硫量子点（SQDs）是一种新型的半导体纳米材料，具有良好的发光特性、生物相容性、水溶液分散性和抗菌性等优点，在生物传感和医学成像等领域被广泛研究。目前已报道有多种合成SQDs的方法，其中大多数使用氢氧化钠（NaOH）为蚀刻剂，聚乙二醇-400（PEG-400）为配体。由于蚀刻剂和配体的选择较为单一，致使合成的SQDs的光致发光（PL）波长较短，绝大多数为蓝光，这会限制SQDs的实际应用。电化学发光（ECL）分析方法具有灵敏度高、背景信号低、测试速度快、线性范围宽等优势。迄今为止，有关SQDs的PL特性研究较多，但是关于SQDs的ECL性能的研究和应用相对较少，一方面因为蚀刻剂选择的单一性（NaOH）导致SQDs自身只能发射蓝色PL，这使得SQDs在ECL过程中不太可能被用作近红外ECL发光体；另一方面，配体选择的单一性（PEG-400）使得SQDs的ECL效率较低。因此，探究蚀刻剂和配体选择对合成SQDs的发光性能的调控作用具有重要研究意义。基于此，以蚀刻剂和配体为出发点，旨在开发新型SQDs，使得合成的SQDs具有长波长发射的PL和ECL或高的ECL发光效率。具体研究内容如下：

      （1）长波长发射SQDs的合成及其ECL性能研究：以升华硫为硫源，牛血清蛋白（BSA）为配体，碳酸钠（Na₂CO₃）为蚀刻剂，采用简单的一步水热法，在优化的反应条件下，合成了具有红光PL特性的SQDs，合成的SQDs的PL波长在575 nm处具有良好的发光稳定性和较高的发光效率，荧光量子产率（QY）为1.03%；通过选择不同蚀刻剂（NaOH或Na₂CO₃），可实现SQDs的PL波长在蓝光和红光范围的调谐，其中，以Na₂CO₃为蚀刻剂合成的SQDs具有较大的量子尺寸和新的紫外可见吸收带，这是其具有长波长PL发射的主要原因。此外，在中性或碱性溶液中，SQDs在过硫酸钾（K₂S₂O₈）共反应试剂存在时，反应体系在−1.4 V的负电位下产生强的ECL信号；酚类物质的代表间苯二酚（RS）能够增强SQDs-K₂S₂O₈体系的ECL强度，当RS浓度在2.5 ~ 25 nM范围内时，RS浓度与反应体系的ECL强度呈良好的线性关系，线性方程为ΔI = 76.6C（nM） + 126.5，R² = 0.994，检出限为0.61 nM；标准偏差（RSD）为1.9%（n = 7），稳定性较好；基于SQDs-K₂S₂O₈体系的ECL强度与RS浓度具有良好的线性关系，建立了检测RS的分析新方法，并应用于河水中RS的检测，取得了良好的回收率；探讨了体系的ECL发光机理，SQDs在ECL过程中是重要的发光体，其ECL发射波长为575 nm，SQDs的ECL机理属于共反应剂型的还原氧化机理。

       （2）基于不同配体调控合成SQDs及其ECL性能研究：以升华硫为硫源，以NaOH为蚀刻剂，选择不同的配体：PEG-400，BSA，聚苯乙烯磺酸钠（PSS）合成SQDs；在合成的SQDs上进一步修饰聚3，4-乙烯二氧噻吩/聚苯乙烯磺酸盐（PEDOT:PSS）导电剂，研究了配体种类、浓度及导电剂修饰对SQDs的ECL性能的影响；三种配体都能够成功制备SQDs，成功制备SQDs是其具有ECL性能的前提，导电剂的修饰能显著增强SQDs的ECL信号；考察了以PEG-400为配体合成的SQDs在K₂S₂O₈共反应试剂存在时的ECL行为，合成的SQDs在负电位区（−1.4 V）表现出较强的ECL信号。

      本研究通过选择调控蚀刻剂的种类合成了具有红光发射的SQDs，合成的SQDs具有较好的PL稳定性和优异的ECL性能。为ECL和PL分析提供了新的发光体，对SQDs在发光分析、生物标记、生物成像等领域的应用具有重要的科学意义。研究了不同配体及导电剂修饰对SQDs的ECL性能的调控作用，为开发高ECL发光效率的SQDs提供参考，丰富ECL分析理论。

