Superparamagnetic manganese ferrite (MnFe2O4) nanoparticles have been deposited on graphene oxide (GO) by the thermal decomposition of manganese (II) acetylacetonate and iron (III) acetylacetonate precursors in triethylene glycol. The resulting GO/MnFe2O4 nanohybrids show very low cytotoxicity, negligible hemolytic activity, and imperceptible in vivo toxicity. In vitro and in vivo magnetic resonance imaging experiments demonstrate that GO/MnFe2O4 nanohybrids could be used as an effective T2 contrast agent. The strong optical absorbance in the near-infrared (NIR) region and good photothermal stability of GO/MnFe2O4 nanohybrids result in the highly efficient photothermal ablation of cancer cells. GO/MnFe2O4 nanohybrids can be further loaded with doxorubicin (DOX) by π–π conjugate effect for chemotherapy. DOX release from GO/MnFe2O4 is significantly influenced by pH and can be triggered by NIR laser. The enhanced cancer cell killing by GO/MnFe2O4/DOX composites has been achieved when irradiated with near-infrared light, suggesting that the nanohybrids could deliver both DOX chemotherapy and photothermal therapy with a synergistic effect.
LiuZRobinsonJTSunXM. PEGylated nanographene oxide for delivery of water-insoluble cancer drugs. J Am Chem Soc2008; 130: 10876–10877.
5.
YangXYZhangXYLiuZF. High-efficiency loading and controlled release of doxorubicin hydrochloride on graphene oxide. J Phys Chem C2008; 112: 17554–17558.
6.
ZhangHCGrunerGZhaoYL. Recent advancements of graphene in biomedicine. J Mater Chem B2013; 1: 2542–2567.
7.
ZhangLMLuZXZhaoQH. Enhanced chemotherapy efficacy by sequential delivery of siRNA and anticancer drugs using PEI-grafted graphene oxide. Small2011; 7: 460–464.
8.
JaqueDMaestroLMdel RosalB. Nanoparticles for photothermal therapies. Nanoscale2014; 6: 9494–9530.
9.
RobinsonJTTabakmanSMLiangYY. Ultrasmall reduced graphene oxide with high near-infrared absorbance for photothermal therapy. J Am Chem Soc2011; 133: 6825–6831.
10.
YangKZhangSZhangGX. Graphene in mice: Ultrahigh in vivo tumor uptake and efficient photothermal therapy. Nano Lett2010; 10: 3318–3323.
11.
VilaMMatesanzMCGoncalvesG. Triggering cell death by nanographene oxide mediated hyperthermia. Nanotechnology2014; 25: 035101–035101.
12.
NguyenKTZhaoYL. Integrated graphene/nanoparticle hybrids for biological and electronic applications. Nanoscale2014; 6: 6245–6266.
13.
CongHPHeJJLuY. Water-soluble magnetic-functionalized reduced graphene oxide sheets: in situ synthesis and magnetic resonance imaging applications. Small2010; 6: 169–173.
14.
BianXSongZLQianY. Fabrication of graphene-isolated-Au-nanocrystal nanostructures for multimodal cell imaging and photothermal-enhanced chemotherapy. Sci Rep2014; 4: 6093–6093.
15.
GaoJHGuHWXuB. Multifunctional magnetic nanoparticles: Design, synthesis, and biomedical applications. Accounts Chem Res2009; 42: 1097–1107.
16.
ZhengSWHuangMHongRY. RGD-conjugated iron oxide magnetic nanoparticles for magnetic resonance imaging contrast enhancement and hyperthermia. J Biomater Appl2014; 28: 1051–1059.
17.
ColomboMCarregal-RomeroSCasulaMF. Biological applications of magnetic nanoparticles. Chem Soc Rev2012; 41: 4306–4334.
18.
LimJMajetichSA. Composite magnetic-plasmonic nanoparticles for biomedicine: manipulation and imaging. Nano Today2013; 8: 98–113.
19.
LeeJHHuhYMJunY. Artificially engineered magnetic nanoparticles for ultra-sensitive molecular imaging. Nat Med2007; 13: 95–99.
20.
YangHZhangCXShiXY. Water-soluble superparamagnetic manganese ferrite nanoparticles for magnetic resonance imaging. Biomaterials2010; 31: 3667–3673.
21.
PengEWChooESGChandrasekharanP. Synthesis of manganese ferrite/graphene oxide nanocomposites for biomedical applications. Small2012; 8: 3620–3630.
22.
HummersWSOffemanRE. Preparation of graphitic oxide. J Am Chem Soc1958; 80: 1339–1339.
23.
