新型荧光碳点的制备及其在微量金属离子测定中的应用

刘娟娟; 陈永雷; 陈兴国

doi:10.15898/j.cnki.11-2131/td.201907100099

新型荧光碳点的制备及其在微量金属离子测定中的应用

1.
兰州大学化学化工学院, 甘肃兰州 730000

2.
兰州大学第二医院, 甘肃兰州 730030

基金项目:
国家自然科学基金项目（21675068）

详细信息

作者简介: 刘娟娟, 博士, 从事新型碳点荧光探针的合成及应用研究。E-mail:jjliu14@lzu.edu.cn

通讯作者: 陈兴国, 教授, 博士生导师, 从事纳米材料在分析化学中的应用研究。E-mail:chenxg@lzu.edu.cn

中图分类号: O657.39;O614

收稿日期: 2019-07-10

修回日期: 2019-09-09

录用日期: 2019-10-21

A Review of the Preparation of Novel Fluorescent Carbon Dot and Its Application for the Determination of Trace Metal Ions

1.
College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China

2.
Lanzhou University Second Hospital, Lanzhou 730030, China

More Information

Corresponding author: Xing-guo CHEN, chenxg@lzu.edu.cn

Received Date: 10 July 2019

Revised Date: 09 September 2019

Accepted Date: 21 October 2019

摘要

摘要: 碳点（CD）具有粒径小、抗光漂白性好、荧光稳定性高、发射光谱可调、表面易功能化、毒性低及生物相容性好等优点，已在催化、生物成像、药物传递、荧光检测、光电子器件等方面得到了广泛的应用。近年来，利用不同原料制备高性能荧光CD的合成方法备受关注。此外，通过CD直接与目标分析物相互作用，特异性配体修饰后的CD与目标分析物相互作用、CD与其他物质形成复合物后与目标分析物相互作用构建荧光探针，并将其用于微量金属离子的检测得到了迅速发展和广泛应用。本文阐述了CD的光学性质和合成原料，对其常用的自上而下法和自下而上法两类合成方法的过程及特点进行了总结。在此基础上，详细评述了基于CD与目标分析物的三种相互作用方式所构建的荧光探针在测定Fe³⁺、Zn²⁺、Cu²⁺等具有生化作用的离子和Hg²⁺、As³⁺、Pb²⁺、Cr⁶⁺、Cd²⁺等重金属离子的应用进展。本文指出，深入研究检测机理，发展新型检测模式，针对特定金属离子和样品组成设计构建荧光探针，建立可用于复杂样品的分析方法是开展构建新型CD荧光探针所面临的挑战和发展方向。
- 碳点 /
- 荧光探针 /
- 光学性质 /
- 合成原料 /
- 金属离子
Abstract: BACKGROUNDOwing to their small particle size, good stability against photobleaching, high fluorescence stability, tunable fluorescence emission, easy surface functionalization, low toxicity and excellent biocompatibility, carbon dot (CD) has been widely applied in many fields including catalyst, cell imaging, drug delivery, fluorescence detection and photoelectronic devices. In recent years, synthetic methods for preparing high-performance fluorescent CD using different raw materials have attracted much attention. In addition, detection of trace metal ions by a fluorescent probe has been rapidly developed and widely used. The fluorescent probe can be constructed thus:the CD directly interact with the target analyte, the CD modified by the specific ligand interact with the target analyte, and the CD forming a complex with other substances interact with the target analyte. OBJECTIVESTo provide references for researchers to synthesize CD and construct fluorescent probes based on CD for the determination of trace metal ions in complex samples. METHODSThe optical properties and synthetic raw materials of CD were described. The process and characteristics of the commonly used top-down and bottom-up methods were summarized. The application progress of fluorescent probes constructed by the three interaction modes between CD and target analytes for the determination of biochemical reaction ions, Fe³⁺, Zn²⁺ and Cu²⁺, and other heavy metal ions such as Hg²⁺, As³⁺, Pb²⁺, Cr⁶⁺ and Cd²⁺ were reviewed. RESULTSDifferent raw materials had been utilized for synthesizing CD with different properties. The prepared CD were used to construct fluorescent probes for the determination of micro metal ions with high selectivity and sensitivity. CONCLUSIONSFurther research on the determination mechanisms, development of new detection modes, construction of fluorescent probes for specific metal ions and sample components, and establishment of analytical methods, which can be applied to complex samples are the challenges and development orientation of the fluorescent probes based on CD.
- carbon dot /
- fluorescent probe /
- optical properties /
- synthetic materials /
- metal ions

HTML全文

图 1 (a) RGDE CD的制备及(b)用于检测细胞中ONOO^-的示意图

Figure 1.

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图 2 RYDE CD和RODE CD的制备及RYDE CD作为比率荧光探针用于测定亚硝酸盐的示意图

Figure 2.

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图 3 CD-AuNCs比率荧光探针的构建及其用于检测S^2-的示意图

Figure 3.

