, J.; Ju, Y. M.; Zhao, L. Y.; Chu, X.; Yang, W. L.; Tian, Y. L.; Sheng, F. G.; Lin, J.; Liu, F.; Dong, Y. H. et al. Multistimuli-regulated photochemothermal cancer therapy remotely controlled via Fe5C2 nanoparticles. ACS Nano 2016, 10, 159–169.
DOI Google Scholar
9

Anselmo, A. C.; Mitragotri, S. A review of clinical translation of inorganic nanoparticles. AAPS J. 2015, 17, 1041–1054.
DOI Google Scholar
10

Tassa, C.; Shaw, S. Y.; Weissleder, R. Dextran-coated iron oxide nanoparticles: A versatile platform for targeted molecular imaging, molecular diagnostics, and therapy. Acc. Chem. Res. 2011, 44, 842–852.
DOI Google Scholar
11

Wu, H. X.; Liu, G.; Zhuang, Y. M.; Wu, D. M.; Zhang, H. Q.; Yang, H.; Hu, H.; Yang, S. P. The behavior after intravenous injection in mice of multiwalled carbon nanotube/Fe3O4 hybrid MRI contrast agents. Biomaterials 2011, 32, 4867–4876.
DOI Google Scholar
12

Kwon, O. S.; Park, S. J.; Jang, J. A high-performance VEGF aptamer functionalized polypyrrole nanotube biosensor. Biomaterials 2010, 31, 4740–4747.
DOI Google Scholar
13

Runge, M. B.; Dadsetan, M.; Baltrusaitis, J.; Knight, A. M.; Ruesink, T.; Lazcano, E. A.; Lu, L. C.; Windebank, A. J.; Yaszemski, M. J. The development of electrically conductive polycaprolactone fumarate-polypyrrole composite materials for nerve regeneration. Biomaterials 2010, 31, 5916–5926.
DOI Google Scholar
14

Fonner, J. M.; Forciniti, L.; Nguyen, H.; Byrne, J. D.; Kou, Y.-F.; Syeda-Nawaz, J.; Schmidt, C. E. Biocompatibility implications of polypyrrole synthesis techniques. Biomed. Mater. 2008, 3, 034124.
DOI Google Scholar
15

Ramanaviciene, A.; Kausaite, A.; Tautkus, S.; Ramanavicius, A. Biocompatibility of polypyrrole particles: An in-vivo study in mice. J. Pharm. Pharmacol. 2007, 59, 311–315.
DOI Google Scholar
16

Zha, Z. B.; Yue, X. L.; Ren, Q. S.; Dai, Z. F. Uniform polypyrrole nanoparticles with high photothermal conversion efficiency for photothermal ablation of cancer cells. Adv. Mater. 2013, 25, 777–782.
DOI Google Scholar
17

Yang, K.; Xu, H.; Cheng, L.; Sun, C. Y.; Wang, J.; Liu, Z. In vitro and in vivo near-infrared photothermal therapy of cancer using polypyrrole organic nanoparticles. Adv. Mater. 2012, 24, 5586–5592.
DOI Google Scholar
18

Cheng, L.; Yang, K.; Chen, Q.; Liu, Z. Organic stealth nanoparticles for highly effective in vivo near-infrared photothermal therapy of cancer. ACS Nano 2012, 6, 5605– 5613.
DOI Google Scholar
19

Bardhan, R.; Chen, W. X.; Perez-Torres, C.; Bartels, M.; Huschka, R. M.; Zhao, L. L.; Morosan, E.; Pautler, R. G.; Joshi, A.; Halas, N. J. Nanoshells with targeted simultaneous enhancement of magnetic and optical imaging and photo­thermal therapeutic response. Adv. Funct. Mater. 2009, 19, 3901–3909.
DOI Google Scholar
20

Wang, J.; Zhu, G. Z.; You, M. X.; Song, E. Q.; Shukoor, M. I.; Zhang, K. J.; Altman, M. B.; Chen, Y.; Zhu, Z.; Huang, C. Z. et al. Assembly of aptamer switch probes and photosensitizer on gold nanorods for targeted photothermal and photodynamic cancer therapy. ACS Nano 2012, 6, 5070–5077.
DOI Google Scholar
21

