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作为一种新型的荧光碳纳米材料,由于其生物相容性好、稳定性高和制备修饰简单等独特性质,碳点被广泛应用于生物医学等多个领域.根据其结构和性质,碳点可分为石墨烯量子点(GQDs)、碳纳米点(CNDs)、聚合物点(PDs).本文概述了"自上而下"和"自下而上"两种碳点合成策略和相应的合成方法,并初步阐述了量子尺寸效应,表面态效应,分子态和碳核态,交联增强荧光效应(CEE效应)等碳点发光机理.最后,总结并展望了碳点在生物成像、药物负载、探针检测、脑部疾病的研究和光诊疗等方面的生物应用.
Abstract:As a novel kind of fluorescent nanomaterials, carbon dots(CDs)have been widely used in biomedical and other research due to their unique properties such as good biocompatibility,high stability, and facile and low-cost synthesis and functionalization. CDs includes graphene quantum dots(GQDs), carbon nanodots(CNDs)and polymer dots(PDs). In this review, two synthetic approaches of top-down and bottom-top were summarized as well as corresponding reactions of ablating and oxidating bulk carbon materials and carbonization of small molecules,biomass, and polymers, respectively. The fluorescent mechanisms of CDs including quantum confinement effect, surface/edge state, molecule state, carbon core state, and crosslink-enhanced emission effect(CEE effect)were discussed, followed by their applications in biological imaging,drug loading, probe detection, brain disease research, optical diagnosis and treatment.
[1]XU X,RAY R,GU Y,et al.Electrophoretic analysis and purification of fluorescent single-walled carbon nanotube fragments[J].Journal of the American Chemical Society,2004.126(40):12736-12737.
[2]HUANG X,ZHANG F,ZHU L,et al.Effect of injection routes on the biodistribution,clearance,and tumor uptake of carbon dots[J].ACS Nano,2013,7(7):5684-5693.
[3]HARDMAN R.A toxicologic review of quantum dots:toxicity depends on physicochemical and environmental factors[J].Environmental Health Perspectives,2006,114(2):165-172.
[4]LIU Y,ZHOU L,LI Y,et al.Facile synthesis of nitrogen-doped carbon dots with robust fluorescence in a strongly alkaline solution and a reversible fluorescence‘off-on’switch between strongly acidic and alkaline solutions[J].RSC Advances,2016,6(110):108203-108208.
[5]YANG M,LI B,ZHONG K,et al.Photoluminescence properties of N-doped carbon dots prepared in different solvents and applications in p H sensing[J].Journal of Materials Science,2018,53(4):2424-2433.
[6]YUAN F,WANG Z,LI X,et al.Bright multicolor bandgap fluorescent carbon quantum dots for electroluminescent ligh-emitting diodes[J].Advanced Materials,2017,29(3):1604436.
[7]ZHANG W,ZHOU Y,DONG C,et al.Carbon-dot-modified Ti O2-x mesoporous single crystals with enhanced photocatalytic activity for degradation of phenol[J].Research on Chemical Intermediates,2018,44(8):4797-4807.
[8]SARKAR T,BOHIDAR H B,SOLANKI P R.Carbon dots-modified chitosan based electrochemical biosensing platform for detection of vitamin D[J].International Journal of Biological Macromolecules,2018,109:687-697.
[9]LIU J H,LI D Y,HE J H,et al.Polarity-sensitive polymer carbon dots prepared at room-temperature for monitoring the cell polarity dynamics during autophagy[J].ACS Applied Materials&Interfaces,2020,12(4):4815-4820.
[10]YANG S T,CAO L,LUO P G,et al.Carbon dots for optical imaging in vivo[J].Journal of the American Chemical Society,2009,131(32):11308-11309.
[11]KUNDU A,LEE J,PARK B,et al.Facile approach to synthesize highly fluorescent multicolor emissive carbon dots via surface functionalization for cellular imaging[J].Journal of Colloid and Interface Science,2018,513:505-514.
[12]WANG Q,HUANG X,LONG Y,et al.Hollow luminescent carbon dots for drug delivery[J].Carbon,2013,59:192-199.