       Sulfur quantum dots (SQDs) are a new type of semiconductor nanomaterial with excellent luminescence properties, biocompatibility, aqueous dispersion and antibacterial properties, and have been widely studied in the fields of biosensing and medical imaging. At present, a variety of synthesis methods of SQDs have been reported, most of which use sodium hydroxide (NaOH) as the etching agent and PEG-400 as ligand. Due to the relatively simple selection of etching agent and ligand, the photoluminescence (PL) wavelengths of synthesized SQDs is short, and most of it is blue range, which will limit its practical application. Electrochemiluminescence (ECL) analytical methods offer several advantages, including low background signal, high sensitivity, temporal and spatial controllability, fast test speed and wide linear range. Currently, there has been more research on the fluorescence properties of SQDs than on their ECL properties. On the one hand, SQDs itself can only emit blue PL because of the singleness of etching agent selection (most use NaOH), which makes SQDs unlikely to be used as a near infrared ECL emitter in ECL process. On the other hand, the singleness of ligand selection (most use PEG-400) makes the ECL of SQDs less efficient. Therefore, it is of great significance to explore the regulatory effect of etching agent and ligand selection on the luminescence properties of synthetic SQDs. Based on this, we aim to synthesize SQDs with long wavelength emission of PL and ECL or high ECL luminous efficiency using etching agent and ligand as starting point. The specific research contents are as follows:

      (1) Facile synthesis of SQDs with red light emission and implications for electrochemiluminescence analysis application: SQDs with red light PL characteristics were synthesized by a simple one-step hydrothermal method under optimized reaction conditions, using sublimed sulfur as sulfur source, bovine serum protein (BSA) as ligand stabilizer, and sodium carbonate (Na₂CO₃) as etching agent. The PL wavelength of the synthesized SQDs has good luminescence stability and high luminescence efficiency at 575 nm, and the quantum yield is 1.03%; The PL wavelength of SQDs can be tuned in the blue and red ranges by selecting different etching agents (NaOH or Na₂CO₃), SQDs synthesized by Na₂CO₃ as an etching agent has a large quantum size and a new UV-visible absorption band, which is the main reason for the long wavelength of its emission; In neutral or alkaline solution, in the presence of potassium persulfate (K₂S₂O₈) co-reactive reagent, the reaction system produces a strong ECL signal at a negative potential of -1.4 V; Resorcinol (RS), a representative phenolic substance, can enhance the ECL strength of SQDs-K₂S₂O₈ system. When the concentration of RS is in the range of 2.5 ~ 25 nM, there is a good linear relationship between the concentration of RS and the ECL intensity of the reaction system. The linear equation is ΔI = 76.6C（nM）+ 126.5, R² = 0.994, and the detection limit is 0.61 nM; When RS concentration is 25 nM, 7 repeated scans are performed, the relative standard deviation is 1.9%, which show that the stability of SQDs-K₂S₂O₈ system is good. Based on the linear relationship between ECL strength and RS concentration of SQDs- K₂S₂O₈ system, a new method for RS detection was established and applied to the detection of RS in river water, and a good recovery rate was obtained; The ECL luminescence mechanism of the system is discussed. SQDs is an important luminescent body in the ECL process, and its ECL wavelength is located in the near infrared region. The ECL mechanism of SQDs belongs to the reduction and oxidation mechanism of co-reactive solvents.

       (2) SQDs synthesis and ECL performance of different ligands: Using sublimed sulfur as sulfur source and NaOH as etching agent, SQDs was synthesized by selecting different ligands: PEG-400, BSA, Sodium Polystyrene Sulfonate (PSS); Poly3, 4-vinyldioxthiophene/polystyrene sulfonate (PEDOT:PSS) conductive agent was further modified on the synthesized SQDs, and the effects of ligand type, concentration and conductive agent modification on the ECL performance of SQDs were studied. The successful preparation of SQDs is the prerequisite for its good ECL performance. The modification of conductive agent can significantly enhance the ECL signal of SQDs. The ECL behavior of the optimized SQDs in the presence of K₂S₂O₈ co-reactive reagent was investigated. The synthesized SQDs showed a strong ECL signal in the negative potential region(−1.4 V).

       In this study, SQDs with red PL emission were synthesized by changing the type of bases, and the synthesized SQDs have better PL stability and excellent ECL performance. It provides a new luminophor for ECL and PL analysis, and has important scientific significance for the application of SQDs in luminescence analysis, biomarkers, biological imaging and other fields. The effects of different ligands and conductive modifications on the ECL performance of SQDs were studied, which can provide a reference for the development of SQDs with high ECL luminous efficiency and enrich the theory of ECL analysis.