Song, X. J.; Gong, H.; Yin, S. N.; Cheng, L.; Wang, C.; Li, Z. W.; Li, Y. G.; Wang, X. Y.; Liu, G.; Liu, Z. Ultra-small iron oxide doped polypyrrole nanoparticles for in vivo multimodal imaging guided photothermal therapy. Adv. Funct. Mater. 2014, 24, 1194–1201.
DOI Google Scholar
22

Tian, Q. W.; Wang, Q.; Yao, K. X.; Teng, B. Y.; Zhang, J. Z.; Yang, S. P.; Han, Y. Multifunctional polypyrrole@Fe3O4 nanoparticles for dual-modal imaging and in vivo photo­thermal cancer therapy. Small 2014, 10, 1063–1068.
DOI Google Scholar
23

Wang, C.; Xu, H.; Liang, C.; Liu, Y. M.; Li, Z. W.; Yang, G. B.; Cheng, L.; Li, Y. G.; Liu, Z. Iron oxide@polypyrrole nanoparticles as a multifunctional drug carrier for remotely controlled cancer therapy with synergistic antitumor effect. ACS Nano 2013, 7, 6782–6795.
DOI Google Scholar
24

Gong, H.; Cheng, L.; Xiang, J.; Xu, H.; Feng, L. Z.; Shi, X. Z.; Liu, Z. Near-infrared absorbing polymeric nanoparticles as a versatile drug carrier for cancer combination therapy. Adv. Funct. Mater. 2013, 23, 6059–6067.
DOI Google Scholar
25

Xiao, Q.; Tan, X. K.; Ji, L. L.; Xue, J. Preparation and characterization of polyaniline/nano-Fe3O4 composites via a novel pickering emulsion route. Synth. Met. 2007, 157, 784–791.
DOI Google Scholar
26

Minehan, D. S.; Marx, K. A.; Tripathy, S. K. Kinetics of DNA binding to electrically conducting polypyrrole films. Macromolecules 1994, 27, 777–783.
DOI Google Scholar
27

Zhang, H.; Zhong, X.; Xu, J. J.; Chen, H.-Y. Fe3O4/ polypyrrole/Au nanocomposites with core/shell/shell structure: Synthesis, characterization, and their electrochemical properties. Langmuir 2008, 24, 13748–13752.
DOI Google Scholar
28

Zhang, X.; Xu, X.; Li, T.; Lin, M.; Lin, X.; Zhang, H.; Sun, H.; Yang, B. Composite photothermal platform of polypyrrole-enveloped Fe3O4 nanoparticle self-assembled superstructures. ACS Appl. Mater. Interfaces 2014, 6, 14552–14561.
DOI Google Scholar
29

Zhang, Z. M.; Li, Q.; Yu, L. M.; Cui, Z. J.; Zhang, L. J.; Bowmaker, G. A. Highly conductive polypyrrole/γ-Fe2O3 nanospheres with good magnetic properties obtained through an improved chemical one-step method. Macromolecules 2011, 44, 4610–4615.
DOI Google Scholar
30

Gai, L. G.; Han, X. Y.; Hou, Y. H.; Chen, J.; Jiang, H. H.; Chen, X. C. Surfactant-free synthesis of Fe3O4@PANI and Fe3O4@PPy microspheres as adsorbents for isolation of pcr-ready DNA. Dalton Trans. 2013, 42, 1820–1826.
DOI Google Scholar
31

Jiang, W.; Kim, B. Y. S.; Rutka, J. T.; Chan, W. C. W. Nanoparticle-mediated cellular response is size-dependent. Nat. Nanotechnol. 2008, 3, 145–150.
DOI Google Scholar
32

Stigliano, C.; Key, J.; Ramirez, M.; Aryal, S.; Decuzzi, P. Radiolabeled polymeric nanoconstructs loaded with docetaxel and curcumin for cancer combinatorial therapy and nuclear imaging. Adv. Funct. Mater. 2015, 25, 3371–3379.
DOI Google Scholar
33

Xuan, S. H.; Wang, F.; Wang, Y. X. J.; Yu, J. C.; Leung, K. C. F. Facile synthesis of size-controllable monodispersed ferrite nanospheres. J. Mater. Chem. 2010, 20, 5086–5094.
DOI Google Scholar
34

Gao, Q.; Zhang, J. L.; Hong, G.-Y.; Ni, J. Z. Solvothermal synthesis of the magnetite micro-nano particles (Fe3O4) with different morphologies. Chem. J. Chin. Univ. 2011, 32, 552–559.
Google Scholar
35

