A fluorescence probe based on aluminum-doped carbon dots for the quantitative detection of naphthenic acid

doi:10.16085/j.issn.1000-6613.2024-1509

Abstract

Abstract:

A fluorescent probe based on aluminum-doped carbon dots (Al-CDs) was developed for the quantitative detection of 1-adamantanecarboxylic acid as a model naphthenic acid. Firstly, the binary deep eutectic solvent (B-DES) was formed by using L-arginine as the carbon source and hydrogen bond acceptor, and ethylene glycol as the hydrogen bond donor. Then, the ternary deep eutectic solvents (T-DES) was synthesized by adding AlCl₃‧6H₂O as the aluminum source, and finally Al-CDs were synthesized from T-DES by hydrothermal method. The results showed that by synthesizing Al-CDs with deep eutectic solvent (DES), on the one hand, the size distribution of the prepared Al-CDs could be uniform and the structure was stable, on the other hand, the target functional groups could be modified on the surface of Al-CDs and the successful doping of aluminum elements could be achieved. The prepared Al-CDs had excellent fluorescence stability and good fluorescence response to the model naphthenic acid, showing a linear relationship within the concentration range of 0.5—20mmol/L of the model naphthenic acid with the detection limit of 0.163mmol/L. The detection was realized by the static quenching mechanism generated by the coordination between Al-CDs and the model naphthenic acid. Al-CDs was applied to the detection of labeled wastewater and the detection results were consistent with results of gas chromatography. The present work provided new insights into the fluorescence detection of carbon dots in the petrochemical industry and broadened the application of carbon dots in the detection of organic pollutants.

Key words: aluminum-doped carbon dots, fluorescence probe, naphthenic acids, static quenching mechanism, stability, selectivity, deep eutectic solvents, size distribution

摘要：

开发了一种基于铝掺杂碳点（Al-CDs）的荧光探针，用于1-金刚烷羧酸作为模型环烷酸的定量检测方法。首先以L-精氨酸为碳源和氢键受体、乙二醇为氢键供体形成二元低共熔溶剂（B-DES），再添加AlCl₃‧6H₂O为铝源，合成三元低共熔溶剂（T-DES），最后T-DES经过水热法合成了Al-CDs。结果表明，通过低共熔溶剂（DES）合成Al-CDs，一方面可以使制备的Al-CDs尺寸分布均匀且结构稳定，另一方面可以有针对性地将目标官能团在Al-CDs表面进行修饰，同时实现了铝元素的成功掺杂。所制备的Al-CDs具有优异的荧光稳定性，对模型环烷酸具有良好的荧光响应，在0.5~20mmol/L的模型环烷酸浓度范围内呈线性关系，检出限0.163mmol/L，检测是通过Al-CDs和模型环烷酸之间发生配位作用产生的静态淬灭机制实现的，将Al-CDs应用于加标废水的检测，检测结果与气相色谱法结果一致。本工作为碳点在石化工业中的荧光检测提供了新的见解，拓宽了碳点在有机污染物检测中的应用。

关键词: 铝掺杂碳点, 荧光探针, 环烷酸, 静态淬灭机制, 稳定性, 选择性, 低共熔溶剂, 粒度分布

CLC Number:

TE991

WANG Ping, SONG Weiyu, REN Hongwei, DUAN Erhong, CHEN Chunmao. A fluorescence probe based on aluminum-doped carbon dots for the quantitative detection of naphthenic acid[J]. Chemical Industry and Engineering Progress, 2025, 44(11): 6674-6687.

王平, 宋卫余, 任红威, 段二红, 陈春茂. 基于铝掺杂碳点的荧光探针用于环烷酸的定量检测[J]. 化工进展, 2025, 44(11): 6674-6687.