[1]Yang W, Yang Y, Li H, et al. Integration of Cd: ZnS QDs into ZIF-8 for enhanced selectivity toward Cu2+ detection[J]. Inorganic Chemistry Frontiers, 2020, 7(19): 3718-3726.

[2]Hu J, He X, Pu H, et al. The influence of exposed surface on trap state of PbS quantum dots[J]. Superlattices and Microstructures, 2020, 145: 106616.

[3]Melnychuk C, Guyot-Sionnest P. Thermodynamic limits to HgTe quantum dot infrared detector performance[J]. Journal of Electronic Materials, 2022, 51(3): 1428-1435.

[4]Winnik F M, Maysinger D. Quantum dot cytotoxicity and ways to reduce it[J]. Accounts of Chemical Research, 2013, 46(3): 672-680.

[5]Wang B, Lu S. The light of carbon dots: From mechanism to applications[J]. Matter, 2022, 5(1): 110-149.

[6] Ju Y Y, Shi X X, Xu S Y, et al. Atomically precise water-soluble graphene quantum dot for cancer sonodynamic therapy[J]. Advanced Science, 2022, 9(19): 2105034.

[7]Ma Y, Mei H, Li Y, et al. A novel raiometric fluorescence probe based on silicon quantum dots and copper nanoclusters for visual assay of L-cysteine in milks[J]. Food Chemistry, 2022, 379: 132155.

[8]Meyer B. Elemental sulfur[J]. Chemical Reviews, 1976, 76(3): 367-388.

[9]Li S, Chen D, Zheng F, et al. Water-soluble and lowly toxic sulfur quantum dots[J]. Advanced Functional Materials, 2014, 24(45): 7133-7138.

[10]Shen L, Wang H, Liu S, et al. Assembling of sulfur quantum dots in fission of sublimed sulfur[J]. Journal of the American Chemical Society, 2018, 140(25): 7878-7884.

[11]Song Y, Tan J, Wang G, et al. Oxygen accelerated scalable synthesis of highly fluorescent sulfur quantum dots[J]. Chemical Science, 2020, 11(3): 772-777

[12]Wang H, Wang Z, Xiong Y, et al. Hydrogen peroxide assisted synthesis of highly lumines-cent sulfur quantum dots[J]. Angewandte Chemie International Edition, 2019, 131(21): 7114-7118.

[13]Gong X, Cai Q, Zhang J, et al. Protein-directed synthesis of fluorescent sulfur quantum dots for highly robust detection of pyrophosphate[J]. Microchimica Acta, 2023, 190(3): 104.

[14]Gao N, Zeng H, Wang X, et al. Graphdiyne: a new carbon allotrope for electrochemiluminescence[J]. Angewandte Chemie International Edition, 2022, 61(28): e202204485.

[15]Qi H, Zhang C. Electrogenerated chemiluminescence biosensing[J]. Analytical Chemistry, 2019, 92(1): 524-534.

[16]Wang N, Gao H, Li Y, et al. Dual intramolecular electron transfer for in situ coreactant-embedded electrochemiluminescence microimaging of membrane protein[J]. Angewandte Chemie International Edition, 2021, 60(1): 197-201.

[17]Sun Y, Zhang Y, Zhang H X, et al. Integrating highly efficient recognition and signal transition of g-C3N4 embellished Ti3C2 MXene hybrid nanosheets for electrogenerated chemiluminescence analysis of protein kinase activity[J]. Analytical Chemistry, 2020, 92(15): 10668-10676.

[18]Sun Y, Li P, Zhu Y, et al. In situ growth of TiO2 nanowires on Ti3C2 MXenes nanosheets as highly sensitive luminol electrochemiluminescent nanoplatform for glucose detection in fruits, sweat and serum samples[J]. Biosensors and Bioelectronics, 2021, 194: 113600.

[19]Li P, Xu Z, Zhao L, et al. Nanoluminophores composed of 1, 1-Ferrocenedicarboxylic acid and tetrakis-(4-carboxyphenyl) porphyrin for electrochemiluminescence sensing[J]. ACS Applied Nano Materials, 2022, 5(11): 16278-16288.

