Preparation and Biological Application of Graphene Quantum Dots

doi:10.15541/jim20150424

Abstract

Abstract:

As the derivatives of graphene, graphene quantum dots (GQDs) have the excellent properties of graphene, and photoluminescence (PL) properties that ordinary graphene does not possess, which is attributed to quantum confinement effect and boundary effect. Moreover, GQDs perform well in terms of cytotoxicity and biocompatibility. Recently, the synthetic method of GQDs is increasingly diverse, which is usually divided into two main groups: top-down and bottom-up. With increasing application of GQDs in biomedical field, higher requirements on their morphology and size control are put forward. In this paper, we focus on the synthetic methods that are promising to control morphology and size of GQDs. Advantages and disadvantages of these methods are listed and analyzed comparatively. The biological applications of GQDs, including biological imaging, biological sensors, drug delivery and antibacterial agents, etc. are introduced. Suggestions on the choice of synthetic method for preparation of GQDs are given based on the requirements of diverse applications. The remained problems and the development directions in the research of GQDs are put forward.

Key words: graphene quantum dots, morphology and size control, synthetic methods, biological applications, review

CLC Number:

O613

SUN Xiao-Dan, LIU Zhong-Qun, YAN Hao. Preparation and Biological Application of Graphene Quantum Dots[J]. Journal of Inorganic Materials, 2016, 31(4): 337-344.