[13]ZUO G,XIE A,PAN X,et al.Fluorine-doped cationic carbon dots for efficient gene delivery[J].ACSApplied Nano Materials,2018,1(5):2376-2385.
[14]HUANG P,LIN J,WANG X,et al.Light-triggered theranostics based on photosensitizer-conjugated carbon dots for simultaneous enhance-fluorescence imaging and photodynamic therapy[J].Advanced Materials,2012,24(37):5104-5110.
[15]WANG H,MU Q,WANG K,et al.Nitrogen and boron dual-doped graphene quantum dots for nearinfrared second window imaging and photothermal therapy[J].Applied Materials Today,2019,14:108-117.
[16]TAO S,ZHU S,FENG T,et al.The polymeric characteristics and photoluminescence mechanism in polymer carbon dots:A review[J].Materials Today Chemistry,2017,6:13-25.
[17]ZHU S,SONG Y,ZHAO X,et al.The photoluminescence mechanism in carbon dots(graphene quantum dots,carbon nanodots,and polymer dots):current state and future perspective[J].Nano Research,2015,8(2):355-381.
[18]XIAO L,SUN H.Novel properties and applications of carbon nanodots[J].Nanoscale Horizons,2018,3(6):565-597.
[19]HU C,LI M,QIU J,et al.Design and fabrication of carbon dots for energy conversion and storage[J].Chemical Society Reviews,2019,48(8):2315-2337.
[20]LIU J J,LI D,ZHANG K,et al.One-step hydrothermal synthesis of nitrogen-doped conjugated carbonized polymer dots with 31%efficient red emission for in vivo imaging[J].Small,2018,14(15):1703919.
[21]ZHAO Q L,ZHANG Z L,HUANG B H,et al.Facile preparation of low cytotoxicity fluorescent carbon nanocrystals by electrooxidation of graphite[J].Chemical Communications,2008(41):5116-5118.
[22]WU M,WANG Y,WU W,et al.Preparation of functionalized water-soluble photoluminescent carbon quantum dots from petroleum coke[J].Carbon,2014,78:480-489.
[23]JAISWAL A,GHOSH S S,Chattopadhyay A.One step synthesis of C-dots by microwave mediated caramelization of poly(ethylene glycol)[J].Chemical Communications,2012,48(3):407-409.
[24]ZHU C,ZHAI J,DONG S.Bifunctional fluorescent carbon nanodots:green synthesis via soy milk and application as metal-free electrocatalysts for oxygen reduction[J].Chemical Communications,2012,48(75):9367-9369.
[25]ANILKUMAR P,WANG X,CAO L,et al.Toward quantitatively fluorescent carbon-based“quantum”dots[J].Nanoscale,2011,3(5):2023-2027.
[26]WANG Q,HUANG X,LONG Y,et al.Hollow luminescent carbon dots for drug delivery[J].Carbon,2013,59:192-199.
[27]DIMOS K.Carbon quantum dots:surface passivation and functionalization[J].Current Organic Chemistry,2016,20(6):682-695.
[28]SUN Y P,ZHOU B,LIN Y,et al.Quantum-sized carbon dots for bright and colorful photoluminescence[J].Journal of the American Chemical Society,2006,128(24):7756-7757.
[29]ZHANG X,HE X,LI Y,et al.A cytotoxicity study of fluorescent carbon nanodots using human bronchial epithelial cells[J].Journal of Nanoscience and Nanotechnology,2013,13(8):5254-5259.
[30]ZHENG M,LIU S,LI J,et al.Integrating oxaliplatin with highly luminescent carbon dots:an unprecedented theranostic agent for personalized medicine[J].Advanced Materials,2014,26(21):3554-3560.
[31]DING C,ZHU A,TIAN Y.Functional surface engineering of C-dots for fluorescent biosensing and in vivo bioimaging[J].Accounts of Chemical Research,2014,47(1):20-30.
