Materials Today Chemistry
Volume 17, September 2020, 100322
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Adhesive graphene grown on bioceramics with photothermal property

https://doi.org/10.1016/j.mtchem.2020.100322Get rights and content

Highlights

  • Graphene growing on bioceramics via CVD method without using any catalysts.

  • The prepared graphene film adhesion strongly on the bioceramics.

  • The prepared graphene film exhibition excellent photothermal effects.

Abstract

Recently, graphene has been applied to modify biomaterials due to excellent physicochemical property and biocompatibility. However, some problems still exist especially the weak binding force between graphene and other biomaterials. Herein, a promising platform with photothermal property was constructed by fabricating the adhesive graphene in situ on the surface of β-tricalcium phosphate (β-Ca3(PO4)2, β-TCP) bioceramics using chemical vapor deposition (CVD). The result of ultrasonic cleaning treatment of graphene modified β-TCP (G-TCP) demonstrated that the prepared graphene coating could firmly modified on β-TCP due to the occurrence of carbothermal reduction on the ceramic surface to promote the nucleation and growth of graphene. G-TCP composites exhibited excellent photothermal effects when irradiated with 808 nm near-infrared laser (NIR). The photothermal effect of G-TCP composites could induce more than 90% of osteosarcoma cell (MNNG) death in vitro. These results confirmed that the graphene could be successfully fabricated in situ on the surface of β-TCP by CVD method, and exhibited high firmness and excellent photothermal performance, revealing a promising application in the photothermal therapy of bone tumors.

Introduction

Nowadays, graphene and its derivatives, such as graphene oxide (GO) [1,2], reduced graphene oxide (rGO) [3], and graphene quantum dots (GQD) [4,5], have been applied in a variety of disciplines [6]. Due to the high specific surface area, excellent thermal conductivity, good photoelectric effect, satisfactory cell compatibility, and no obvious toxicity in the body, they have received more and more attentions in biomedicine field [[7], [8], [9], [10], [11], [12], [13]], including drug delivery [14], tissue regeneration [[15], [16], [17], [18], [19]], gene delivery [20], optical imaging [21,22] and tumor treatment [[21], [22], [23], [24]], etc. Particularly, graphene and its derivatives can be used to modify other biological materials for multifunctionality because of the unique physical and chemical properties [21,[25], [26], [27]]. For example, the composite scaffold was prepared by mixing functionalized GO with polycaprolactone (PCL), which could be used for photothermal treatment of breast cancer and adipose tissue regeneration [28]. Ma et al. [29] modified GO nanosheets on the surface of bioceramic scaffolds by immersing and drying to achieve photothermal anti-bone tumor effect and promote bone tissue regeneration. Other studies have proven that the composite scaffold prepared by GO and collagen can effectively promote mineralization in vitro and bone repair in vivo [15]. In addition, rGO and nano-hydroxyapatite (nHA) were utilized to form a bionic three-dimensional porous scaffold for bone tissue engineering via self-assembly approach [30].

At present, most of the graphene composite materials for biomedical applications were prepared by employing GO nanosheets made by the modified Hummers method [31], and then hybridizing with other biological material via different approaches, such as blending [32], solution soaking [29], self-assembly [30], and hot isostatic pressing (HIP) [33]. However, the Hummers method may inevitably introduce Mn2+ and acids into GO, and the residues of Mn2+ and acids will generate potential biological safety [[34], [35], [36]]. Furthermore, the traditional methods for nanocomposite fabrication mostly depend on physical adsorption method [26]. Therefore, considering the safety and effectiveness of biological materials based on graphene modification, it is very important to develop a method combining graphene with biological substrate materials stably.

Chemical vapor deposition (CVD) is one of the most promising methods for producing high-quality graphene. It has been reported that the CVD method has been applied for constructing graphene on nickel (Ni) through the carbon segregation or precipitation process [37]. With the help of CVD method, graphene has also been introduced to the surface of copper (Cu) because of surface adsorption [38]. Herein, CVD was applied to construct adhesive graphene modified layers in situ on the surface of β-TCP bioceramics without using any metal catalyst [[39], [40], [41]], which could avoid the potential toxicity derived from the residual metal ions. The adhesion property of the graphene on β-TCP was examined by comparison with that of the counterpart prepared by the physical adsorption method. In addition, the laser power density-dependent photothermal performance of the prepared materials in dry and wet states was investigated. Eventually, the in vitro photothermal-therapeutic capability of the composite materials was also evaluated based on the appropriate laser power density.

Section snippets

Preparation and characterization of graphene modified β-TCP bioceramics

Preparation of β-TCP bioceramics: the commercial β-TCP ceramic powders (Kunshan Huaqiao Technology New Material Co., Ltd.) were stirred adequately after adding 8% polyvinyl alcohol (PVA) solution as binder and pressed into pellets with a diameter of 10 mm and a thickness of 2 mm. And then, they were sintered at 1,090 °C for 2 h [42].

CVD growth of graphene on β-TCP: the as-fabricated β-TCP bioceramic pieces were placed in the middle of the quartz tube in a three-inch tube furnace. Then, they

Preparation and characterization of G-TCP

As shown in Fig. 1a, pure β-TCP bioceramic looked white, and G-TCP bioceramics exhibited light gray. From XRD patterns (Fig. 1b), it could be seen that the defraction peaks of G-TCP and β-TCP are identical, suggesting that the CVD growth did not change the phase structure of β-TCP. No characteristic peaks of graphene are observed, possibly because of low graphene content grown on the β-TCP bioceramic surface. As shown in Fig. 1c, β-TCP bioceramics did not show any characteristic peaks, while

Conclusions

Adhesive graphene coating was successfully grown in situ on the surface of β-TCP bioceramics by CVD. The graphene coating had excellent stability and was not easy to fall off. The graphene modified β-TCP bioceramics (G-TCP) had remarkable photothermal effect, which could regulate local temperature within a certain range, and could effectively kill MNNG tumor cells. These results showed that the prepared G-TCP materials via in-situ CVD method could be helpful for photothermal treatment. This

Author statement

A.S. Investigated the method, prepared the samples and write the manuscript. C.Z. performed the cell culture experiment and help writing the manuscript. L.M. analyzed the data and help revision the manuscript. Y.W., B.Z. and K.L. supervised the findings of this work, put forward research ideas, designed the experiments.

Declaration of competing interest

The authors declared no potential conflicts of interest.

Acknowledgments

Funding for this study were provided by the National Natural Science Foundation of China (81701020), Program of Shanghai Academic/Technology Research Leader (19XD1434500), Double Hundred Plan (20191819), the Science and Technology Commission of Shanghai Municipality (18060502300), the Shanghai Municipal Commission of Health and Family Planning (201740035), and Medical-Engineering Cross Fund of University of Shanghai for Science and Technology (10-20-310-402).

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