Citation: Zhifeng CAI, Ying WU, Yanan LI, Guiyu MENG, Tianyu MIAO, Yihao ZHANG. Effective detection of malachite green by folic acid stabilized silver nanoclusters[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(5): 983-993. doi: 10.11862/CJIC.20240394 shu

Effective detection of malachite green by folic acid stabilized silver nanoclusters

College of Chemistry and Materials, Taiyuan Normal University, Jinzhong, Shanxi 030619, China

Corresponding author: Zhifeng CAI, caizhifeng15@mails.ucas.ac.cn Ying WU, ceyingwu@126.com
Received Date: 2 November 2024
Revised Date: 30 March 2025

Figures(6)

Herein, a one-pot chemical reduction method was reported to prepare folic acid (FA)-stabilized silver nanoclusters (FA@Ag NCs), in which FA, hydrazine hydrate, and silver nitrate were used as capping agent, reducing agent, and precursor, respectively. Several technologies were employed to investigate the structures and optical properties of FA@Ag NCs, including transmission electron microscopy (TEM), X ray photoelectron spectrometer (XPS), Fourier transform infrared spectrometer (FTIR), X-ray diffractometer (XRD), fluorescence spectrometer, and ultraviolet visible absorption spectrometer. FA@Ag NCs were suggested to be highly dispersed and spherical with a size of around 2.8 nm. Moreover, the maximum excitation and emission wavelengths of FA@Ag NCs were 370 and 447 nm, respectively. Under the optimal detection conditions, FA@Ag NCs could be used to effectively detect malachite green with the linear detection range of 0.5-200 μmol·L^-1. The detection limit was 0.084 μmol·L^-1. The fluorescence-quenching mechanism was ascribed to the static quenching. The detection system based on FA@Ag NCs was successfully used for the detection of malachite green in actual samples with good accuracy and reproducibility.
- fluorescence probe,
- silver nanoclusters,
- folic acid,
- malachite green,
- static quenching
1. [1]
  KEANJUN N, RATTANAWONGWIBOON T, SRICHAROEN P, LAKSEE S, SAENGSANE N, THEPCHUAY Y, PORRAWATKUL P, PIMSEN R, KUYYOGSUY A, NUENGMATCHA P, CHANTHAI S, SUBSADSANA M, LIMCHOOWONG N. Ultrasound-assisted forma-tion of composite materials from fish scale waste hydroxyapatite in the presence of gamma-irradiated chitosan for the removal of malachite green[J]. RSC Adv., 2024,14:29737-29747. doi: 10.1039/D4RA03102D
2. [2]
  LIANMAWII L, MOHONDAS S N. Effect of additives on the photocat-alytic degradation of malachite green using NiS: Tb³⁺nanoparticle and their photoluminescence properties[J]. J. Mol. Struct., 2025,1320139748. doi: 10.1016/j.molstruc.2024.139748
3. [3]
  KONG Y J, HOU G Z, HAN L J. A europium-based CP fluorescent probe for sensing malachite green, ascorbic acid and uric acid[J]. Polyhedron, 2024,261117164. doi: 10.1016/j.poly.2024.117164
4. [4]
  SHARMA P, SHARMA S, KUMAR S S, SHAO Y F, GUO F Q, ICHIKAWA T, JAIN A, SHRIVASTAVA K. Evaluation of optimized conditions for the adsorption of malachite green by SnO₂-modified sugarcane bagasse biochar nanocomposites[J]. RSC Adv., 2024,14:29201-29214. doi: 10.1039/D4RA05442C
5. [5]
  JOHN C J, SHARMILA L I, SATHIYAN A, PRINCY M J. Fabrica-tion of Cu₃Mo₂O₉ doped MWCNT nanocomposites as efficient photo-catalyst for malachite green dye degradation[J]. Opt. Mater., 2024,156115935. doi: 10.1016/j.optmat.2024.115935
6. [6]