[20]Ji T, Xu X, Wang X, et al. Background-free chromatographic detection of sepsis biomarker in clinical human serum through near-infrared to near-infrared upconversion immunolabeling[J]. ACS Nano, 2020, 14(12): 16864-16874.

[21]Zhao L, Song X, Ren X, et al. Rare self-luminous mixed-valence Eu-MOF with a self-enhanced characteristic as a near-infrared fluorescent ECL probe for nondestructive immunodetection[J]. Analytical Chemistry, 2021, 93(24): 8613-8621.

[22]Zhao L, Song X, Ren X, et al. Ultrasensitive near-infrared electrochemiluminescence biosensor derived from Eu-MOF with antenna effect and high efficiency catalysis of specific CoS2 hollow triple shelled nanoboxes for procalcitonin[J]. Biosensors and Bioelectronics, 2021, 191: 113409.

[23]Kim J H, Kim J. Post-synthesis modification of photoluminescent and electrochemiluminescent Au nanoclusters with dopamine[J]. Nanomaterials, 2020, 11(1): 46.

[24]Zhou Y Y, Ding Y M, Zhao W, et al. Efficient NIR electrochemiluminescent dyes based on Ruthenium (II) complexes containing an N-heterocyclic carbene ligand[J]. Chemical Communications, 2021, 57(10): 1254-1257.

[25]Li P, Luo L, Cheng D, et al. Regulation of the structure of zirconium-based porphyrinic metal-organic framework as highly electrochemiluminescence sensing platform for thrombin[J]. Analytical Chemistry, 2022, 94(14): 5707-5714.

[26]Yin X, Zhang C, Guo Y, et al. PbS QD-based photodetectors: future-oriented near-infrared detection technology[J]. Journal of Materials Chemistry C, 2021, 9(2): 417-438.

[27]Zhang C, Zhang P, Ji X, et al. Ultrasonication-promoted synthesis of luminescent sulfur nano-dots for cellular imaging applications[J]. Chemical Communications, 2019, 55(86): 13004-13007.

[28]Arshad F, Sk M P, Maurya S K, et al. Mechanochemical synthesis of sulfur quantum dots for cellular imaging[J]. ACS Applied Nano Materials, 2021, 4(4): 3339-3344.

[29]Xiao L, Du Q, Huang Y, et al. Rapid synthesis of sulfur nanodots by one-step hydrothermal reaction for luminescence-based applications[J]. ACS Applied Nano Materials, 2019, 2(10): 6622-6628.

[30]Duan Y, Tan J, Huang Z, et al. Facile synthesis of carboxymethyl cellulose sulfur quantum dots for live cell imaging and sensitive detection of Cr (VI) and ascorbic acid [J]. Carbohydrate Polymers, 2020, 249: 116882.

[31]Gao P, Huang Z, Tan J, et al. Efficient conversion of elemental sulfur to robust ultrabright fluorescent sulfur quantum dots using sulfur-ethylenediamine precursor[J]. ACS Sustainable Chemistry & Engineering, 2022, 10(14): 4634-4641.

[32]Yan F, Xu M, Xu J, et al. Facile synthesis of high-performance sulfur quantum dots via an effective ethylenediamine-assisted acceleration strategy for fluorescent sensing[J]. Sensors and Actuators B: Chemical, 2022, 370: 132393.

[33]Chang Y, He R, Wei Y, et al. Polyethyleneimine-sulfur quantum dot composites for dual-channel detection of tetracycline by colorimetric and fluorescence sensing[J]. ACS Applied Nano Materials, 2023, 6(9): 7414-7421.

[34]Xia M, Mei H, Qian Q, et al. Sulfur quantum dot-based “ON-OFF-ON” fluorescence platform for detection and bioimaging of Cr (VI) and ascorbic acid in complex environmental matrices and biological tissues[J]. RSC Advances, 2021, 11(18): 10572-10581.

[35]Shen L, Chen X, Chen Y, et al. One-step hydrothermal synthesis of sulfur quantum dots for photoelectrochemical catalysis for dye degradation[J]. Journal of Electronic Materials, 2022, 51(6): 3092-3100.

[36]Zhang W, Liang H, Qin X, et al. Double-network luminescent films constructed using sulfur quantum dots and lanthanide complexes[J]. ACS Applied Materials & Interfaces, 2022, 14(35): 40136-40144.

[37]丁鹭榕, 傅文轩, 丁昊等. 电化学发光显微成像：从机理解析到生化分析[J]. 分析化学, 2021, 49(07): 1188-1197.