[32]SU Y,XIE M,LU X,et al.Facile synthesis and photoelectric properties of carbon dots with upconversion fluorescence using arc-synthesized carbon by-products[J].Rsc Advances,2014,4(10):4839-4842.
[33]HU S L,NIU K Y,SUN J,et al.One-step synthesis of fluorescent carbon nanoparticles by laser irradiation[J].Journal of Materials Chemistry,2009,19(4):484-488.
[34]ZHOU J,BOOKER C,LI R,et al.An electrochemical avenue to blue luminescent nanocrystals from multiwalled carbon nanotubes(MWCNTs)[J].Journal of the American Chemical Society,2007,129(4):744-745.
[35]LI H,HE X,KANG Z,et al.Water-soluble fluorescent carbon quantum dots and photocatalyst design[J].Angewandte Chemie International Edition,2010,49(26):4430-4434.
[36]LIU M,XU Y,NIU F,et al.Carbon quantum dots directly generated from electrochemical oxidation of graphite electrodes in alkaline alcohols and the applications for specific ferric ion detection and cell imaging[J].Analyst,2016,141(9):2657-2664.
[37]QI B P,BAO L,ZHANG Z L,et al.Electrochemical methods to study photoluminescent carbon nanodots:Preparation,photoluminescence mechanism and sensing[J].ACS Applied Materials&Interfaces,2016,8(42):28372-28382.
[38]BAO L,ZHANG Z L,TIAN Z Q,et al.Electrochemical tuning of luminescent carbon nanodots:from preparation to luminescence mechanism[J].Advanced Materials,2011,23(48):5801-5806.
[39]LIU H,YE T,MAO C.Fluorescent carbon nanoparticles derived from candle soot[J].Angewandte Chemie International Edition,2007,46(34):6473-6475.
[40]PENG H,TRAVAS-SEJDIC J.Simple aqueous solution route to luminescent carbogenic dots from carbohydrates[J].Chemistry of Materials,2009,21(23):5563-5565.
[41]TIAN L,GHOSH D,CHEN W,et al.Nanosized carbon particles from natural gas soot[J].Chemistry of Materials,2009,21(13):2803-2809.
[42]QIAO Z A,WANG Y,GAO Y,et al.Commercially activated carbon as the source for producing multicolor photoluminescent carbon dots by chemical oxidation[J].Chemical Communications,2010,46(46):8812-8814.
[43]PENG J,GAO W,GUPTA B K,et al.Graphene quantum dots derived from carbon fibers[J].Nano Letters,2012,12(2):844-849.
[44]BOURLINOS A B,STASSINOPOULOS A,ANGLOS D,et al.Surface functionalized carbogenic quantum dots[J].Small,2008,4(4):455-458.
[45]KRYSMANN M J,KELARAKIS A,DALLAS P,et al.Formation mechanism of carbogenic nanoparticles with dual photoluminescence emission[J].Journal of the American Chemical Society,2012,134(2):747-750.
[46]ZHU H,WANG X,LI Y,et al.Microwave synthesis of fluorescent carbon nanoparticles with electrochemiluminescence properties[J].Chemical Communications,2009(34):5118-5120.
[47]JIANG J,HE Y,LI S,et al.Amino acids as the source for producing carbon nanodots:microwave assisted one-step synthesis,intrinsic photoluminescence property and intense chemiluminescence enhancement[J].Chemical Communications,2012,48(77):9634-9636.
[48]ZHENG J,WANG Y,ZHANG F,et al.Microwave-assisted hydrothermal synthesis of solid-state carbon dots with intensive emission for white light-emitting devices[J].Journal of Materials Chemistry C,2017,5(32):8105-8111.
[49]TANG L,JI R,CAO X,et al.Deep ultraviolet photoluminescence of water-soluble self-passivated graphene quantum dots[J].ACS Nano,2012,6(6):5102-5110.
[50]SUN S,ZHANG L,JIANG K,et al.Toward high-efficient red emissive carbon dots:facile preparation,unique properties,and applications as multifunctional theranostic agents[J].Chemistry of Materials,2016,28 (23):8659-8668.