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图 4 N-CD用于检测Fe³⁺的示意图

Figure 4.

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图 5 基于CD的荧光探针的合成及其用于检测Zn²⁺的示意图

Figure 5.

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参考文献(112)

[1]	Xu X, He L, Long Y W, et al.S-doped carbon dots capped ZnCdTe quantum dots for ratiometric fluorescence sensing of guanine[J]. Sensors and Actuators B:Chemical, 2019, 279:44-52. doi: 10.1016/j.snb.2018.09.102
[2]	李庆霞, 刘亚轩, 陈卫明, 等.荧光光谱法分析油气化探样品中的芳烃[J].岩矿测试, 2014, 33(4):561-569. doi: 10.3969/j.issn.0254-5357.2014.04.018 http://www.ykcs.ac.cn/article/id/828f9ba4-bd16-4175-a33b-fa73d4cebcb3 Li Q X, Liu Y X, Chen W M, et al.Analysis of aromatic hydrocarbons in oil and gas geochemical exploration samples by fluorescence spectrometry[J]. Rock and Mineral Analysis, 2014, 33(4):561-569. doi: 10.3969/j.issn.0254-5357.2014.04.018 http://www.ykcs.ac.cn/article/id/828f9ba4-bd16-4175-a33b-fa73d4cebcb3
[3]	Sun X C, Lei Y.Fluorescent carbon dots and their sensing applications[J]. TrAC Trends in Analytical Chemistry, 2017, 89:163-180. doi: 10.1016/j.trac.2017.02.001
[4]	许金钩.荧光分析法近年来的某些进展[J].岩矿测试, 1992, 11(1):53-57. http://www.ykcs.ac.cn/article/id/ykcs_19920108 Xu J G.Some recent advances in fluorimetry[J]. Rock and Mineral Analysis, 1992, 11(1):53-57. http://www.ykcs.ac.cn/article/id/ykcs_19920108
[5]	Prapainop K, Mekseriwattana W, Siangproh W, et al.Successive detection of benzoic acid and total parabens in foodstuffs using mercaptosuccinic acid capped cadmium telluride quantum dots[J]. Food Control, 2019, 96:508-516. doi: 10.1016/j.foodcont.2018.10.009
[6]	Huo F J, Su J, Sun Y Q, et al.A rhodamine-based dual chemosensor for the visual detection of copper and the ratiometric fluorescent detection of vanadium[J]. Dyes and Pigments, 2010, 86(1):50-55. doi: 10.1016/j.dyepig.2009.11.007
[7]	Liu J J, Chen Y L, Wang W F, et al."Switch-on" fluorescent sensing of ascorbic acid in food samples based on carbon quantum dots-MnO₂ probe[J]. Journal of Agricultural and Food Chemistry, 2015, 64(1):371-380. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=26ab717c7faaa55438d2ef48b5c05d2a
[8]	Peng Z L, Han X, Li S H, et al.Carbon dots:Bioma-cromolecule interaction, bioimaging and nanomedicine[J]. Coordination Chemistry Reviews, 2017, 343:256-277. doi: 10.1016/j.ccr.2017.06.001
[9]	Shah S N A, Lin J M.Recent advances in chemilumin-escence based on carbonaceous dots[J]. Advances in Colloid and Interface Science, 2017, 241:24-36. doi: 10.1016/j.cis.2017.01.003
[10]	Hong G S, Diao S, Antaris A L, et al.Carbon nanoma-terials for biological imaging and nanomedicinal therapy[J]. Chemical Reviews, 2015, 115(19):10816-10906. doi: 10.1021/acs.chemrev.5b00008
[11]	Bartelmess J, Quinn S J, Giordani S.Carbon nanoma-terials:Multi-functional agents for biomedical fluorescence and Raman imaging[J]. Chemical Society Reviews, 2015, 44(14):4672-4698. doi: 10.1039/C4CS00306C
[12]	Kroto H W, Heath J R, O'Brien S C.C60:Buckmin-sterfullerene[J]. Nature, 1985, 318(6042):162-163. doi: 10.1038/318162a0
[13]	Iijima S.Helical microtubules of graphitic carbon[J]. Nature, 1991, 354(6348):56-58. doi: 10.1038/354056a0
[14]	Novoselov K S, Geim A K, Morozov S V, et al.Electric field effect in atomically thin carbon films[J]. Science, 2004, 306(5696):666-669. doi: 10.1126/science.1102896
[15]	Jiang J J, Ye G, Wang Z, et al.Heteroatom-doped carbon dots (CDs) as a class of metal-free photocatalysts for PET-RAFT polymerization under visible light and sunlight[J]. Angewandte Chemie International Edition, 2018, 57(37):12037-12042. doi: 10.1002/anie.201807385
[16]	Li F, Li T Y, Sun C X, et al.Selenium-doped carbon quantum dots for free-radical scavenging[J]. Angewandte Chemie International Edition, 2017, 56(33):9910-9914. doi: 10.1002/anie.201705989