WuHXLiuGZhuangYM. The behavior after intravenous injection in mice of multiwalled carbon nanotube/Fe3O4 hybrid MRI contrast agents. Biomaterials2011; 32: 4867–4876.
24.
XiaoYLZaiJTTaoLQ. MnFe2O4–graphene nanocomposites with enhanced performances as anode materials for Li-ion batteries. Phys Chem Chem Phys2013; 15: 3939–3945.
25.
FuYSXiongPChenHQ. High photocatalytic activity of magnetically separable manganese ferrite graphene heteroarchitectures. Ind Eng Chem Res2012; 51: 725–731.
26.
LuJMaSLSunJY. Manganese ferrite nanoparticle micellar nanocomposites as MRI contrast agent for liver imaging. Biomaterials2009; 30: 2919–2928.
27.
WangHBZhangQChuX. Graphene oxide-peptide conjugate as an intracellular protease sensor for caspase-3 activation imaging in live cells. Angew Chem Int Ed2011; 50: 7065–7069.
28.
YangXYWangYSHuangX. Multi-functionalized graphene oxide based anticancer drug-carrier with dual-targeting function and pH-sensitivity. J Mater Chem2011; 21: 3448–3454.
29.
XiongHMZhaoXChenJS. New polymer-inorganic nanocomposites: PEO–ZnO and PEO–ZnO–LiClO4 films. J Phys Chem B2001; 105: 10169–10174.
30.
YangXYZhangXYMaYF. Superparamagnetic graphene oxide–Fe3O4 nanoparticles hybrid for controlled targeted drug carriers. J Mater Chem2009; 19: 2710–2714.
31.
SlowingIIWuCWVivero-EscotoJL. Mesoporous silica nanoparticles for reducing hemolytic activity towards mammalian red blood cells. Small2009; 5: 57–62.
32.
YangKWanJMZhangS. The influence of surface chemistry and size of nanoscale graphene oxide on photothermal therapy of cancer using ultra-low laser power. Biomaterials2012; 33: 2206–2214.
33.
BarretoJAO'MalleyWKubeilM. Nanomaterials: Applications in cancer imaging and therapy. Adv Mater2011; 23: H18–H40.
34.
HobbsSKMonskyWLYuanF. Regulation of transport pathways in tumor vessels: Role of tumor type and microenvironment. Proc Natl Acad Sci USA1998; 95: 4607–4612.
35.
ZhangLMXiaJGZhaoQH. Functional graphene oxide as a nanocarrier for controlled loading and targeted delivery of mixed anticancer drugs. Small2010; 6: 537–544.
36.
LiuZSunXMNakayama-RatchfordN. Supramolecular chemistry on water-soluble carbon nanotubes for drug loading and delivery. ACS Nano2007; 1: 50–56.
37.
SunXMLiuZWelsherK. Nano-graphene oxide for cellular imaging and drug delivery. Nano Res2008; 1: 203–212.
38.
TangYLeiTJManchandaR. Simultaneous delivery of chemotherapeutic and thermal-optical agents to cancer cells by a polymeric (PLGA) nanocarrier: An in vitro study. Pharm Res2012; 27: 2242–2253.
39.
MaXXTaoHQYangK. A functionalized graphene oxide–iron oxide nanocomposite for magnetically targeted drug delivery, photothermal therapy, and magnetic resonance imaging. Nano Res2012; 5: 199–212.
40.
FrangioniJV. In vivo near-infrared fluorescence imaging. Curr Opin Chem Biol2003; 7: 626–634.
41.
SuYYWeiXPPengF. Gold nanoparticles-decorated silicon nanowires as highly efficient near-infrared hyperthermia agents for cancer cells destruction. Nano Lett2012; 12: 1845–1850.
42.
ZhangHWuHXWangJ. Graphene oxide-BaGdF5 nanocomposites for multi-modal imaging and photothermal therapy. Biomaterials2015; 42: 66–77.
43.
SherlockSPTabakmanSMXieLM. Photothermally enhanced drug delivery by ultrasmall multifunctional FeCo/graphitic shell nanocrystals. ACS Nano2011; 5: 1505–1512.
44.
YouJZhangGDLiC. Exceptionally high payload of doxorubicin in hollow gold nanospheres for near-infrared light-triggered drug release. ACS Nano2010; 4: 1033–1041.
45.
YouJShaoRPWeiX. Near-infrared light triggers release of paclitaxel from biodegradable microspheres: Photothermal effect and enhanced antitumor activity. Small2010; 6: 1022–1031.
46.
WuWTShenJBanerjeeP. Core-shell hybrid nanogels for integration of optical temperature-sensing, targeted tumor cell imaging, and combined chemo-photothermal treatment. Biomaterials2010; 31: 7555–7566.