[51]YANG Z C,WANG M,YONG A M,et al.Intrinsically fluorescent carbon dots with tunable emission derived from hydrothermal treatment of glucose in the presence of monopotassium phosphate[J].Chemical Communications,2011,47(42):11615-11617.
[52]HSU P C,CHANG H T.Synthesis of high-quality carbon nanodots from hydrophilic compounds:role of functional groups[J].Chemical Communications,2012,48(33):3984-3986.
[53]QU D,ZHENG M,ZHANG L,et al.Formation mechanism and optimization of highly luminescent N-doped graphene quantum dots[J].Scientific Reports,2014,4(1):5294.
[54]LIU H,LI Z,SUN Y,et al.Synthesis of luminescent carbon dots with ultrahigh quantum yield and inherent folate receptor-positive cancer cell targetability[J].Scientific Reports,2018,8(1):1086.
[55]ZONG J,ZHU Y,YANG X,et al.Synthesis of photoluminescent carbogenic dots using mesoporous silica spheres as nanoreactors[J].Chemical Communications,2011,47(2):764-766.
[56]YANG Y,WU D,HAN S,et al.Bottom-up fabrication of photoluminescent carbon dots with uniform morphology via a soft-hard template approach[J].Chemical Communications,2013,49(43):4920-4922.
[57]GU Z G,LI D J,ZHENG C,et al.MOF-templated synthesis of ultrasmall photoluminescent carbonnanodot arrays for optical applications[J].Angewandte Chemie International Edition,2017,56(24):6853-6858.
[58]WILSON W L,SZAJOWSKI P F,BRUS L E.Quantum confinement in size-selected,surface-oxidized silicon nanocrystals[J].Science,1993,262(5137):1242-1244.
[59]EDA G,LIN Y Y,MATTEVI C,et al.Blue photoluminescence from chemically derived graphene oxide[J].Advanced Materials,2010,22(4):505-509.
[60]WANG Y,DONG L,XIONG R,et al.Practical access to bandgap-like N-doped carbon dots with dual emission unzipped from PAN@PMMA core-shell nanoparticles[J].Journal of Materials Chemistry C,2013,1(46):7731-7735.
[61]ZHAI X,ZHANG P,LIU C,et al.Highly luminescent carbon nanodots by microwave-assisted pyrolysis[J].Chemical Communications,2012,48(64):7955-7957.
[62]RAY S C,SAHA A,JANA N R,et al.Fluorescent carbon nanoparticles:synthesis,characterization,and bioimaging application[J].The Journal of Physical Chemistry C,2009,113(43):18546-18551.
[63]SONG Y,ZHU S,ZHANG S,et al.Investigatio n from chemical structure to photoluminescent mechanism:a type of carbon dots from the pyrolysis of citric acid and an amine[J].Journal of Materials Chemistry C,2015,3(23):5976-5984.
[64]KHAN S,GUPTA A,VERMA N C,et al.Time-resolved emission reveals ensemble of emissive states as the origin of multicolor fluorescence in carbon dots[J].Nano Letters,2015,15(12):8300-8305.
[65]KO H Y,CHANG Y W,PARAMASIVAM G,et al.In vivo imaging of tumour bearing near-infrared fluorescence-emitting carbon nanodots derived from tire soot[J].Chemical Communications,2013,49(87):10290-10292.
[66]WANG H,MU Q,WANG K,et al.Nitrogen and boron dual-doped graphene quantum dots for nearinfrared second window imaging and photothermal therapy[J].Applied Materials Today,2019,14:108-117.
[67]SUN Y P,WANG X,LU F,et al.Doped c arbon nanoparticles as a new platform for highly photoluminescent dots[J].The Journal of Physical Chemistry C,2008,112(47):18295-18298.
[68]FOWLEY C,NOMIKOU N,MCHALE A P,et al.Extending the tissue penetration capability of conventional photosensitisers:a carbon quantum dot-protoporphyrin IX conjugate for use in two-photon excited photodynamic therapy[J].Chemical Communications,2013,49(79):8934-8936.