[17]	Gong P W, Sun L, Wang F, et al.Highly fluorescent N-doped carbon dots with two-photon emission for ultrasensitive detection of tumor marker and visual monitor anticancer drug loading and delivery[J]. Chemical Engineering Journal, 2019, 356:994-1002. doi: 10.1016/j.cej.2018.09.100
[18]	Moniruzzaman M, Kim J S.Mechanistic studies on the β-resorcylic acid mediated carbon dots for the pH-induced fluorescence switch and sensing application[J]. Dyes and Pigments, 2019, 163:538-546. doi: 10.1016/j.dyepig.2018.12.041
[19]	Qu S N, Wang X Y, Lu Q P, et al.A biocompatible fluorescent ink based on water-soluble luminescent carbon nanodots[J]. Angewandte Chemie International Edition, 2012, 51(49):12215-12218. doi: 10.1002/anie.201206791
[20]	Xu X Y, Ray R, Gu Y L, 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. doi: 10.1021/ja040082h
[21]	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. doi: 10.1021/ja062677d
[22]	Zheng M, Xie Z G, Qu D, et al.On-off-on fluorescent carbon dot nanosensor for recognition of chromium(Ⅵ) and ascorbic acid based on the inner filter effect[J]. Applied Materials & Interfaces, 2013, 5(24):13242-13247.
[23]	Baker S N, Baker G A.Luminescent carbon nanodots:Emergent nanolights[J]. Angewandte Chemie International Edition, 2010, 49(38):6726-6744. doi: 10.1002/anie.200906623
[24]	Goryacheva I Y, Sapelkin A V, Sukhorukov G B.Carbon nanodots:Mechanisms of photoluminescence and principles of application[J]. TrAC Trends in Analytical Chemistry, 2017, 90:27-37. doi: 10.1016/j.trac.2017.02.012
[25]	Zheng L Y, Chi Y W, Dong Y Q, et al.Electrochemi-luminescence of water-soluble carbon nanocrystals released electrochemically from graphite[J]. Journal of the American Chemical Society, 2009, 131(13):4564-4565. doi: 10.1021/ja809073f
[26]	Zhang P J, Xue Z J, Luo D, et al.Dual-peak electro-generated chemiluminescence of carbon dots for iron ions detection[J]. Analytical Chemistry, 2014, 86(12):5620-5623. doi: 10.1021/ac5011734
[27]	Liu H P, Ye T, Mao C D.Fluorescent carbon nano-particles derived from candle soot[J]. Angewandte Chemie International Edition, 2007, 46(34):6473-6475. doi: 10.1002/anie.200701271
[28]	Qiao Z A, Wang Y F, 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. doi: 10.1039/c0cc02724c
[29]	Zhu S J, Meng Q N, Wang L, et al.Highly photo-luminescent carbon dots for multicolor patterning, sensors, and bioimaging[J]. Angewandte Chemie International Edition, 2013, 52(14):3953-3957. doi: 10.1002/anie.201300519
[30]	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. doi: 10.1021/ja204661r
[31]	Dong Y Q, Pang H C, Yang H B, et al.Carbon-based dots Co-doped with nitrogen and sulfur for high quantum yield and excitation-independent emission[J]. Angewandte Chemie International Edition, 2013, 52(30):7800-7804. doi: 10.1002/anie.201301114
[32]	Huang H, Lü J J, Zhou D L, et al.One-pot green synthesis of nitrogen-doped carbon nanoparticles as fluorescent probes for mercury ions[J]. RSC Advances, 2013, 3(44):21691-21696. doi: 10.1039/c3ra43452d
[33]	Yang X M, Zhuo Y, Zhu S S, et al.Novel and green synthesis of high-fluorescent carbon dots originated from honey for sensing and imaging[J]. Biosensors and Bioelectronics, 2014, 60:292-298. doi: 10.1016/j.bios.2014.04.046
[34]	Wang L, Zhou H S.Green synthesis of luminescent nitrogen-doped carbon dots from milk and its imaging application[J]. Analytical Chemistry, 2014, 86(18):8902-8905. doi: 10.1021/ac502646x
[35]	Li C L, Ou C M, Huang C C, et al.Carbon dots prepared from ginger exhibiting efficient inhibition of human hepatocellular carcinoma cells[J]. Journal of Materials Chemistry B, 2014, 2(28):4564-4571. doi: 10.1039/c4tb00216d
[36]	Wu Z L, Zhang P, Gao M X, et al.One-pot hydro-thermal synthesis of highly luminescent nitrogen-doped amphoteric carbon dots for bioimaging from Bombyx mori silk-natural proteins[J]. Journal of Materials Chemistry B, 2013, 1(22):2868-2873. doi: 10.1039/c3tb20418a