[38]Moreno-Alcantar G, Aliprandi A, De Cola L. Aggregation-induced emission in electrochemiluminescence: advances and perspectives[J]. Aggregation-Induced Emission, 2021: 65-90.

[39]罗秋霞. 共轭微孔聚合物设计合成及电化学发光性能研究[D]. 南昌：南昌大学, 2023.

[40]Huang Y, Zhao D, Chen Y, et al. Ratiometric electrochemiluminescence biosensor for hepatitis C virus E2 protein based on block copolymers-solubilized Ir(ppy)3 with high electrochemiluminescence efficiency[J]. Electrochimica Acta, 2022, 429: 141028.

[41]Lian S, Huang Z, Lin Z, et al. A highly selective melamine sensor relying on intensified electrochemiluminescence of the silica nanoparticles doped with [Ru(bpy)3]2+/molecularly imprinted polymer modified electrode[J]. Sensors and Actuators B: Chemical, 2016, 236: 614-620.

[42]Lei Y M, Wu D, Pan M C, et al. Dynamic surface reconstruction of individual gold nanoclusters by using a co-reactant enables color-tunable electrochemiluminescence[J]. Chemical Science, 2024, 15(9): 3255-3261.

[43]Tan L, Ge J, Jie G, et al. Ultrasensitive electrochemiluminescence biosensor based on dual quenching effects of silver nanoclusters and multiple cycling amplification for detection of ATP[J]. Talanta, 2024, 271: 125668.

[44]He S J, Chu K, Wong J M, et al. Electrochemiluminescence of bare glassy carbon with benzoyl peroxide as the coreactant in N, N-dimethylformamide[J]. Journal of Analysis and Testing, 2020, 4: 257-263.

[45]Yan K, Wang P, Wang M, et al. Solvothermal synthesis of luminescence molybdenum disulfide QDs and the ECL biosensing application[J]. Microchemical Journal, 2022, 179: 107589.

[46]Liu L, Yang A, Luo W, et al. Ultrasensitive detection of cyclin D1 by a self-enhanced ECL immunosensor based on Bi2S3 quantum dots[J]. Analyst, 2021, 146(6): 2057-2064.

[47]Cao Y, Zhu J J. Recent progress in electrochemiluminescence of halide perovskites[J]. Frontiers in Chemistry, 2021, 9: 629830.

[48]Li H, Zhao G, Yang Y, et al. Bifunctional TEMPO-based catalysis boosts luminol electrochemiluminescence for cholesterol sensing[J]. Sensors and Actuators B: Chemical, 2024, 403: 135186.

[49]Qiao Y, Li Y, Fu W, et al. Enhancing the electrochemiluminescence of luminol by chemically modifying the reaction microenvironment[J]. Analytical Chemistry, 2018, 90(15): 9629-9636.

[50]Zhang X, Wang P, Nie Y, et al. Recent development of organic nanoemitter-based ECL sensing application[J]. TrAC Trends in Analytical Chemistry, 2021, 143: 116410.

[51]Wang B, Zhao L, Li Y, et al. Porphyrin-based metal-organic frameworks enhanced electrochemiluminescence (ECL) by overcoming aggregation-caused quenching: A new ECL emitter for the detection of trenbolone[J]. Analytica Chimica Acta, 2023, 1276: 341616.

[52]Lv W, Yang Q, Li Q, et al. Quaternary ammonium salt-functionalized tetraphenylethene derivative boosts electrochemiluminescence for highly sensitive aqueous-phase biosensing [J]. Analytical Chemistry, 2020, 92(17): 11747-11754.

[53]Zhang N, Wang X T, Xiong Z, et al. Hydrogen bond organic frameworks as a novel electrochemiluminescence luminophore: Simple synthesis and ultrasensitive biosensing [J]. Analytical Chemistry, 2021, 93(51): 17110-17118.

[54]Ma C, Cao Y, Gou X, et al. Recent progress in electrochemiluminescence sensing and imaging [J]. Analytical Chemistry, 2020, 92(1): 431-454.

[55]Li L, Chen Y, Zhu J-J. Recent advances in electrochemiluminescence analysis [J]. Analytical Chemistry, 2016, 89(1): 358-371.

[56]Xiang L, Liu L-L, Yuan R, et al. Aggregation-induced electrochemiluminescence of copper nanoclusters by regulating valence state ratio of Cu(I)/Cu(0) for ultrasensitive detection of microrna [J]. Analytical Chemistry, 2023, 95(9): 4454-4460.