[69]LI H,HE X,KANG Z,et al.Water-soluble fluorescent carbon quantum dots and photocatalyst design[J].Angewandte Chemie International Edition,2010,49(26):4430-4434.
[70]YUAN F,WANG Z,LI X,et al.Bright multicolor bandgap fluorescent carbon quantum dots for electroluminescent light-Emitting diodes[J].Advanced Materials,2017,29(3):1604436.
[71]KWON W,LEE G,DO S,et al.Size-controlled soft-template synthesis of carbon nanodots toward versatile photoactive materials[J].Small,2014,10(3):506-513.
[72]TANG L,JI R,LI X,et al.Size-dependent structural and optical characteristics of glucose-derived graphene quantum dots[J].Particle&Particle Systems Characterization,2013,30(6):523-531.
[73]YU P,WEN X,TOH Y R,et al.Temperature-dependent fluorescence in carbon dots[J].The Journal of Physical Chemistry C,2012,116(48):25552-25557.
[74]WEN X,YU P,TOH Y R,et al.Intrinsic and extrinsic fluorescence in carbon nanodots:ultrafast time-resolved fluorescence and carrier dynamics[J].Advanced Optical Materials,2013,1(2):173-178.
[75]KRYSMANN M J,KELARAKIS A,DALLAS P,et al.Formation mechanism of carbogenic nanoparticles with dual photoluminescence emission[J].Journal of the American Chemical Society,2012,134(2):747-750.
[76]ZHU S,MENG Q,WANG L,et al.Highly photoluminescent carbon dots for multicolor patterning,sensors,and bioimaging[J].Angewandte Chemie International Edition,2013,52(14):3953-3957.
[77]SUN Y,CAO W,LI S,et al.Ultrabright and multicolorful fluorescence of amphiphilic polyethyleneimine polymer dots for efficiently combined imaging and therapy[J].Scientific Reports,2013,3(1):1-6.
[78]ZHU S,WANG L,ZHOU N,et al.The crosslink enhanced emission (CEE) in non-conjugated polymer dots:from the photoluminescence mechanism to the cellular uptake mechanism and internalization[J].Chemical Communications,2014,50(89):13845-13848.
[79]VALLAN L,URRIOLABEITIA E P,RUIP魪REZ F,et al.Supramolecular-enhanced charge transfer within entangled polyamide chains as the origin of the universal blue fluorescence of polymer carbon dots[J].Journal of the American Chemical Society,2018,140(40):12862-12869.
[80]YANG S T,WANG X,WANG H,et al.Carbon dots as nontoxic and high-performance fluorescence imaging agents[J].The Journal of Physical Chemistry C,2009,113(42):18110-18114.
[81]MADANNEJAD R,SHOAIE N,JAHANPEYMA F,et al.Toxicity of carbon-based nanomaterials:Reviewing recent reports in medical and biological systems[J].Chemico-Biological Interactions,2019,307:206-222.
[82]RAJA I S,SONG S J,KANG M S,et al.Toxicity of zero-and one-dimensional carbon nanomaterials[J].Nanomaterials,2019,9(9):1214.
[83]ZHANG X,HE X,LI Y,et al.A cytotoxicity study of fluorescent carbon nanodots using human bronchial epithelial cells[J].Journal of Nanoscience and Nanotechnology,2013,13(8):5254-5259.
[84]YANG S T,CAO L,LUO P G,et al.Carbon dots for optical imaging in vivo[J].Journal of the American Chemical Society,2009,131(32):11308-11309.
[85]WANG Y,ANILKUMAR P,CAO L,et al.Carbon dots of different composition and surface functionalization:cytotoxicity issues relevant to fluorescence cell imaging[J].Experimental Biology and Medicine,2011,236(11):1231-1238.
[86]WANG Y,BAO L,LIU Z,et al.Aptamer biosensor based on fluorescence resonance energy transfer from upconverting phosphors to carbon nanoparticles for thrombin detection in human plasma[J].Analytical Chemistry,2011,83(21):8130-8137.