[37]	Wei J M, Shen J M, Zhang X, et al.Simple one-step synthesis of water-soluble fluorescent carbon dots derived from paper ash[J]. RSC Advances, 2013, 3(32):13119-13122. doi: 10.1039/c3ra41751d
[38]	Hu Y P, Yang J, Tian J W, et al.Waste frying oil as a precursor for one-step synthesis of sulfur-doped carbon dots with pH-sensitive photoluminescence[J]. Carbon, 2014, 77:775-782. doi: 10.1016/j.carbon.2014.05.081
[39]	Zhu L L, Yin Y J, Wang C F, et al.Plant leaf-derived fluorescent carbon dots for sensing, patterning and coding[J]. Journal of Materials Chemistry C, 2013, 1(32):4925-4932. doi: 10.1039/c3tc30701h
[40]	Jiang K, Sun S, Zhang L, et al.Red, green, and blue luminescence by carbon dots:Full-color emission tuning and multicolor cellular imaging[J]. Angewandte Chemie International Edition, 2015, 54(18):5360-5363. doi: 10.1002/anie.201501193
[41]	Liu Y H, Duan W X, Song W, et al.Red emission B, N, S-Co-doped carbon dots for colorimetric and fluorescent dual mode detection of Fe³⁺ ions in complex biological fluids and living cells[J]. ACS Applied Materials & Interfaces, 2017, 9(14):12663-12672. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=5cc07bb3ef443021b79abd60aeaaa428
[42]	Ma Y X, Chen Y L, Liu J J, et al.Ratiometric fluorescent detection of chromium(Ⅵ) in real samples based on dual emissive carbon dots[J]. Talanta, 2018, 185:249-257. doi: 10.1016/j.talanta.2018.03.081
[43]	Liu J J, Dong Y Y, Ma Y X, et al.One-step synthesis of red/green dual-emissive carbon dots for ratiometric sensitive ONOO^- probing and cell imaging[J]. Nanoscale, 2018, 10(28):13589-13598. doi: 10.1039/C8NR04596H
[44]	Liu J J, Chen Y L, Wang L L, et al.Modification-free fabricating ratiometric nanoprobe based on dual-emissive carbon dots for nitrite determination in food samples[J]. Journal of Agricultural and Food Chemistry, 2019, 67(13):3826-3836. doi: 10.1021/acs.jafc.9b00024
[45]	Xu Q, Kuang T R, Liu Y, et al.Heteroatom-doped carbon dots:Synthesis, characterization, properties, photoluminescence mechanism and biological applications[J]. Journal of Materials Chemistry B, 2016, 45(4):7204-7219.
[46]	Yu S J, Kang M W, Chang H C, et al.Bright fluorescent nanodiamonds:No photobleaching and low cytotoxicity[J]. Journal of the American Chemical Society, 2005, 127(50):17604-17605. doi: 10.1021/ja0567081
[47]	Bottini M, Balasubramanian C, Dawson M I, et al.Isolation and characterization of fluorescent nanoparticles from pristine and oxidized electric arc-produced single-walled carbon nanotubes[J]. The Journal of Physical Chemistry B, 2006, 110(2):831-836. doi: 10.1021/jp055503b
[48]	Zhou J G, Booker C, Li R Y, 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. doi: 10.1021/ja0669070
[49]	Liu R L, Wu D Q, Liu S H, et al.An aqueous route to multicolor photoluminescent carbon dots using silica spheres as carriers[J]. Angewandte Chemie International Edition, 2009, 48(25):4598-4601. doi: 10.1002/anie.200900652
[50]	Zhu H, Wang X L, Li Y L, et al.Microwave synthesis of fluorescent carbon nanoparticles with electrochemiluminescence properties[J]. Chemical Communications, 2009, (34):5118-5120. doi: 10.1039/b907612c
[51]	Li H T, He X D, Liu Y, et al.Synthesis of fluorescent carbon nanoparticles directly from active carbon via a one-step ultrasonic treatment[J]. Materials Research Bulletin, 2011, 46(1):147-151. doi: 10.1016/j.materresbull.2010.10.013
[52]	Xu Q, Pu P, Zhao J G, et al.Preparation of highly photoluminescent sulfur-doped carbon dots for Fe(Ⅲ) detection[J]. Journal of Materials Chemistry A, 2015, 3(2):542-546. doi: 10.1039/C4TA05483K
[53]	Li Z P, Zhang J, Li Y X, et al.Carbon dots based photoelectrochemical sensors for ultrasensitive detection of glutathione and its applications in probing of myocardial infarction[J]. Biosensors and Bioelectronics, 2018, 99:251-258. doi: 10.1016/j.bios.2017.07.065
[54]	Konar S, Kumar B N P, Mahto M K, et al.N-doped carbon dot as fluorescent probe for detection of cysteamine and multicolor cell imaging[J]. Sensors and Actuators B:Chemical, 2019, 286:77-85. doi: 10.1016/j.snb.2019.01.117
