logo

SCIENCE CHINA Materials, Volume 61, Issue 8: 1112-1122(2018) https://doi.org/10.1007/s40843-017-9221-4

Rotating magnetic field-controlled fabrication of magnetic hydrogel with spatially disk-like microstructures

More info
  • ReceivedDec 10, 2017
  • AcceptedJan 27, 2018
  • PublishedMar 6, 2018

Abstract

Composite biomaterials with controllable microstructures play an increasingly important role in tissue engineering and regenerative medicine. Here, we report a magnetic hydrogel composite with disk-like microstructure fabricated by assembly of iron oxide nanoparticles during the gelation process in the presence of rotating magnetic field. It should be mentioned that the iron oxide nanoparticles here were synthesized identically following techniques of Ferumoxytol that is the only inorganic nanodrug approved by FDA for clinical applications. The microstructure of nanoparticles inside the hydrogel was ordered three-dimensionally due to the twist of the aligned chains of magnetic nanoparticles which leads to the lowest state of systematic energy. The size of microstructure can be tuned from several micrometers to tens of micrometers by changing the assembly parameters. With the increase of microstructure size, the magnetothermal anisotropy was also augmented. This result confirmed that the assembly-induced anisotropy can occur even for the several micron aggregates of nanoparticles. The rotating magnetic field-assisted technique is cost-effective, simple and flexible for the fabrication of composite hydrogel with ordered microstructure. We believe it will be favorable for the quick, green and intelligent fabrication of some composite materials.


Funded by

the National Key Research and Development Program of China(2017YFA0104301)

the Fundamental Research Funds for the Central Universities

and the Collaborative Innovation Center of Suzhou NanoScience and Technology.


Acknowledgment

This work was supported by the National Key Research and Development Program of China (2017YFA0104301). Sun J is thankful to the Fundamental Research Funds for the Central Universities. Fan F, Sun J, Ma M and Gu N appreciate the supports from Collaborative Innovation Center of Suzhou NanoScience and Technology.


Interest statement

The authors declare that they have no conflict of interest.


Contributions statement

Fan F and Sun J designed and operated the experiments; Chen B and Li Y provided the iron oxide sample. Hu K and Wang P gave some useful advice for our experiments; Ma M contributed to the theoretical analysis. Gu N provided experimental ideas, guided the experimental process. All authors contributed to the general discussion.


Author information

Fengguo Fan is pursuing his PhD degree in biomedical engineering at Southeast University. His research interest is the assembly of nanoparticles.


Jianfei Sun received his PhD degree in biomedical engineering from Southeast University in 2008. He is now an associate professor at the School of Biological Science and Medical Engineering, Southeast University. His research interests include the fabrication of nanoelectronic devices by self-assembly of nanoparticles and their application in biomedical issues.


Ning Gu received his PhD degree in biomedical engineering from the Department of Biomedical Engineering, Southeast University, Nanjing, China, in 1996. Currently he is a Cheung Kong Scholar Chair Professor at the School of Biological Science and Medical Engineering, Southeast University.


Supplement

Supplementary information

Supporting materials are available in the online version of the paper.


References

[1] Park SB, Lih E, Park KS, et al. Biopolymer-based functional composites for medical applications. Prog Polymer Sci, 2017, 68: 77-105 CrossRef Google Scholar

[2] Lin N, Cao L, Huang Q, et al. Functionalization of silk fibroin materials at mesoscale. Adv Funct Mater, 2016, 26: 8885-8902 CrossRef Google Scholar

[3] Chang H, Luo J, Gulgunje PV, et al. Structural and functional fibers. Annu Rev Mater Res, 2017, 47: 331-359 CrossRef Google Scholar

[4] Kim CR, Uemura T, Kitagawa S. Inorganic nanoparticles in porous coordination polymers. Chem Soc Rev, 2016, 45: 3828-3845 CrossRef PubMed Google Scholar

[5] Cezar CA, Mooney DJ. Biomaterial-based delivery for skeletal muscle repair. Adv Drug Deliver Rev, 2015, 84: 188-197 CrossRef PubMed Google Scholar

[6] Arslan E, Garip IC, Gulseren G, et al. Bioactive supramolecular peptide nanofibers for regenerative medicine. Adv Healthcare Mater, 2014, 3: 1357-1376 CrossRef PubMed Google Scholar

[7] Mendes AC, Baran ET, Reis RL, et al. Self-assembly in nature: using the principles of nature to create complex nanobiomaterials. WIREs Nanomed Nanobiotechnol, 2013, 5: 582-612 CrossRef PubMed Google Scholar

[8] Mouw JK, Ou G, Weaver VM. Extracellular matrix assembly: a multiscale deconstruction. Nat Rev Mol Cell Biol, 2014, 15: 771-785 CrossRef PubMed Google Scholar