[57]Valenti G, Scarabino S, Goudeau B, et al. Single cell electrochemiluminescence imaging: From the proof-of-concept to disposable device-based analysis [J]. Journal of the American Chemical Society, 2017, 139(46): 16830-16837.

[58]Ma X, Gao W, Du F, et al. Rational design of electrochemiluminescent devices [J]. Accounts of Chemical Research, 2021, 54(14): 2936-2945.

[59]Chen L, Zhang C, Xing D.Based bipolar electrode-electrochemiluminescence (BPE-ECL) device with battery energy supply and smartphone read-out: a handheld ECL system for biochemical analysis at the point-of-care level[J]. Sensors and Actuators B: Chemical, 2016, 237: 308-317.

[60]Han T, Yang J, Wang Y, et al. Boosted anodic electrochemiluminescence from blue-emissive sulfur quantum dots and its bioanalysis of glutathione[J]. Electrochimica Acta, 2021, 381: 138281.

[61]Ji K, Wang Y, Mao L, et al. Ultrasensitive SQDs-based electrochemiluminescence assay for determination of miRNA-141 with dual-amplification of co-reaction accelerators and DNA walker[J]. Sensors and Actuators B: Chemical, 2021, 345: 130405.

[62]Hu S, Qin D, Meng S, et al. Cathodic electrochemiluminescence based on resonance energy transfer between sulfur quantum dots and dopamine quinone for the detection of dopamine[J]. Microchemical Journal, 2022, 181: 107776.

[63]Wang X, Zhao Y, Hua Q, et al. An ultrasensitive electrochemiluminescence biosensor for the detection of total bacterial count in environmental and biological samples based on a novel sulfur quantum dot luminophore[J]. Analyst, 2022, 147(8): 1716-1721.

[64]Fiamegos Y C, Stalikas C D, Pilidis G A, et al. Synthesis and analytical applications of 4-aminopyrazolone derivatives as chromogenic agents for the spectrophotometric determination of phenols[J]. Analytica Chimica Acta, 2000, 403(1-2): 315-323.

[65]Pistonesi M F, Di Nezio M S, Centurión M E, et al. Determination of phenol, resorcinol and hydroquinone in air samples by synchronous fluorescence using partial least-squares (PLS)[J]. Talanta, 2006, 69(5): 1265-1268.

[66]Fujino K, Yoshitake T, Kehr J, et al. Simultaneous determination of 5-hydroxyindoles and catechols by high-performance liquid chromatography with fluorescence detection following derivatization with benzylamine and 1, 2-diphenylethylenediamine[J]. Journal of Chromatography A, 2003, 1012(2): 169-177.

[67]Asan A, Isildak I. Determination of major phenolic compounds in water by reversed-phase liquid chromatography after pre-column derivatization with benzoyl chloride[J]. Journal of Chromatography A, 2003, 988(1): 145-149.

[68]Bai Z, Shen L, Wei J, et al. Layered sulfur nanosheets prepared by assembly of sulfur quantum dots: implications for wide optical absorption and multiwavelength photoluminescence[J]. ACS Applied Nano Materials, 2020, 3(11): 10749-10756.

[69]Zhu R, Zhang Y, Wang J, et al. A novel anodic electrochemiluminescence behavior of sulfur-doped carbon nitride nanosheets in the presence of nitrogen-doped carbon dots and its application for detecting folic acid[J]. Analytical and Bioanalytical Chemistry, 2019, 411: 7137-7146.

[70]Nie Y, Zhang X, Zhang Q, et al. A novel high efficient electrochemiluminescence sensor based on reductive Cu (I) particles catalyzed Zn-doped MoS2 QDs for HPV 16 DNA determination[J]. Biosensors and Bioelectronics, 2020, 160: 112217.

[71]Ma Z, Xu Y, Li P, et al. Self-catalyzed surface reaction-induced fluorescence resonance energy transfer on cysteine-stabilized MnO2 quantum dots for selective detection of dopamine[J]. Analytical Chemistry, 2021, 93(7): 3586-3593.

[72]Wang M, Sun Y, Yang M. CdS QDs amplified electrochemiluminescence of N, S co-doped graphene quantum dots and its application for Pb (II) determination[J]. Chemistry Letters, 2018, 47(1): 44-47.