  CAO Q M, TAO J, SUN Y Q, SUN W Y, ZHAO L P, YANG R, QU L B. A smartphone-assisted on-site colorimetric sensing for total amount determination of leuco-malachite green and malachite green based on nanozyme selected oxidation strategy[J]. Sensor. Actuator B -Chem., 2024,418136180. doi: 10.1016/j.snb.2024.136180
7. [7]
  LIU Z W, WANG X L, XIAN H J, ZHONG J H, YE X G, YANG Y X, HU Y, CHEN Y, LI D M, HUANG C. Highly efficient malachite green adsorption by bacterial cellulose and bacterial cellulose/locust bean gum composite[J]. Int. J. Biol. Macromol., 2024,279134991. doi: 10.1016/j.ijbiomac.2024.134991
8. [8]
  CHEN M, HUANG Y Q, MIAO J J, FAN Y X, LAI K Q. A highly sen-sitive surface-enhanced Raman scattering sensor with MIL-100(Fe)/Au composites for detection of malachite green in fish pond water[J]. Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 2023,292122432. doi: 10.1016/j.saa.2023.122432
9. [9]
  ZHOU J Y, ZHU J, WENG G J, LI J J, ZHAO J W. Fabrication of SERS composite substrates using Ag nanotriangles-modified SiO₂ photonic crystal and the application of malachite green detection[J]. Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 2024,318124472. doi: 10.1016/j.saa.2024.124472
10. [10]
  CHEN G, MIAO S. HPLC determination and MS confirmation of malachite green, gentian violet, and their leuco metabolite residues in channel catfish muscle[J]. J. Agric. Food Chem., 2010,58:7109-7114. doi: 10.1021/jf9043925
11. [11]
  WANG Y, LIAO K, HUANG X, YUAN D. Simultaneous determina-tion of malachite green, crystal violet and their leuco-metabolites in aquaculture water samples using monolithic fiber-based solid-phase microextraction coupled with high performance liquid chromatogra-phy[J]. Anal. Methods, 2015,7:8138-8145. doi: 10.1039/C5AY01611H
12. [12]
  NEBOT C, IGLESIAS A, BARREIRO R, MANUEL M J, VÁZQUEZB , MANUEL F C, CEPEDA A. A simple and rapid meth-od for the identification and quantification of malachite green and its metabolite in hake by HPLC-MS/MS[J]. Food Control, 2013,31:102-107. doi: 10.1016/j.foodcont.2012.09.020
13. [13]
  DENG P H, FENG J X, WEI Y P, XIAO J Y, LI J H, HE Q G. Fast and ultrasensitive trace malachite green detection in aquaculture and fisheries by using hexadecylpyridinium bromide modified elec-trochemical sensor[J]. J. Food Compos. Anal., 2021,102104003. doi: 10.1016/j.jfca.2021.104003
14. [14]
  LUO Y Z, LI Z Y. A sensitive electrochemical sensor manufactured from multi-wall carbon nanotubes-polyethylenimine nanocomposite for malachite green detection[J]. J. Alloy. Compd., 2022,897163216. doi: 10.1016/j.jallcom.2021.163216
15. [15]
  MOHAMMAD D N, LAVAEE P, RAMEZANI M, ALIBOLANDI M, KIANFAR M, ALINEZHAD N M, ABNOUS K, MOHAMMAD T S. An electrochemical sensing method based on an oligonucleotide structure for ultrasensitive detection of malachite green[J]. Microchem. J., 2021,160105598. doi: 10.1016/j.microc.2020.105598
16. [16]
  HU Q, MAO Q Y, CUI Y K, GONG S Y, XIAO L X, GONG X J, GUAN T Z, YANG Z Q. Carbon dots-based fluorescence micro-spheres for ultrasensitive detection of malachite green in fish sam-ples[J]. J. Food Compos. Anal., 2024,134106497. doi: 10.1016/j.jfca.2024.106497
17. [17]
  HU Y P, GAO Z J, LUO J F. Fluorescence detection of malachite green in fish tissue using red emissive Se, N, Cl-doped carbon dots[J]. Food Chem., 2021,335127677. doi: 10.1016/j.foodchem.2020.127677