[9] Rising A, Johansson J. Toward spinning artificial spider silk. Nat Chem Biol, 2015, 11: 309-315 CrossRef PubMed Google Scholar

[10] Wong Po Foo C, Patwardhan SV, Belton DJ, et al. Novel nanocomposites from spider silk-silica fusion (chimeric) proteins. Proc Natl Acad Sci USA, 2006, 103: 9428-9433 CrossRef PubMed ADS Google Scholar

[11] Yin X, Mead BE, Safaee H, et al. Engineering stem cell organoids. Cell Stem Cell, 2016, 18: 25-38 CrossRef PubMed Google Scholar

[12] Quarta M, Brett JO, DiMarco R, et al. An artificial niche preserves the quiescence of muscle stem cells and enhances their therapeutic efficacy. Nat Biotechnol, 2016, 34: 752-759 CrossRef PubMed Google Scholar

[13] Le Ferrand H, Bouville F, Niebel TP, et al. Magnetically assisted slip casting of bioinspired heterogeneous composites. Nat Mater, 2015, 14: 1172-1179 CrossRef PubMed ADS arXiv Google Scholar

[14] Wang M, He L, Yin Y. Magnetic field guided colloidal assembly. Mater Today, 2013, 16: 110-116 CrossRef Google Scholar

[15] Xu X, Li H, Zhang Q, et al. Self-sensing, ultralight, and conductive 3D graphene/iron oxide aerogel elastomer deformable in a magnetic field. ACS Nano, 2015, 9: 3969-3977 CrossRef PubMed Google Scholar

[16] Ahniyaz A, Sakamoto Y, Bergström L. Magnetic field-induced assembly of oriented superlattices from maghemite nanocubes. Proc Natl Acad Sci USA, 2007, 104: 17570-17574 CrossRef PubMed ADS Google Scholar

[17] Martin JE, Snezhko A. Driving self-assembly and emergent dynamics in colloidal suspensions by time-dependent magnetic fields. Rep Prog Phys, 2013, 76: 126601 CrossRef PubMed ADS Google Scholar

[18] Snezhko A, Aranson IS, Kwok WK. Surface wave assisted self-assembly of multidomain magnetic structures. Phys Rev Lett, 2006, 96: 078701 CrossRef PubMed ADS Google Scholar

[19] Thévenot J, Oliveira H, Sandre O, et al. Magnetic responsive polymer composite materials. Chem Soc Rev, 2013, 42: 7099-7116 CrossRef PubMed Google Scholar

[20] Kango S, Kalia S, Celli A, et al. Surface modification of inorganic nanoparticles for development of organic–inorganic nanocomposites—A review. Prog Polymer Sci, 2013, 38: 1232-1261 CrossRef Google Scholar

[21] Thoniyot P, Tan MJ, Karim AA, et al. Nanoparticle-hydrogel composites: concept, design, and applications of these promising, multi-functional materials. Adv Sci, 2015, 2: 1400010 CrossRef PubMed Google Scholar

[22] Hu K, Sun J, Guo Z, et al. A novel magnetic hydrogel with aligned magnetic colloidal assemblies showing controllable enhancement of magnetothermal effect in the presence of alternating magnetic field. Adv Mater, 2015, 27: 2507-2514 CrossRef PubMed Google Scholar

[23] Nair M, Guduru R, Liang P, et al. Externally controlled on-demand release of anti-HIV drug using magneto-electric nanoparticles as carriers. Nat Commun, 2013, 4: 1707 CrossRef PubMed ADS Google Scholar

[24] Sun J, Fan F, Wang P, et al. Orientation-dependent thermogenesis of assembled magnetic nanoparticles in the presence of an alternating magnetic field. ChemPhysChem, 2016, 17: 3377-3384 CrossRef PubMed Google Scholar

[25] Fan F, Liu J, Sun J, et al. Magnetic energy-based understanding the mechanism of magnetothermal anisotropy for macroscopically continuous film of assembled Fe3O4 nanoparticles. AIP Adv, 2017, 7: 085109 CrossRef Google Scholar

[26] Qian Y, Zhang X, Qi D, et al. Thin-film organic semiconductor devices: from flexibility to ultraflexibility. Sci China Mater, 2016, 59: 589-608 CrossRef Google Scholar

[27] Martin JJ, Fiore BE, Erb RM. Designing bioinspired composite reinforcement architectures via 3D magnetic printing. Nat Commun, 2015, 6: 8641 CrossRef PubMed ADS Google Scholar

[28] Richardson JJ, Björnmalm M, Caruso F. Technology-driven layer-by-layer assembly of nanofilms. Science, 2015, 348: aaa2491-aaa2491 CrossRef PubMed Google Scholar

