石墨烯量子点的制备及其生物应用
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摘要
石墨烯量子点(GQDs)作为石墨烯材料的衍生物,在兼顾了石墨烯优良特性的同时,又依靠量子限域效应和边界效应而具备了光致发光(PL)等石墨烯所不具备的性质,而且在细胞毒性、生物相容性等方面也有更好的表现。近年来,GQDs的制备方法日趋多样化,通常将其分为Top-down和Bottom-up两种方法。随着GQDs在生物医学领域应用的不断深化,对其形貌和尺寸控制也提出了更高的要求,因此本文对Bottom-up法等一些有希望精确控制GQDs形貌和尺寸的方法进行了重点介绍,并对各种方法的优缺点进行了对比。目前GQDs的生物应用主要包括生物成像、生物传感器、药物输运和抗菌剂等,本文对其各种应用分别进行了介绍,并结合各种应用对GQDs的要求给出了制备方法的建议。文章最后还指出了GQDs研究中存在的问题及发展方向。
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.
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.
引文
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[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.
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[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.
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[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 watersoluble,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 greenluminescent 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.LIU
[27]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-bandaids used for wound disinfection.ACS Nano,2014,8(6):6202–6210.