Figures/Tables 18

References 45

[1]	ZHANG Huanxin, CUI Lihua, SI Panpan, et al. Environmentally relevant concentrations of naphthenic acids initiate intestinal injury and gut microbiota dysbiosis in marine medaka (Oryzias melastigma)[J]. Aquatic Toxicology, 2024, 273: 106996.
[2]	HUGHES Sarah A, HUANG Rongfu, MAHAFFEY Ashley, et al. Comparison of methods for determination of total oil sands-derived naphthenic acids in water samples[J]. Chemosphere, 2017, 187: 376-384.
[3]	MESHREF Mohamed N A, IBRAHIM Mohamed D, HUANG Rongfu, et al. Fourier transform infrared spectroscopy as a surrogate tool for the quantification of naphthenic acids in oil sands process water and groundwater[J]. Science of the Total Environment, 2020, 734: 139191.
[4]	KLEMZ Ana Caroline, DAMAS Mayra Stéphanie Pascoal, GONZÁLEZ Sergio Yesid Gómez, et al. The use of oilfield gaseous byproducts as extractants of recalcitrant naphthenic acids from synthetic produced water[J]. Separation and Purification Technology, 2020, 248: 117123.
[5]	YEN Tin-Wing, MARSH William P, MACKINNON Michael D, et al. Measuring naphthenic acids concentrations in aqueous environmental samples by liquid chromatography[J]. Journal of Chromatography A, 2004, 1033(1): 83-90.
[6]	LU Weibing, EWANCHUK Andrea, Leonidas PEREZ-ESTRADA, et al. Limitation of fluorescence spectrophotometry in the measurement of naphthenic acids in oil sands process water[J]. Journal of Environmental Science and Health Part A, Toxic/Hazardous Substances & Environmental Engineering, 2013, 48(4): 429-436.
[7]	WANG Chengjin, HUANG Rongfu, KLAMERTH Nikolaus, et al. Positive and negative electrospray ionization analyses of the organic fractions in raw and oxidized oil sands process-affected water[J]. Chemosphere, 2016, 165: 239-247.
[8]	SCOTT Angela C, YOUNG Rozlyn F, FEDORAK Phillip M. Comparison of GC-MS and FTIR methods for quantifying naphthenic acids in water samples[J]. Chemosphere, 2008, 73(8): 1258-1264.
[9]	MERLIN Mireya, GUIGARD Selma E, FEDORAK Phillip M. Detecting naphthenic acids in waters by gas chromatography-mass spectrometry[J]. Journal of Chromatography A, 2007, 1140(1/2): 225-229.
[10]	GUTIERREZ-VILLAGOMEZ Juan Manuel, Juan VÁZQUEZ-MARTÍNEZ, Enrique RAMÍREZ-CHÁVEZ, et al. Profiling low molecular weight organic compounds from naphthenic acids, acid extractable organic mixtures, and oil sands process-affected water by SPME-GC-EIMS[J]. Journal of Hazardous Materials, 2020, 390: 122186.
[11]	MOHAMED Mohamed H, WILSON Lee D, HEADLEY John V, et al. Screening of oil sands naphthenic acids by UV-vis absorption and fluorescence emission spectrophotometry[J]. Journal of Environmental Science and Health Part A, Toxic/Hazardous Substances & Environmental Engineering, 2008, 43(14): 1700-1705.
[12]	DUNCAN Kyle D, HAWKES Jeffrey A, BERG Mykelti, et al. Membrane sampling separates naphthenic acids from biogenic dissolved organic matter for direct analysis by mass spectrometry[J]. Environmental Science & Technology, 2022, 56(5): 3096-3105.
[13]	COLATI Keroly A P, DALMASCHIO Guilherme P, DE CASTRO Eustáquio V R, et al. Monitoring the liquid/liquid extraction of naphthenic acids in Brazilian crude oil using electrospray ionization FT-ICR mass spectrometry (ESI FT-ICR MS)[J]. Fuel, 2013, 108: 647-655.
[14]	HUANG Rongfu, CHEN Yuan, MESHREF Mohamed N A, et al. Characterization and determination of naphthenic acids species in oil sands process-affected water and groundwater from oil sands development area of Alberta, Canada[J]. Water Research, 2018, 128: 129-137.
[15]	HUANG Rongfu, MCPHEDRAN Kerry N, EL-DIN Mohamed Gamal. Ultra performance liquid chromatography ion mobility time-of-flight mass spectrometry characterization of naphthenic acids species from oil sands process-affected water[J]. Environmental Science & Technology, 2015, 49(19): 11737-11745.
[16]	BI Yanxia, XING Baolin, ZENG Huihui, et al. Eco-friendly sustainable fluorescent coal-based carbon dots as a highly selective probe for Cu²⁺ detection[J]. Fuel, 2024, 378: 132933.
[17]	WANG Yao, PAN Gengping, MIAO Chenfang, et al. Effective synthesis of fluorescent carbon dots and their application in controllable detection of deferasirox[J]. Microchemical Journal, 2024, 206: 111536.
[18]	LIANG Le, LIU Yongqing, HUANG Chan, et al. Fluorescent carbon dots based on nitrogen doped dialdehyde starch for highly selective Fe³⁺/glyphosate detection and its applications[J]. Microchemical Journal, 2024, 204: 111084.
[19]	WANG Fei, LI Chen, LI Yaqian, et al. Green synthesis of soybean residue-based nitrogen-chlorine co-doped carbon dots based on deep eutectic solvents: Construction of a PNP fluorescence detection system under the IFE mechanism[J]. Materials Research Bulletin, 2024, 180: 113041.
[20]	ZHANG Daohan, YANG Liang, LI Nan, et al. Detection of ciprofloxacin and pH by carbon dots and rapid, visual sensing analysis[J]. Food Chemistry, 2024, 459: 140313.
[21]	LIU Yize, LI Meiyu, ZHANG Ruoyao, et al. Quantitative detection of naphthenic acids in wastewater based on superior fluorescence performance of nitrogen-rich carbon quantum dots[J]. Science of the Total Environment, 2023, 885: 163773.
[22]	AYAZ Furkan, ALAŞ Melis Özge, Melike OĞUZ, et al. Aluminum doped carbon nanodots as potent adjuvants on the mammalian macrophages[J]. Molecular Biology Reports, 2019, 46(2): 2405-2415.