[73]Kadian S, Manik G, Kalkal A, et al. Effect of sulfur doping on fluorescence and quantum yield of graphene quantum dots: an experimental and theoretical investigation[J]. Nanotechnology, 2019, 30(43): 435704.

[74]Hu S, Qin D, Meng S, et al. Cathodic electrochemiluminescence based on resonance energy transfer between sulfur quantum dots and dopamine quinone for the detection of dopamine[J]. Microchemical Journal, 2022, 181: 107776.

[75]Qiao G, Liu L, Hao X, et al. Signal transduction from small particles: Sulfur nanodots featuring mercury sensing, cell entry mechanism and in vitro tracking performance[J]. Chemical Engineering Journal, 2020, 382: 122907.

[76]Arshad F, Sk M P. Luminescent sulfur quantum dots for colorimetric discrimination of multiple metal ions[J]. ACS Applied Nano Materials, 2020, 3(3): 3044-3049.

[77]Ji K, Wang Y, Mao L, et al. Ultrasensitive SQDs-based electrochemiluminescence assay for determination of miRNA-141 with dual-amplification of co-reaction accelerators and DNA walker[J]. Sensors and Actuators B: Chemical, 2021, 345: 130405.

[78]Song Y, Tan J, Wang G, et al. Oxygen accelerated scalable synthesis of highly fluorescent sulfur quantum dots[J]. Chemical Science, 2020, 11(3): 772-777.

[79]Peng L, Yuan G, Ding H, et al. Engineering a near-infrared nanosensor based on supramolecular self-assembly for Ca2+ detection and imaging in living cells and mice[J]. Sensors and Actuators B: Chemical, 2021, 332: 129539.

[80]Li S, Chen D, Zheng F, et al. Water-soluble and lowly toxic sulphur quantum dots[J]. Advanced Functional Materials, 2014, 24(45): 7133-7138.

[81]Wang H, Wang Z, Xiong Y, et al. Hydrogen peroxide assisted synthesis of highly luminescent sulfur quantum dots[J]. Angewandte Chemie International Edition, 2019, 131(21): 7114-7118.

[82]Wang Y, Zhao Y, Wu J, et al. Negatively charged sulfur quantum dots for treatment of drug-resistant pathogenic bacterial infections[J]. Nano Letters, 2021, 21(22): 9433-9441.

[83]Mahmoud A M, Mahnashi M H, El-Wekil M M. Double protein directed synthesis of chemically etched sulfur doped quantum dots for signal “ON–OFF–ON” sensing of glutathione mediated by copper ions[J]. Analytical Methods, 2023, 15(34): 4296-4303.

[84]Li P, Luo L, Cheng D, et al. Regulation of the structure of zirconium-based porphyrinic metal-organic framework as highly electrochemiluminescence sensing platform for thrombin[J]. Analytical Chemistry, 2022, 94(14): 5707-5714.

[85]Ma Z, Sun Y, Xie J, et al. Facile preparation of MnO2 quantum dots with enhanced fluorescence via microenvironment engineering with the assistance of some reductive biomolecules[J]. ACS Applied Materials & Interfaces, 2020, 12(13): 15919-15927.

[86]Shen L, Wei J, Liu Z, et al. Stable layered sulfur nanosheets prepared by one-step liquid-phase exfoliation of natural sublimed sulfur with bovine serum albumin for photocatalysis[J]. Chemistry of Materials, 2020, 32(24): 10476-10481.

[87]Manan N S A, Aldous L, Alias Y, et al. Electrochemistry of sulfur and polysulfides in ionic liquids[J]. The Journal of Physical Chemistry B, 2011, 115(47): 13873-13879.

[88]Li X, Wang Y, Shi L, et al. A novel ECL biosensor for the detection of concanavalin A based on glucose functionalized NiCo2S4 nanoparticles-grown on carboxylic graphene as quenching probe[J]. Biosensors and Bioelectronics, 2017, 96: 113-120.

[89]Li P, Luo L, Cheng D, et al. Regulation of the structure of zirconium-based porphyrinic metal-organic framework as highly electrochemiluminescence sensing platform for thrombin[J]. Analytical Chemistry, 2022, 94(14): 5707-5714.

[90]Dick J E, Poirel A, Ziessel R, et al. Electrochemistry, electrogenerated chemiluminescence, and electropolymerization of oligothienyl-BODIPY derivatives[J]. Electrochimica Acta, 2015, 178: 234-239.