Levin, C. S.; Hofmann, C.; Ali, T. A.; Kelly, A. T.; Morosan, E.; Nordlander, P.; Whitmire, K. H.; Halas, N. J. Magnetic-plasmonic core–shell nanoparticles. ACS Nano 2009, 3, 1379–1388.
DOI Google Scholar
36

Di Corato, R.; Béalle, G.; Kolosnjaj-Tabi, J.; Espinosa, A.; Clément, O.; Silva, A. K. A.; Ménager, C.; Wilhelm, C. Combining magnetic hyperthermia and photodynamic therapy for tumor ablation with photoresponsive magnetic liposomes. ACS Nano 2015, 9, 2904–2916.
DOI Google Scholar
37

Wang, Y. Q.; Zou, B. F.; Gao, T.; Wu, X. P.; Lou, S. Y.; Zhou, S. M. Synthesis of orange-like Fe3O4/PPy composite microspheres and their excellent Cr(Ⅵ) ion removal properties. J. Mater. Chem. 2012, 22, 9034–9040.
DOI Google Scholar
38

Alves, K. G. B.; Andrade, C. A. S.; Campello, S. L.; de Souza, R. E.; de Melo, C. P. Magnetite/polypyrrole hybrid nanocomposites as a promising magnetic resonance imaging contrast material. J. Appl. Polym. Sci. 2013, 128, 3170–3176.
DOI Google Scholar
39

Kim, S.; Oh, W. K.; Jeong, Y. S.; Hong, J. Y.; Cho, B. R.; Hahn, J. S.; Jang, J. Cytotoxicity of, and innate immune response to, size-controlled polypyrrole nanoparticles in mammalian cells. Biomaterials 2011, 32, 2342–2350.
DOI Google Scholar
40

Walter, A.; Billotey, C.; Garofalo, A.; Ulhaq-Bouillet, C.; Lefèvre, C.; Taleb, J.; Laurent, S.; Vander Elst, L.; Muller, R. N.; Lartigue, L. et al. Mastering the shape and composition of dendronized iron oxide nanoparticles to tailor magnetic resonance imaging and hyperthermia. Chem. Mater. 2014, 26, 5252–5264.
DOI Google Scholar
41

Xu, J. K.; Shi, G. Q.; Xu, Z. J.; Chen, F. G.; Hong, X. Y. Low potential electrochemical polymerization of 3-chlorothiophene in mixed electrolytes of boron trifluoride diethyl etherate and trifluoroacetic acid. J. Electroanalyt. Chem. 2001, 514, 16–25.
DOI Google Scholar
42

Kvarnström, C.; Neugebauer, H.; Blomquist, S.; Ahonen, H. J.; Kankare, J.; Ivaska, A. In situ spectroelectrochemical characterization of poly(3, 4-ethylenedioxythiophene). Electrochim. Acta 1999, 44, 2739–2750.
DOI Google Scholar
43

Liu, Y.; Song, Z. J.; Zhang, Q. H.; Zhou, Z. X.; Tang, Y. J.; Wang, L. J.; Zhu, J. J.; Luo, W.; Jiang, W. Preparation of bulk AgNWs/PEDOT: PSS composites: A new model towards high-performance bulk organic thermoelectric materials. RSC Adv. 2015, 5, 45106–45112.
DOI Google Scholar
44

Sun, Z. C.; Geng, Y. H.; Li, J.; Jing, X. B.; Wang, F. S. Chemical polymerization of aniline with hydrogen peroxide as oxidant. Synth. Met. 1997, 84, 99–100.
DOI Google Scholar
45

Rohrer, M.; Bauer, H.; Mintorovitch, J.; Requardt, M.; Weinmann, H. J. Comparison of magnetic properties of MRI contrast media solutions at different magnetic field strengths. Invest. Radiol. 2005, 40, 715–724.
DOI Google Scholar
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Publication history
Copyright
Acknowledgements

Publication history

Received: 19 August 2016
Revised: 04 October 2016
Accepted: 12 October 2016
Published: 23 November 2016
Issue date: February 2017

Copyright

© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2016

Acknowledgements

Acknowledgements

The authors are grateful for the professional tech­nical support for the MRI analysis by Center for Biomedical Imaging Research, Tsinghua University. We thank Tsinghua University Initiative Scientific Research Program (No. 20131089199), National Key Research and Development Program of China (No. 2016YFB0700800), and National Natural Science Foundation of China (Nos. 81172182 and 81671829) for support of funding.

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