[55]	Li H X, Yan X, Qiao S P, et al.Yellow-emissive carbon dot-based optical sensing platforms:Cell imaging and analytical applications for biocatalytic reactions[J]. ACS Applied Materials & Interfaces, 2018, 10(9):7737-7744.
[56]	Kumari A, Kumar A, Sahu S K, et al.Synthesis of green fluorescent carbon quantum dots using waste polyolefins residue for Cu²⁺ ion sensing and live cell imaging[J]. Sensors and Actuators B:Chemical, 2018, 254:197-205. doi: 10.1016/j.snb.2017.07.075
[57]	Demir B, Lemberger M M, Panagiotopoulou M, et al.Tracking hyaluronan:Molecularly imprinted polymer coated carbon dots for cancer cell targeting and imaging[J]. ACS Applied Materials & Interfaces, 2018, 10(4):3305-3313.
[58]	Zhang R Z, Chen W. Nitrogen-doped carbon quantum dots: Facile synthesis and application as a "turn-off" fluorescent probe for detection of Hg²⁺ ions[J]. Biosensors and Bioelectronics, 2014, 55:83-90. doi: 10.1016/j.bios.2013.11.074
[59]	Li G L, Kong W H, Zhao M, et al.A fluorescence resonance energy transfer (FRET) based "turn-on" nanofluorescence sensor using a nitrogen-doped carbon dot-hexagonal cobalt oxyhydroxide nanosheet architecture and application to α-glucosidase inhibitor screening[J]. Biosensors and Bioelectronics, 2016, 79:728-735. doi: 10.1016/j.bios.2015.12.094
[60]	Zhang H J, Chen Y L, Liang M J, et al.Solid-phase synthesis of highly fluorescent nitrogen-doped carbon dots for sensitive and selective probing ferric ions in living cells[J]. Analytical Chemistry, 2014, 86(19):9846-9852. doi: 10.1021/ac502446m
[61]	Dong Y Q, Wang R X, Li G L, et al.Polyamine-functionalized carbon quantum dots as fluorescent probes for selective and sensitive detection of copper ions[J]. Analytical Chemistry, 2012, 84(14):6220-6224. doi: 10.1021/ac3012126
[62]	Liang M J, Chen Y L, Zhang H J, et al.Fluorescence resonance energy transfer-based ratiometric fluorescent assay for highly sensitive and selective determination of sulfide anions[J]. Analyst, 2015, 140(19):6711-6719. doi: 10.1039/C5AN01378J
[63]	Qu Z B, Zhou X G, Gu L, et al.Boronic acid functiona-lized graphene quantum dots as a fluorescent probe for selective and sensitive glucose determination in microdialysate[J]. Chemical Communications, 2013, 49(84):9830-9832. doi: 10.1039/c3cc44393k
[64]	Xu H, Huang S S, Liao C Y, et al.Highly selective and sensitive fluorescence probe based on thymine-modified carbon dots for Hg²⁺ and L-cysteine detection[J]. RSC Advances, 2015, 5(108):89121-89127. doi: 10.1039/C5RA18432K
[65]	Zhai W Y, Wang C X, Yu P, et al.Single-layer MnO₂ nanosheets suppressed fluorescence of 7-hydroxycoumarin:Mechanistic study and application for sensitive sensing of ascorbic acid in vivo[J]. Analytical Chemistry, 2014, 86(24):12206-12213. doi: 10.1021/ac503215z
[66]	Deng J H, Lu Q J, Hou Y X, et al.Nanosensor composed of nitrogen-doped carbon dots and gold nanoparticles for highly selective detection of cysteine with multiple signals[J]. Analytical Chemistry, 2015, 87(4):2195-2203. doi: 10.1021/ac503595y
[67]	Wang Q, Zhang S R, Zhong Y G, et al.Preparation of yellow-green-emissive carbon dots and their application in constructing a fluorescent turn-on nanoprobe for imaging of selenol in living cells[J]. Analytical Chemistry, 2017, 89(3):1734-1741. doi: 10.1021/acs.analchem.6b03983
[68]	Qian Z S, Chai L J, Zhou Q, et al.Reversible fluorescent nanoswitch based on carbon quantum dots nanoassembly for real-time acid phosphatase activity monitoring[J]. Analytical Chemistry, 2015, 87(14):7332-7339. doi: 10.1021/acs.analchem.5b01488
[69]	Miao X, Qu D, Yang D X, et al.Synthesis of carbon dots with multiple color emission by controlled graphitization and surface functionalization[J]. Advanced Materials, 2018, 30(1):1704740. doi: 10.1002/adma.201704740