Figures/Tables 7

References 37

[1]	SEABRA A B, PAULA A J, LIMA R, et al.Nanotoxicity of graphene and graphene oxide.Chem. Res. Toxicol., 2014, 27(2): 159-168.
[2]	WU X, TIAN F, WANG W, et al.Fabrication of highly fluorescent graphene quantum dots using L-glutamic acid for in vitro/in vivo imaging and sensing.J. Mater. Chem. C, 2013, 1(31): 4676-4684.
[3]	ZHANG X, YIN J, PENG C, et al.Distribution and biocompatibility studies of graphene oxide in mice after intravenous administration.Carbon, 2011, 49(3): 986-995.
[4]	NURUNNABI M, KHATUN Z, HUH K M, et al.In Vivo biodistribution and toxicology of carboxylated graphene quantum dots.ACS Nano, 2013, 7(8): 6858-6867.
[5]	LIAO K, LIN Y, MACOSKO C W, et al.Cytotoxicity of graphene oxide and graphene in human erythrocytes and Skin Fibroblasts.ACS Appl. Mater. Interfaces, 2011, 3(7): 2607-2615.
[6]	ZHU S, ZHANG J, QIAO C, et al.Strongly green-photoluminescent graphene quantum dots for bioimaging applications.Chem. Commun., 2011, 47(24): 6858-6860.
[7]	CHUNG C, KIM Y, SHIN D, et al.Biomedical applications of graphene and graphene oxide.Accounts of Chemical Research, 2013, 46(10): 2211-2224.
[8]	ZHENG X T, ANANTHANARAYANAN A, LUO K Q, et al.Glowing graphene quantum dots and carbon dots: properties, syntheses, and biological applications.Small, 2015, 11(14): 1620-1636.
[9]	YANG K, FENG L, SHI X, et al.Nano-graphene in biomedicine: theranostic applications.Chem. Soc. Rev., 2013, 42(2): 530-547.
[10]	ROBINSON J T, TABAKMAN S M, LIANG Y, et al.Ultrasmall reduced graphene oxide with high near-Infrared absorbance for photothermal therapy. J. Am. Chem. Soc. 2011, 133(17): 6825-6831.
[11]	PAN D, ZHANG J, LI Z, et al.Hydrothermal route for cutting graphene sheets into blue-Luminescent graphene quantum dots.Adv. Mater. 2010, 22(6): 734-738.
[12]	PAN D, GUO L, ZHANG J, et al.Cutting sp2 clusters in graphene sheets into colloidal graphene quantum dots with strong green fluorescence. J. Mater. Chem., 2012, 22(8): 3314-3318.
[13]	SHEN J, ZHU Y, YANG X, et al.One-pot hydrothermal synthesis of graphene quantum dots surface-passivated by polyethylene glycol and their photoelectric conversion under near-infrared light.New J. Chem., 2012, 36(1): 97-101.
[14]	CHEN S, LIU J, CHEN M, et al.Unusual emission transformation of graphene quantum dots induced by self-assembled aggregation.Chem. Commun., 2012, 48(61): 7637-7639.
[15]	LI L, JI J, FEI R, et al.A facile microwave avenue to electrochemiluminescent two-color graphene quantum dots.Adv. Funct. Mater., 2012, 22(14): 2971-2979.
[16]	LU J, YANG J, WANG J, et al.One-pot synthesis of fluorescent carbon nanoribbons, nanoparticles, and graphene by the exfoliation of graphite in ionic liquids.ACS Nano, 2009, 3(8): 2367-2375.
[17]	ANANTHANARAYANAN A, WANG X, ROUTH P, et al.Facile synthesis of graphene quantum dots from 3d graphene and their application for Fe3+ sensing. Adv. Funct. Mater., 2014, 24(20): 3021-3026.
[18]	ZHANG M, BAI L, SHANG W, et al.Facile synthesis of water- soluble, highly fluorescent graphene quantum dots as a robust biological label for stem cells. J. Mater. Chem., 2012, 22(15): 7461-7467.
[19]	LI Y, HU Y, ZHAO Y, et al.An electrochemical avenue to green- luminescent graphene quantum dots as potential electron-acceptors for photovoltaics.Adv. Mater., 2011, 23(6): 776-780.
[20]	PENG J, GAO W, GUPTA B K, et al.Graphene quantum dots derived from carbon fibers.Nano Lett., 2012, 12(2): 844-849.
[21]	SHIH Y, TSENG G, HSIEH C, et al.Graphene quantum dots derived from platelet graphite nanofibers by liquid-phase exfoliation.Acta Materialia. 2014, 78(2): 314-319.
[22]	PONOMARENKO L A, SCHEDIN F., KATSNELSON M I, et al.Chaotic dirac billiard in graphene quantum dots.Science, New Series., 2008, 320( 5874): 356-358.
[23]	LU J, YEO P S, GAN C K, et al.Transforming C60 molecules into graphene quantum dots.Nat. Nanotechnol., 2011, 6(4): 247-252.
[24]	YAN X, CUI X, LI L, et al.Synthesis of large, stable colloidal graphene quantum dots with tunable size.J. Am. Chem. Soc., 2010, 132(17): 5944-5945.
[25]	TANG L, JI R, CAO X, et al.Deep ultraviolet photoluminescence of water-soluble self-passivated graphene quantum dots.ACS Nano, 2012, 6(6): 5102-5110.
[26]	DONG Y, SHAO J, CHEN C, et al.Blue luminescent graphene quantum dots and graphene oxide prepared by tuning the carbonization degree of citric acid.Carbon, 2012, 50(12): 4738-4743.
[27]	LIU R, WU D, FENG X, et al.Bottom-up fabrication of photoluminescent graphene quantum dots with uniform morphology. J. Am. Chem. Soc., 2011, 133(39): 15221-15223.
[28]	NURUNNABI M, KHATUN Z, NAFIUJJAMAN M, et al.Surface coating of graphene quantum dots using mussel-inspired polydopamine for biomedical optical imaging.ACS Appl. Mater. Interfaces, 2013, 5(16): 8246-8253.
[29]	ZHAO H, CHANG Y, LIU M, et al.A universal immunosensing strategy based on regulation of the interaction between graphene and graphene quantum dots.Chem. Commun., 2013, 49(3): 234-236.
[30]	LI S, LI Y, CAO J, et al.Sulfur-doped graphene quantum dots as a novel fluorescent probe for highly selective and sensitive detection of Fe3+.Anal. Chem., 2014, 86(20): 10201-10207.
[31]	WANG Z, XIA J, ZHOU C, et al.Synthesis of strongly green-photoluminescent graphene quantum dots for drug carrier. Colloids and Surfaces B: Biointerfaces, 2013, 112c(3): 192-196.
[32]	NAHAIN A A, LEE J, IN I, et al.Target delivery and cell imaging using hyaluronic acid-functionalized graphene quantum dots.Mol. Pharmaceutics, 2013, 10(10): 3736-3744.
[33]	RISTIC B Z, MILENKOVIC M M, DAKIC I R, et al.Photodynamic antibacterial effect of graphene quantum dots.Biomaterials, 2014, 35(15): 4428-4435.
[34]	MARKOVIC Z M, RISTIC BILJANA Z, ARSIKIN K M,et al.Graphene quantum dots as autophagy-inducing photodynamic agents.Biomaterials, 2012, 33(29): 7084-7092.
[35]	GE J, LAN M, ZHOU B, et al.A graphene quantum dot photodynamic therapy agent with high singlet oxygen generation. Nature Communications, 2014, 5: 4596.
[36]	GUI R, LIU X, JIN H, et al. N, S co-doped graphene quantum dots from a single source precursor used for photodynamic cancer therapy under two-photon excitation. Chemical Communications, 2015, 51: 10066-1-4.
[37]	SUN H, GAO N, DONG K, et al.Graphene quantum dots-band- aids used for wound disinfection.ACS Nano, 2014, 8(6): 6202-6210.