18. [18]
  GU J S, HAN T, PENG X D, KANG H, DONG L J. Highly sensitive fluorescent probe and portable test strip based on polyacrylic acid functionalized quantum dots for rapid visual detection of malachite green[J]. Talanta, 2024,268125359. doi: 10.1016/j.talanta.2023.125359
19. [19]
  QIU J Y, NA L H, LI Y M, BAI W F, ZHANG J P, JIN L. N, S-GQDs mixed with CdTe quantum dots for ratiometric fluorescence visual detection and quantitative analysis of malachite green in fish[J]. Food Chem., 2022,390133156. doi: 10.1016/j.foodchem.2022.133156
20. [20]
  HU C C, LIU C, ZHANG X, TONG W, YIN Y, LIU J Q, YANG S Y. "Silver effect"enhanced fluorescence for sensitive detection of crys-tal violet utilizing long wavelength emission bimetallic gold-silver nanoclusters[J]. Microchem. J., 2024,205111304. doi: 10.1016/j.microc.2024.111304
21. [21]
  SAM S, SWATHY S, GIRISH K K. Lysozyme functionalized silver nanoclusters as a dual channel optical sensor for the effective deter-mination of glutathione[J]. Talanta, 2024,277126326. doi: 10.1016/j.talanta.2024.126326
22. [22]
  SWATHY S, SAM S, KUMAR K G. Polyethyleneimine capped silver nanoclusters based turn-off-on fluorescence sensor for the determination of glutathione[J]. Talanta, 2024,278126541. doi: 10.1016/j.talanta.2024.126541
23. [23]
  TIKHOMIROV V K, RODRÍGUEZ V D, KUZNETSOV A, KIRILENKO D, VAN T G, MOSHCHALKOV V V. Preparation and luminescence of bulk oxyfluoride glasses doped with Ag nanoclusters[J]. Opt. Express, 2010,18(21):22032-22040. doi: 10.1364/OE.18.022032
24. [24]
  CHANDRAN A, GIRISH K K. Folic acid capped bimetallic nanopar-ticle based fluorescence sensor for the nanomolar determination of bilirubin[J]. J. Photochem. Photobiol. A-Chem., 2024,448115287. doi: 10.1016/j.jphotochem.2023.115287
25. [25]
  ZHANG S, NIE X, REN Y, GUO Y Y. One-pot facile synthesis of fluorescent copper nanoclusters for highly selective and sensitive detection of tetracycline[J]. Spectroc. Acta Pt. A -Molec. Biomolec. Spectr., 2024,315124301. doi: 10.1016/j.saa.2024.124301
26. [26]
  BARUAH D, YADAV R N S, YADAV A, DAS A M. Alpinia nigra fruits mediated synthesis of silver nanoparticles and their antimicro-bial and photocatalytic activities[J]. J. Photochem. Photobiol. B-Biol., 2019,201111649. doi: 10.1016/j.jphotobiol.2019.111649
27. [27]
  ZHANG Z H, SONG Y, WANG J, LIN Y L, MENG J M, CUI W B, LIU X X. Vanadium oxides with amorphous-crystalline heterointer-face network for aqueous zinc-ion batteries[J]. Angew. Chem. -Int. Edit., 2023,62(13)e202216290. doi: 10.1002/anie.202216290
28. [28]
  ZHOU B X, MAHMOOD K I, DING X W, NIAZI S, ZHANG Y, WANG Z P. Fluorescent DNA-silver nanoclusters in food safety detection: From synthesis to application[J]. Talanta, 2024,273125834. doi: 10.1016/j.talanta.2024.125834
29. [29]
  LI Y Y, LU X L, LIU X Y, ZHANG L, JING S. Red-emitting selenium-doped carbon dots for versatile applications in biosensing and anti-bacterial activities[J]. Chinese J. Inorg. Chem., 2024,40(1):173-181.
30. [30]
  YUAN Y N, WANG Z X, WANG C Y, SONG Y Y, WANG Q L, YANG C. Zinc(Ⅱ) and cadmium(Ⅱ) complexes derived from 4'-(2-pyr-idyl)-2, 2': 6', 2″-terpyridine: Crystal structures and fluorescence property[J]. Chinese J. Inorg. Chem., 2022,38(9):1878-1886.