[29] Wang J, Cheng Q, Lin L, et al. Synergistic toughening of bioinspired poly(vinyl alcohol)–clay–nanofibrillar cellulose artificial nacre. ACS Nano, 2014, 8: 2739-2745 CrossRef PubMed Google Scholar

[30] Chen B, Li Y, Zhang X, et al. An efficient synthesis of ferumoxytol induced by alternating-current magnetic field. Mater Lett, 2016, 170: 93-96 CrossRef Google Scholar

[31] Li Y, Hu K, Chen B, et al. Fe3O4@PSC nanoparticle clusters with enhanced magnetic properties prepared by alternating-current magnetic field assisted co-precipitation. Colloids Surfs A-Physicochem Eng Aspects, 2017, 520: 348-354 CrossRef Google Scholar

[32] Aharoni A. Demagnetizing factors for rectangular ferromagnetic prisms. J Appl Phys, 1998, 83: 3432-3434 CrossRef ADS Google Scholar

[33] Bergmann G, Lu JG, Tao Y, et al. Frustrated magnetization in Co nanowires: Competition between crystal anisotropy and demagnetization energy. Phys Rev B, 2008, 77: 054415 CrossRef ADS Google Scholar

[34] Normile PS, Andersson MS, Mathieu R, et al. Demagnetization effects in dense nanoparticle assemblies. Appl Phys Lett, 2016, 109: 152404 CrossRef ADS Google Scholar

[35] Yuan J, Gao H, Schacher F, et al. Alignment of tellurium nanorods via a magnetization−alignment−demagnetization (“MAD”) process assisted by an external magnetic field. ACS Nano, 2009, 3: 1441-1450 CrossRef PubMed Google Scholar

  • Figure 1

    (a) SEM characterization of the Fe3O4@PSC nanoparticles (bar: 2 μm). Inset: SEM image in a larger magnification (bar: 400 nm). (b) TEM characterization of the Fe3O4@PSC nanoparticles, and the average statistics diameter is shown in the insert figure (bar: 20 nm). (c) Top and side views of a conceptual rotating magnetic field platform, and the magnet hydrogels sample. (d) Simulated magnetic field intensity of center point with distance between two magnets (inset: magnetic field simulation). (e) The simulated magnetic field intensity in central region by adjusting the distance between two poles from 1 to 10 cm.

  • Figure 2

    Characterization of a typical magnetic hydrogel sample. (a) The longitudinal section of magnetic hydrogel in optical imaging (bar: 100 μm). Right part of the figure was the corresponding binary image. (b) The transverse section of magnetic hydrogel in optical imaging (bar: 100 μm). (c) The longitudinal (bar: 4 μm) and transverse (bar: 4 μm) SEM images of a single microdisk and the local magnification (bar: 2 μm and 200 nm). (d) The longitudinal section (bar: 10 μm) and transverse section (bar: 10 μm) LSCM images of a single microdisk. (e) Fe element mapping of a single microdisk (bar: 10 μm).

  • Figure 3

    (a) Average statistical size of the microstructure with alteration of field intensity. (b) Average statistical size of the microstructure with alteration of field frequency. (c) Average statistical size of the microstructure with alteration of colloidal concentration. (d) LSCM characterization of a series of microdisks with different size (Diameter from the left to the right: 7, 12, 15, 18 and 23 μm. Thickness from the left to the right: 3, 5, 7, 8 and 8 μm. Bar: 10 μm).

  • Figure 4

    A possible mechanism for the formation of disk-like structure. (a) The iron oxide nanoparticles inside hydrogel at initial state (bar: 2 μm). (b) At the beginning of rotating magnetic field (bar: 2 μm). (c) With continuing rotating magnetic field (bar: 1 μm). (d) Intermediate state (bar: 2 μm). (e) Final state (bar: 4 μm). (f) Schematic diagram of formation process based on three forces. (g) OOMMF simulations of the demagnetization energy variation in angle range from 0° to 360° for different assembled morphology in the presence of a rotating magnetic field.

  • Figure 5

    (a) Magnetothermal measurements of an assembled magnetic hydrogel with the different incident direction of alternating magnetic field (0°, 30°, 60° and 90°). (b and c) The hysteresis loops for assembled magnetic hydrogel and disorganized magnetic hydrogel, respectively. (d) Comparison of anisotropy degree for the assembled magnetic hydrogels with different size and the disorganized magnetic hydrogel. Average statistical diameters for the three assembled magnetic hydrogel were 6, 15 and 22 μm, respectively. Average statistical thicknesses were 3, 4 and 4 μm, respectively.

Copyright 2019 Science China Press Co., Ltd. 《中国科学》杂志社有限责任公司 版权所有

京ICP备18024590号-1