[23]	GAO Xiao, YU Hongquan, CONG Shanshan, et al. LED application and temperature-sensitive properties of white carbon dots doped with aluminum triacetylacetone without the N element[J]. Journal of Alloys and Compounds, 2024, 1002: 175405.
[24]	JAYAWEERA Supuli, YIN Ke, HU Xiao, et al. Fluorescent N/Al co-doped carbon dots from cellulose biomass for sensitive detection of manganese (Ⅶ)[J]. Journal of Fluorescence, 2019, 29(6): 1291-1300.
[25]	YU Chaojie, SUN Qinxing, WANG Zongzhen, et al. Aluminium-doped carbon dots for the simultaneous selective detection of five tetracycline antibiotics[J]. Journal of Fluorescence, 2024.
[26]	SHEIKHI Mehdi, RAFIEMANZELAT Fatemeh, SADEGHPOUR Narges, et al. Deep eutectic solvents based on L-arginine and glutamic acid as green catalysts and conductive agents for epoxy resins[J]. Journal of Molecular Liquids, 2021, 343: 117568.
[27]	DING Wei, WANG Tao, ZENG Peng, et al. Amino acids assisted to improve the voltage window of deep eutectic electrolyte formed by ethylene glycol and tetra methyl ammonium chloride[J]. Chemical Engineering Journal, 2023, 457: 141143.
[28]	IBRAHIM Rusul Khaleel, HAYYAN Maan, ALSAADI Mohammed Abdulhakim, et al. Physical properties of ethylene glycol-based deep eutectic solvents[J]. Journal of Molecular Liquids, 2019, 276: 794-800.
[29]	REN Hongwei, LI Meiyu, LIU Yize, et al. Nitrogen-rich carbon quantum dots (N-CQDs) based on natural deep eutectic solvents: Simultaneous detection and treatment of trace Co²⁺ under saline conditions[J]. Science of the Total Environment, 2022, 811: 152389.
[30]	REN Hongwei, LIU Yize, ZHANG Ruoyao, et al. Near-infrared carbon quantum dots from PEG-based deep eutectic solvents for high-accuracy quantitative analysis of naphthenic acids in wastewater[J]. Journal of Environmental Chemical Engineering, 2023, 11(3): 109988.
[31]	ZHANG Ruoyao, ZHENG Yi, ZHANG Qiuya, et al. Nitrogen-doped carbon quantum dots based on deep eutectic solvents precursors to detect Cr⁶⁺ in environmental water[J]. Journal of Environmental Chemical Engineering, 2024, 12(3): 112391.
[32]	LIU Jinkun, LUO Yimeng, RAN Zhun, et al. Calcination temperature tuning of RTP and TADF with wide range of emission color from carbon dots confined in Al₂O₃ [J]. Chemical Engineering Journal, 2023, 474: 145597.
[33]	HE Pinyi, BAI Jianliang, QIN Fu, et al. Catalyst regulation of o-phenylenediamine-based carbon dots to achieve single red emission[J]. Applied Surface Science, 2024, 652: 159367.
[34]	YUAN Kang, ZHANG Xinghua, LI Xiang, et al. Great enhancement of red emitting carbon dots with B/Al/Ga doping for dual mode anti-counterfeiting[J]. Chemical Engineering Journal, 2020, 397: 125487.
[35]	IATSUNSKYI Igor, Mateusz KEMPIŃSKI, JANCELEWICZ Mariusz, et al. Structural and XPS characterization of ALD Al₂O₃ coated porous silicon[J]. Vacuum, 2015, 113: 52-58.
[36]	ARKIN Kamile, ZHENG Yuxin, BEI Yuyang, et al. Construction of dual-channel ratio sensing platform and molecular logic gate for visual detection of oxytetracycline based on biomass carbon dots prepared from cherry tomatoes stalk[J]. Chemical Engineering Journal, 2023, 464: 142552.
[37]	LIU Yongli, ZHOU Penghui, WU Yalin, et al. Fast and efﬁcient “on-off-on” ﬂuorescent sensor from N-doped carbon dots for detection of mercury and iodine ions in environmental water[J]. Science of the Total Environment, 2022, 827: 154357.
[38]	LIN Xiaofeng, XIONG Mogao, ZHANG Jingwen, et al. Carbon dots based on natural resources: Synthesis and applications in sensors[J]. Microchemical Journal, 2021, 160: 105604.
[39]	TANG Siyuan, CHEN Da, GUO Guoqiang, et al. A smartphone-integrated optical sensing platform based on Lycium ruthenicum derived carbon dots for real-time detection of Ag⁺ [J]. Science of the Total Environment, 2022, 825: 153913.
[40]	ZHOU Yan, CHEN Guoqing, MA Chaoqun, et al. A fluorescent probe based on carbon quantum dots with spectral selectivity for sensitive detection of Cr(Ⅵ) and Hg(Ⅱ) in environmental waters[J]. Dyes and Pigments, 2024, 222: 111845.
[41]	CHEN Xueqi, SONG Zihui, YUAN Bingnan, et al. Fluorescent carbon dots crosslinked cellulose nanofibril/chitosan interpenetrating hydrogel system for sensitive detection and efficient adsorption of Cu(Ⅱ) and Cr(Ⅵ)[J]. Chemical Engineering Journal, 2022, 430: 133154.
[42]	XU Ouwen, YANG Jing, SONG Hanyang, et al. Novel Zn/Co-N co-doped carbon quantum dot-based “on-off-on” fluorescent sensor for Fe(Ⅲ) and ascorbic acid[J]. Talanta Open, 2023, 7: 100162.
[43]	CHEN Yihong, WANG Zihan, LIANG Meiqi, et al. High-efficient nickel-doped lignin carbon dots as a fluorescent and smartphone-assisted sensing platform for sequential detection of Cr(Ⅵ) and ascorbic acid[J]. International Journal of Biological Macromolecules, 2024, 274: 133790.
[44]	LIN Min, ZOU Hongyan, YANG Tong, et al. An inner ﬁlter effect based sensor of tetracycline hydrochloride as developed by loading photoluminescent carbon nanodots in the electrospun nanoﬁbers[J]. Nanoscale, 2016, 8(5): 2999-3007.
[45]	YUAN Yusheng, JIANG Junze, LIU Shaopu, et al. Fluorescent carbon dots for glyphosate determination based on fluorescence resonance energy transfer and logic gate operation[J]. Sensors and Actuators B: Chemical, 2017, 242: 545-553.