31. [31]
  WANG M J, LUO X J, JIANG M H, ZHANG L Y, ZHOU Q, WU C J, HE Y. Ratio-fluorescence sensor based on carbon dots and PtRu/CN nanozyme for efficient detection of melatonin in tablet[J]. Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 2024,321124699. doi: 10.1016/j.saa.2024.124699
32. [32]
  SYIEMLIEH C, NARAYANAN M, VELUSAMY M, KATHIRAVAN A. Pyrene based AIE-active probe for selective detection of picric acid through the inner filter effect channel in aqueous medium[J]. J. Mol. Liq., 2024,407125125. doi: 10.1016/j.molliq.2024.125125
33. [33]
  ZHANG J, NAN D Y, PAN S, LIU H, YANG H, HU X L. N, S co-doped carbon dots as a dual-functional fluorescent sensor for sensi-tive detection of baicalein and temperature[J]. Spectroc. Acta Pt. A-Molec. Biomolec. Spectr., 2019,221117161. doi: 10.1016/j.saa.2019.117161
34. [34]
  YANG S, ZHU H M, CAI S H, CHEN Z F, LIANG X, LI Z, PENG N N, YANG Y, WANG J M, WANG Y Z. Dual-emission carbon dots for ratiometric fluorescence sensing of thiabendazole in fruits[J]. Talanta, 2024,270125555. doi: 10.1016/j.talanta.2023.125555
35. [35]
  ZHOU C Q, HE X X, YA D M, ZHONG J, DENG B Y. One step hydrothermal synthesis of nitrogen-doped graphitic quantum dots as a fluorescent sensing strategy for highly sensitive detection of meta-cycline in mice plasma[J]. Sensor. Actuat. B-Chem., 2017,249:256-264. doi: 10.1016/j.snb.2017.04.092
1. [1]
  Shuwen SUN , Gaofeng WANG . Design and synthesis of a Zn(Ⅱ)-based coordination polymer as a fluorescent probe for trace monitoring 2, 4, 6-trinitrophenol. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 753-760. doi: 10.11862/CJIC.20240399
2. [2]
  Peng XU , Shasha WANG , Nannan CHEN , Ao WANG , Dongmei YU . Preparation of three-layer magnetic composite Fe₃O₄@polyacrylic acid@ZiF-8 for efficient removal of malachite green in water. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 544-554. doi: 10.11862/CJIC.20230239
3. [3]
  Wenya Jiang , Jianyu Wei , Kuan-Guan Liu . Atomically precise superatomic silver nanoclusters stabilized by O-donor ligands. Chinese Journal of Structural Chemistry, 2024, 43(9): 100371-100371. doi: 10.1016/j.cjsc.2024.100371
4. [4]
  Ya-Wen Zhang , Ming-Ming Gan , Li-Ying Sun , Ying-Feng Han . Supramolecular dinuclear silver(I) and gold(I) tetracarbene metallacycles and fluorescence sensing of penicillamine. Chinese Journal of Structural Chemistry, 2024, 43(9): 100356-100356. doi: 10.1016/j.cjsc.2024.100356
5. [5]
  Gongcheng Ma , Qihang Ding , Yuding Zhang , Yue Wang , Jingjing Xiang , Mingle Li , Qi Zhao , Saipeng Huang , Ping Gong , Jong Seung Kim . Palladium-free chemoselective probe for in vivo fluorescence imaging of carbon monoxide. Chinese Chemical Letters, 2024, 35(9): 109293-. doi: 10.1016/j.cclet.2023.109293
6. [6]
  Yiyue Ding , Qiuxiang Zhang , Lei Zhang , Qilu Yao , Gang Feng , Zhang-Hui Lu . Exceptional activity of amino-modified rGO-immobilized PdAu nanoclusters for visible light-promoted dehydrogenation of formic acid. Chinese Chemical Letters, 2024, 35(7): 109593-. doi: 10.1016/j.cclet.2024.109593
7. [7]
  Zhoupeng Zheng , Shengyi Gong , Qianhua Li , Shiya Zhang , Guoqiang Feng . Lipid droplets and gallbladder targeted fluorescence probe for ratiometric NO imaging in gallstones disease models. Chinese Chemical Letters, 2025, 36(5): 110191-. doi: 10.1016/j.cclet.2024.110191
8. [8]
  Zhaorui Song , Qiulian Hao , Bing Li , Yuwei Yuan , Shanshan Zhang , Yongkuan Suo , Hai-Hao Han , Zhen Cheng . NIR-Ⅱ fluorescence lateral flow immunosensor based on efficient energy transfer probe for point-of-care testing of tumor biomarkers. Chinese Chemical Letters, 2025, 36(1): 109834-. doi: 10.1016/j.cclet.2024.109834