[91]Kirschbaum-Harriman S, Mayer M, Duerkop A, et al. Signal enhancement and low oxidation potentials for miniaturized ECL biosensors via N-butyldiethanolamine[J]. Analyst, 2017, 142(13): 2469-2474.

[92]Cheng C, Huang Y, Tian X, et al. Electrogenerated chemiluminescence behavior of graphite-like carbon nitride and its application in selective sensing Cu2+[J]. Analytical Chemistry, 2012, 84(11): 4754-4759.

[93]Chen Y, Liu X, Zhang S, et al. Ultrasensitive and simultaneous detection of hydroquinone, catechol and resorcinol based on the electrochemical co-reduction prepared Au-Pd nanoflower/reduced graphene oxide nanocomposite[J]. Electrochimica Acta, 2017, 231: 677-685.

[94]Yang S, Yang M, Yao X, et al. A zeolitic imidazolate framework/carbon nanofiber nanocomposite based electrochemical sensor for simultaneous detection of co-existing dihydroxybenzene isomers[J]. Sensors and Actuators B: Chemical, 2020, 320: 128294.

[95]Zhang C, Han M, Yu L, et al. Fabrication an electrochemical sensor based on composite of Cu-TCPP nanosheets and PSS functionalized graphene for simultaneous and sensitive determination of dihydroxybenzene isomers[J]. Journal of Electroanalytical Chemistry, 2021, 890: 115232.

[96]Zhang W, Zheng J, Lin Z, et al. Highly sensitive simultaneous electrochemical determination of hydroquinone, catechol and resorcinol based on carbon dot/reduced graphene oxide composite modified electrodes[J]. Analytical Methods, 2015, 7(15): 6089-6094.

[97]Ye Z, Wang Q, Qiao J, et al. In situ synthesis of sandwich MOFs on reduced graphene oxide for electrochemical sensing of dihydroxybenzene isomers[J]. Analyst, 2019, 144(6): 2120-2129.

[98]Mashhadizadeh M H, Kalantarian S M, Azhdeh A. A novel electrochemical sensor for simultaneous determination of hydroquinone, catechol, and resorcinol using a carbon paste electrode modified by Zn-MOF, nitrogen-doped graphite, and AuNPs[J]. Electroanalysis, 2021, 33(1): 160-169.

[99]Li G, Huang J, Zhu H, et al. Surface ligand engineering for near-unity quantum yield inorganic halide perovskite QDs and high-performance QLEDs[J]. Chemistry of Materials, 2018, 30(17): 6099-6107.

[100]Wang Z, Shen X, Tang C, et al. Efficient and stable CF3PEAI-passivated CsPbI3 QDs toward red LEDs[J]. ACS Applied Materials & Interfaces, 2022, 14(6): 8235-8242.

[101]Xu X, Liu A, Pang D. Rational design of capping ligands of quantum dots for biosensing[J]. Chemical Research in Chinese Universities, 2024, 40(2): 162-172.

[102]Gao S, Zhang J L, Zhang J L, et al. Enhancing electrochemiluminescence by assembling ACQ ligands into Hf-based metal-organic framework nanosheet: A novel ECL emitter for fabricating ultrasensitive biosensor[J]. Sensors and Actuators B: Chemical, 2023, 382: 133558.

[103]Kuang K, Zhou C, Jing M, et al. Enhanced electrochemiluminescence of rod-shape 25-atom AuAg nanoclusters through ligand engineering[J]. ChemElectroChem, 2024, 11(2): e202300503.

[104]Fang D, Pan M, Yi H, et al. Enhanced electrochemiluminescence of luminol-DBAE system based on self-assembled mesocrystalline hybrid for the detection of ovarian cancer marker[J]. Sensors and Actuators B: Chemical, 2019, 286: 608-615.

[105]Lu M L, Zhang X Y, Song J Q, et al. In-situ growth of hydrogen-bonded organic framework on conductive PEDOT: PSS polymer to realize conductivity-enhanced electrochemiluminescence for fabricating ultrasensitive biosensor[J]. Sensors and Actuators B: Chemical, 2024, 401: 134974.

[106]Wang H, Liu P, Peng J, et al. Poly (3, 4-ethylenedioxythiophene): poly (styrene sulfonate) modified metal-organic frameworks boosting carbon dots electrochemiluminescence emission for sensitive miRNA detection[J]. Biosensors and Bioelectronics, 2024, 249: 116015.

[107]郑立炎. 电致化学发光新材料的研究[D]. 福建：福州大学, 2011.