[70]	Fu F L, Wang Q.Removal of heavy metal ions from wastewaters:A review[J]. Journal of Environmental Management, 2011, 92(3):407-418. doi: 10.1016/j.jenvman.2010.11.011
[71]	Karaaslan N M, Yaman M.Assessment and ICP-MS determination of toxic metal content (Cd, Cr, Ni, and Pb) in Turkish chicken meat for use as bioindicator for human health[J]. Atomic Spectroscopy, 2018, 39(1):16-21. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=9ef9111b7ffc34b8503db60491a25024
[72]	Paulino A T, Minasse F A S, Guilherme M R, et al.Novel adsorbent based on silkworm chrysalides for removal of heavy metals from wastewaters[J]. Journal of Colloid and Interface Science, 2006, 301(2):479-487. doi: 10.1016/j.jcis.2006.05.032
[73]	Bush A I, Pettingell W H, Multhaup G, et al.Rapid induction of Alzheimer A beta amyloid formation by zinc[J]. Science, 1994, 265(5177):1464-1467. doi: 10.1126/science.8073293
[74]	Zhang L, Peng D, Liang R P, et al.Graphene-based optical nanosensors for detection of heavy metal ions[J]. TrAC Trends in Analytical Chemistry, 2018, 102:280-289. doi: 10.1016/j.trac.2018.02.010
[75]	Waheed A, Mansha M, Ullah N.Nanomaterials-based electrochemical detection of heavy metals in water:Current status, challenges and future direction[J]. TrAC Trends in Analytical Chemistry, 2018, 105:37-51. doi: 10.1016/j.trac.2018.04.012
[76]	田志仁, 封雪, 姜晓旭, 等.生态环境监测工作中应用AAS/AFS和XRF法测定土壤重金属数据质量评价[J].岩矿测试, 2019, 38(5):479-488. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.201811080119 Tian Z R, Feng X, Jiang X X, et al.Evaluation of data quality on the detection of heavy metals in soils by atomic absorption spectrometry or atomic fluorescence spectrometry and X-ray fluorescence spectrometry in ecological environment monitoring[J]. Rock and Mineral Analysis, 2019, 38(5):479-488. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.201811080119
[77]	徐进力, 邢夏, 唐瑞玲, 等.动能歧视模式ICP-MS测定地球化学样品中14种痕量元素[J].岩矿测试, 2019, 38(4):394-402. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.201812070131 Xu J L, Xing X, Tang R L, et al.Determination of 14 trace elements in geochemical samples by ICP-MS using kinetic energy discrimination mode[J]. Rock and Mineral Analysis, 2019, 38(4):394-402. http://www.ykcs.ac.cn/article/doi/10.15898/j.cnki.11-2131/td.201812070131
[78]	Tel-Cyana G, Ullaha Z, Öztürka M, et al.Heavy metals, trace and major elements in 16 wild mushroom species determined by ICP-MS[J]. Atomic Spectroscopy, 2018, 39(1):29-37. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=6bd25226c89b8fdecc76151f978b676e
[79]	Ananthanarayanan A, Wang X W, Routh P, et al.Facile synthesis of graphene quantum dots from 3D graphene and their application for Fe³⁺ sensing[J]. Advanced Functional Materials, 2014, 24(20):3021-3026. doi: 10.1002/adfm.201303441
[80]	Zhang S W, Li J X, Zeng M Y, et al.Polymer nanodots of graphitic carbon nitride as effective fluorescent probes for the detection of Fe³⁺ and Cu²⁺ ions[J]. Nanoscale, 2014, 6(8):4157-4162. doi: 10.1039/c3nr06744k
[81]	Ho A J, Chang H C, Su W T.DOPA-mediated reduction allows the facile synthesis of fluorescent gold nanoclusters for use as sensing probes for ferric ions[J]. Analytical Chemistry, 2012, 84(7):3246-3253. doi: 10.1021/ac203362g
[82]	Qu X Y, Liu Q, Ji X N, et al.Enhancing the Stokes' shift of BODIPY dyes via through-bond energy transfer and its application for Fe³⁺-detection in live cell imaging[J]. Chemical Communications, 2012, 48(38):4600-4602. doi: 10.1039/c2cc31011b
[83]	Wu P, Li Y, Yan X P.CdTe quantum dots (QDs) based kinetic discrimination of Fe²⁺ and Fe³⁺, and CdTe QDs-Fenton hybrid system for sensitive photoluminescent detection of Fe²⁺[J]. Analytical Chemistry, 2009, 81(15):6252-6257. doi: 10.1021/ac900788w
[84]	Yang C X, Ren H B, Yan X P.Fluorescent metal-organic framework MIL-53(Al) for highly selective and sensitive detection of Fe³⁺ in aqueous solution[J]. Analytical Chemistry, 2013, 85(15):7441-7446. doi: 10.1021/ac401387z