[87]CAO L,WANG X,MEZIANI M J,et al.Carbon dots for multiphoton bioimaging[J].Journal of the American Chemical Society,2007,129(37):11318-11319.
[88]LI Q,OHULCHANSKYY T Y,LIU R,et al.Photoluminescent carbon dots as biocompatible nanoprobes for targeting cancer cells in vitro[J].The Journal of Physical Chemistry C,2010,114(28):12062-12068.
[89]XU Y,WU M,LIU Y,et al.Nitroge-doped carbon dots:a facile and general preparation method,photoluminescence investigation,and imaging applications[J].Chemistry-A European Journal,2013,19(7):2276-2283.
[90]LIU J H,CAO L,LECROY G E,et al.Carbon“quantum”dots for fluorescence labeling of cells[J].ACS Applied Materials&Interfaces,2015,7(34):19439-19445.
[91]KANG Y F,FANG Y W,LI Y H,et al.Nucleus-staining with biomolecule-mimicking nitrogen-doped carbon dots prepared by a fast neutralization heat strategy[J].Chemical Communications,2015,51(95):16956-16959.
[92]GENG X,SUN Y,LI Z,et al.Retrosynthesis of tunable fluorescent carbon dots for precise long-term mitochondrial tracking[J].Small,2019,15(48):1901517.
[93]WANG Q,HUANG X,LONG Y,et al.Hollow luminescent carbon dots for drug delivery[J].Carbon,2013,59:192-199.
[94]ZHAO S,SUN S,JIANG K,et al.In situ synthesis of fluorescent mesoporous silica-carbon dot nanohybrids featuring folate receptor-overexpressing cancer cell targeting and drug delivery[J].NanoMicro Letters,2019,11(1):32.
[95]ZHENG M,LIU S,LI J,et al.Integrating oxaliplatin with highly luminescen t carbon dots:an unprecedented theranostic agent for personalized medicine[J].Advanced Materials,2014,26(21):3554-3560.
[96]DU F,MIN Y,ZENG F,et al.A targeted and FRE-based ratiometric fluorescent nanoprobe for imaging mitochondrial hydrogen peroxide in living cells[J].Small,2014,10(5):964-972.
[97]LIU Y,TIAN Y,TIAN Y,et al.Carbo-do-based nanosensors for the detection of intracellular redox state[J].Advanced Materials,2015,27(44):7156-7160.
[98]LIU J H,LI D Y,HE J H,et al.A polarity-sensitive polymer carbon dots prepared at room-temperature for monitoring the cell polarity dynamics during autophagy[J].ACS Applied Materials&Interfaces,2020,12(4):4815-4820.
[99]LI S,LEBLANC R M.Aggregation of insulin at the interface[J].The Journal of Physical Chemistry B,2014,118(5):1181-1188.
[100]CAI Q,WANG L,DENG G,et al.Systemic delivery to central nervous system by engineered PLGA nanoparticles[J].American Journal of Translational Research,2016,8(2):749.
[101]BILENSOY E.Cationic nanoparticles for cancer therapy[J].Expert Opinion on Drug Delivery,2010,7(7):795-809.
[102]XIE J,LEE S,CHEN X.Nanoparticle-based theranostic agents[J].Advanced Drug Delivery Reviews,2010,62(11):1064-1079.
[103]NIU Y,TAN H,LI X,et al.Protein-carbon dot nanohybrid-based early blood-brain barrier damage theranostics[J].ACS Applied Materials&Interfaces,2020,12(3):3445-3452.
[104]WANG H,MU Q,WANG K,et al.Nitrogen and boron dual-doped graphene quantum dots for nearinfrared second window imaging and photothermal therapy[J].Applied Materials Today,2019,14:108-117.
基本信息:
中图分类号:O657.3;TB383.1
引用信息:
[1]陈一,朱雪儿,周沁雨,等.碳点的合成、光学性能及生物应用[J].汕头大学学报(自然科学版),2021,36(03):3-26+2.
基金信息:
广东省普通高校特色创新类项目(2018KTSCX060)
2021-08-15
2021-08-15