Methods		Advantages	Disadvantages	Ref
Top-down	Hydrothermal synthesis; solvothermal synthesis; acidic oxidation; electrochemical exfoliation	Large output; simple operation.	Irregularly size and shape; lots of oxygen-containing functional groups left on the GQDs surface; strong reductants are needed; numerous defects.	[11-19]
	Oxidation cutting of CF	Simple operation; large output; relatively cheap raw materials.	Too many oxygen-containing functional groups; low quantum yield(QY).	[21]
	Ultrasonic exfoliation	Simple operation; no reduction process; fewer surface defects and more stable electronic properties.	Depending on the quality of carbon fiber; special equipments are needed.	[22]
	Electron beam lithography	Precise control on both size and shape of resultant GQDs	Complex operation; expensive equipments; extremely low output.	[23]
Bottom-up	Solution chemical approaches	Well-defined monodispersed structures; easy control of both size and shape; high purity.	Low-output; difficulty to prevent aggregation.	[21], [24-26]
	Carbonization of organic molecules	Well-defined monodispersed structures; high QY; simple operation	Low-output.	[24], [27-28]
	Cage-opening of C60	Well-defined monodispersed structures; precise control on both size and shape; high QY.	Strict reaction conditions; very high heating temperature; expensive raw materials; low-output.	[24]

Methods		Advantages	Disadvantages	Ref
Top-down	Hydrothermal synthesis; solvothermal synthesis; acidic oxidation; electrochemical exfoliation	Large output; simple operation.	Irregularly size and shape; lots of oxygen-containing functional groups left on the GQDs surface; strong reductants are needed; numerous defects.	[11-19]
	Oxidation cutting of CF	Simple operation; large output; relatively cheap raw materials.	Too many oxygen-containing functional groups; low quantum yield(QY).	[21]
	Ultrasonic exfoliation	Simple operation; no reduction process; fewer surface defects and more stable electronic properties.	Depending on the quality of carbon fiber; special equipments are needed.	[22]
	Electron beam lithography	Precise control on both size and shape of resultant GQDs	Complex operation; expensive equipments; extremely low output.	[23]
Bottom-up	Solution chemical approaches	Well-defined monodispersed structures; easy control of both size and shape; high purity.	Low-output; difficulty to prevent aggregation.	[21], [24-26]
	Carbonization of organic molecules	Well-defined monodispersed structures; high QY; simple operation	Low-output.	[24], [27-28]
	Cage-opening of C60	Well-defined monodispersed structures; precise control on both size and shape; high QY.	Strict reaction conditions; very high heating temperature; expensive raw materials; low-output.	[24]