[85]	Feng J, Chen Y L, Han Y L, et al.Fluorescent carbon nanoparticles:A low-temperature trypsin-assisted preparation and Fe³⁺ sensing[J]. Analytica Chimica Acta, 2016, 926:107-117. doi: 10.1016/j.aca.2016.04.039
[86]	Oyaro N, Ogendi J, Murago E N M, et al.The contents of Pb, Cu, Zn and Cd in meat in Nairobi, Kenya[J]. Journal of Food, Agriculture & Environment, 2007, 5(3&4):119-121.
[87]	Shi Y P, Chen Z H, Cheng X, et al.A novel dual-emission ratiometric fluorescent nanoprobe for sensing and intracellular imaging of Zn²⁺[J]. Biosensors and Bioelectronics, 2014, 61:397-403. doi: 10.1016/j.bios.2014.05.050
[88]	Moskvin L N, Kamentsev M Y, Grigor'ev G L, et al.Capillary-electrophoretic determination of zinc and cadmium ions in aqueous solutions with ion-exchange preconcentration[J]. Journal of Analytical Chemistry, 2010, 65(1):99-102. doi: 10.1134/S1061934810010193
[89]	Kaur P, Kaur S, Mahajan A, et al.Highly selective colorimetric sensor for Zn²⁺ based on hetarylazo derivative[J]. Inorganic Chemistry Communications, 2008, 11(6):626-629. doi: 10.1016/j.inoche.2008.02.025
[90]	Zhang Z M, Shi Y P, Pan Y, et al.Quinoline derivative-functionalized carbon dots as a fluorescent nanosensor for sensing and intracellular imaging of Zn²⁺[J]. Journal of Materials Chemistry B, 2014, 2(31):5020-5027. doi: 10.1039/C4TB00677A
[91]	Cao Y Y, Liu Y N, Li F, et al.Portable colorimetric detection of copper ion in drinking water via red beet pigment and smartphone[J]. Microchemical Journal, 2019, 150:104176. doi: 10.1016/j.microc.2019.104176
[92]	Liu J M, Lin L P, Wang X X, et al.Highly selective and sensitive detection of Cu²⁺ with lysine enhancing bovine serum albumin modified-carbon dots fluorescent probe[J]. Analyst, 2012, 137(11):2637-2642. doi: 10.1039/c2an35130g
[93]	Aragay G, Pons J, Merkoci A.Recent trends in macro-, micro-, and nanomaterial-based tools and strategies for heavy-metal detection[J]. Chemical Reviews, 2011, 111(5):3433-3458. doi: 10.1021/cr100383r
[94]	Zrazhevskiy P, Sena M, Gao X H.Designing multifun-ctional quantum dots for bioimaging, detection, and drug delivery[J]. Chemical Society Reviews, 2010, 39(11):4326-4354. doi: 10.1039/b915139g
[95]	Yang H, Mao H J, Wan Z H, et al.Micelles assembled with carbocyanine dyes for theranostic near-infrared fluorescent cancer imaging and photothermal therapy[J]. Biomaterials, 2013, 34(36):9124-9133. doi: 10.1016/j.biomaterials.2013.08.022
[96]	Gedda G, Lee C Y, Lin Y C, et al.Green synthesis of carbon dots from prawn shells for highly selective and sensitive detection of copper ions[J]. Sensors and Actuators B:Chemical, 2016, 224:396-403. doi: 10.1016/j.snb.2015.09.065
[97]	Liu Y L, Zhou Q X, Yuan Y Y, et al.Hydrothermal synthesis of fluorescent carbon dots from sodium citrate and polyacrylamide and their highly selective detection of lead and pyrophosphate[J]. Carbon, 2017, 115:550-560. doi: 10.1016/j.carbon.2017.01.035
[98]	Wang H T, Kang B S, Chancellor Jr T F, et al.Fast electrical detection of Hg(Ⅱ) ions with AlGaN/GaNAlGaN/GaN high electron mobility transistors[J]. Applied Physics Letters, 2007, 91(4):042114. doi: 10.1063/1.2764554
[99]	Gupta A, Verma N C, Khan S, et al.Carbon dots for naked eye colorimetric ultrasensitive arsenic and glutathione detection[J]. Biosensors and Bioelectronics, 2016, 81:465-472. doi: 10.1016/j.bios.2016.03.018
[100]	Kiran K, Kumar K, Prasad B, et al.Speciation deter-mination of chromium(Ⅲ) and(Ⅵ) using preconcentration cloud point extraction with flame atomic absorption spectrometry (FAAS)[J]. Journal of Hazardous Materials, 2008, 150(3):582-586. doi: 10.1016/j.jhazmat.2007.05.007
[101]	Niu W J, Shan D, Zhu R H, et al.Dumbbell-shaped carbon quantum dots/AuNCs nanohybrid as an efficient ratiometric fluorescent probe for sensing cadmium(Ⅱ) ions and L-ascorbic acid[J]. Carbon, 2016, 96:1034-1042. doi: 10.1016/j.carbon.2015.10.051