粒径分布/nm	平均值/nm	质量分数/%
1~1.3	1.15	3.3
1.3~1.6	1.45	19.3
1.6~1.9	1.75	26.0
1.9~2.2	2.05	22.7
2.2~2.5	2.35	14.7
2.5~2.8	2.65	9.7
2.8~3.1	2.95	3.7
3.1~3.4	3.25	0.3
3.4~3.7	3.55	0.3
3.7~4	3.85	0

粒径分布/nm	平均值/nm	质量分数/%
1~1.3	1.15	3.3
1.3~1.6	1.45	19.3
1.6~1.9	1.75	26.0
1.9~2.2	2.05	22.7
2.2~2.5	2.35	14.7
2.5~2.8	2.65	9.7
2.8~3.1	2.95	3.7
3.1~3.4	3.25	0.3
3.4~3.7	3.55	0.3
3.7~4	3.85	0

项目	n
项目	1	2	3	4	5
环烷酸的浓度/mmol·L^-1	5.58	5.56	5.58	5.55	5.57
平均浓度/mmol·L^-1	5.57
气相色谱法平均浓度/mmol·L^-1	5.52

项目	n
项目	1	2	3	4	5
环烷酸的浓度/mmol·L^-1	5.58	5.56	5.58	5.55	5.57
平均浓度/mmol·L^-1	5.57
气相色谱法平均浓度/mmol·L^-1	5.52