[102]	贺攀红, 吴领军, 杨珍, 等.氢化物发生-电感耦合等离子体发射光谱法同时测定土壤中痕量砷锑铋汞[J].岩矿测试, 2013, 32(2):240-243. doi: 10.3969/j.issn.0254-5357.2013.02.009 http://www.ykcs.ac.cn/article/id/beead5e6-2d93-4ced-a1ef-78bbfcbeb0bc He P H, Wu L J, Yang Z, et al.Simultaneous determination of trace As, Sb, Bi and Hg in soils by hydride generation-inductively coupled plasma-atomic emission spectrometry[J]. Rock and Mineral Analysis, 2013, 32(2):240-243. doi: 10.3969/j.issn.0254-5357.2013.02.009 http://www.ykcs.ac.cn/article/id/beead5e6-2d93-4ced-a1ef-78bbfcbeb0bc
[103]	郭丹, 范华均.汞-碘化钾-甲紫-Triton X-305体系光度法测定痕量汞[J].岩矿测试, 1996, 15(1):39-42. http://www.ykcs.ac.cn/article/id/ykcs_19960113 Guo D, Fan H J.Spectrophotometric determination of trace mercury with the color system of mecury(Ⅱ) potassium iodide-methyl violet-Triton X-305[J]. Rock and Mineral Analysis, 1996, 15(1):39-42. http://www.ykcs.ac.cn/article/id/ykcs_19960113
[104]	Qin X Y, Lu W B, Asiri A M, et al.Microwave-assisted rapid green synthesis of photoluminescent carbon nanodots from flour and their applications for sensitive and selective detection of mercury(Ⅱ) ions[J]. Sensors and Actuators B:Chemical, 2013, 184:156-162. doi: 10.1016/j.snb.2013.04.079
[105]	Liu J J, Chen Y L, Wang W F, et al.Effective synthesis of highly fluorescent nitrogen doped carbon nanoparticles for selective sensing of Hg²⁺ in food and cosmetics samples[J]. RSC Advances, 2016, 6(92):89916-89924. doi: 10.1039/C6RA20861D
[106]	Lu W B, Qin X Y, Liu S, et al.Economical, green synthesis of fluorescent carbon nanoparticles and their use as probes for sensitive and selective detection of mercury(Ⅱ) ions[J]. Analytical Chemistry, 2012, 84(12):5351-5357. doi: 10.1021/ac3007939
[107]	黎香荣, 韦万兴, 崔翔, 等.电感耦合等离子体发射光谱法测定磷矿石中微量有毒元素铅砷镉[J].岩矿测试, 2009, 28(4):370-372. doi: 10.3969/j.issn.0254-5357.2009.04.014 http://www.ykcs.ac.cn/article/id/ykcs_20090414 Li X R, Wei W X, Cui X, et al.Determination of trace toxic elements of lead, arsenic and cadmium in phosphate ores by inductively coupled plasma-atomic emission spectrometry[J]. Rock and Mineral Analysis, 2009, 28(4):370-372. doi: 10.3969/j.issn.0254-5357.2009.04.014 http://www.ykcs.ac.cn/article/id/ykcs_20090414
[108]	Liu Y L, Zhou Q X, Li J, et al.Selective and sensitive chemosensor for lead ions using fluorescent carbon dots prepared from chocolate by one-step hydrothermal method[J]. Sensors and Actuators B:Chemical, 2016, 237:597-604. doi: 10.1016/j.snb.2016.06.092
[109]	张保科, 王蕾, 马生凤, 等.电感耦合等离子体质谱法测定地质样品中铜锌铕钆铽的干扰及校正[J].岩矿测试, 2012, 31(2):253-257. doi: 10.3969/j.issn.0254-5357.2012.02.010 http://www.ykcs.ac.cn/article/id/ykcs_20120210 Zhang B K, Wang L, Ma S F, et al.Interference correction in determination of Cu, Zn, Eu, Gd, Tb in geological samples by inductively coupled plasma-mass spectrometry[J]. Rock and Mineral Analysis, 2012, 31(2):253-257. doi: 10.3969/j.issn.0254-5357.2012.02.010 http://www.ykcs.ac.cn/article/id/ykcs_20120210
[110]	Mutuyimana F P, Liu J J, Nsanzamahoro S, et al.Yellow-emissive carbon dots as a fluorescent probe for chromium(Ⅵ)[J]. Microchimica Acta, 2019, 186(3):163. doi: 10.1007/s00604-019-3284-1
[111]	高琳, 陈圣洁, 陈芳.Triton X-114存在下镉试剂分光光度法测定环境水样中的镉[J].岩矿测试, 2013, 32(1):114-118. doi: 10.3969/j.issn.0254-5357.2013.01.020 http://www.ykcs.ac.cn/article/id/c43d3f1f-5f00-4875-ad59-9484e7ead1dd Gao L, Chen S J, Chen F.Spectrophotometric determination of Cd(Ⅱ) in environmental water samples with cadion in the presence of Triton X-114 surface active agent[J]. Rock and Mineral Analysis, 2013, 32(1):114-118. doi: 10.3969/j.issn.0254-5357.2013.01.020 http://www.ykcs.ac.cn/article/id/c43d3f1f-5f00-4875-ad59-9484e7ead1dd
[112]	Khan S, Soylak M, Alosmanov R, et al.Development of phosphate-containing polymer-based solid phase extraction procedure for the separation, enrichment, and determination of cadmium in water and food samples by FAAS[J]. Atomic Spectroscopy, 2018, 39(4):158-163. http://www.wanfangdata.com.cn/details/detail.do?_type=perio&id=bc3df5a12117279451f3907262a1f848