9. [9]
  Qiuye Wang , Yabing Sun , Liangxue Lai , Haijing Cui , Yonglong Ye , Ming Yang , Weihao Zhu , Bo Yuan , Quanliang Mao , Wenzhi Ren , Aiguo Wu . MMP-9-responsive probe for fluorescence-magnetic resonance dual-mode imaging of hepatocellular carcinoma models with different metastatic capacities. Chinese Chemical Letters, 2025, 36(4): 110212-. doi: 10.1016/j.cclet.2024.110212
10. [10]
  Kaimin WANG , Xiong GU , Na DENG , Hongmei YU , Yanqin YE , Yulu MA . Synthesis, structure, fluorescence properties, and Hirshfeld surface analysis of three Zn(Ⅱ)/Cu(Ⅱ) complexes based on 5-(dimethylamino) isophthalic acid. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1397-1408. doi: 10.11862/CJIC.20240009
11. [11]
  Linfang ZHANG , Wenzhu YIN , Gui YIN . A 2-dicyanomethylene-3-cyano-4,5,5-trimethyl-2,5-dihydrofuran-based near-infrared fluorescence probe for the detection of hydrogen sulfide and imaging of living cells. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 540-548. doi: 10.11862/CJIC.20240405
12. [12]
  Jie ZHANG , Xin LIU , Zhixin LI , Yuting PEI , Yuqi YANG , Huimin LI , Zhiqiang LIU . Assembling a luminescence silencing system based on post-synthetic modification strategy: A highly sensitive and selective turn-on metal-organic framework probe for ascorbic acid detection. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 823-833. doi: 10.11862/CJIC.20230310
13. [13]
  Runze Liu , Yankai Bian , Weili Dai . Qualitative and quantitative analysis of Brønsted and Lewis acid sites in zeolites: A combined probe-assisted 1H MAS NMR and NH3-TPD investigation. Chinese Journal of Structural Chemistry, 2024, 43(4): 100250-100250. doi: 10.1016/j.cjsc.2024.100250
14. [14]
  Yu Mao , Yilin Liu , Xiaochen Wang , Shengyang Ni , Yi Pan , Yi Wang . Acylfluorination of enynes via phosphine and silver catalysis. Chinese Chemical Letters, 2024, 35(8): 109443-. doi: 10.1016/j.cclet.2023.109443
15. [15]
  Chunhui Zhang , Jie Wang , Jieyang Zhan , Runmin Yang , Guanggang Gao , Jiayuan Zhang , Linlin Fan , Mengqi Wang , Hong Liu . Highly sensitive hydrazine detection through a novel Raman scattering quenching mechanism enabled by a crystalline and noble metal–free polyoxometalate substrate. Chinese Chemical Letters, 2025, 36(3): 109719-. doi: 10.1016/j.cclet.2024.109719
16. [16]
  Yu Yao , Jinqiang Zhang , Yantao Wang , Kunsheng Hu , Yangyang Yang , Zhongshuai Zhu , Shuang Zhong , Huayang Zhang , Shaobin Wang , Xiaoguang Duan . Nitrogen-rich carbon for catalytic activation of peroxymonosulfate towards green synthesis. Chinese Chemical Letters, 2024, 35(11): 109633-. doi: 10.1016/j.cclet.2024.109633
17. [17]
  Tengteng Wang , Yiming Ju , Yao Cheng , Haiyang Wang , Dejin Zang . Recent advances in polyoxometalates based strategies for green synthesis of drugs. Chinese Chemical Letters, 2025, 36(5): 109871-. doi: 10.1016/j.cclet.2024.109871
18. [18]
  Luyao Lu , Chen Zhu , Fei Li , Pu Wang , Xi Kang , Yong Pei , Manzhou Zhu . Ligand effects on geometric structures and catalytic activities of atomically precise copper nanoclusters. Chinese Journal of Structural Chemistry, 2024, 43(10): 100411-100411. doi: 10.1016/j.cjsc.2024.100411
19. [19]
  Rakesh Kumar Gupta , Zhi Wang , Di Sun . Shining bright: Revolutionary near-unity NIR phosphorescent metal nanoclusters. Chinese Journal of Structural Chemistry, 2024, 43(11): 100417-100417. doi: 10.1016/j.cjsc.2024.100417
20. [20]
  Jun-Jie Fang , Yun-Peng Xie , Xing Lu . Organooxotin and cobalt/manganese heterometallic nanoclusters exhibiting single-molecule magnetism. Chinese Journal of Structural Chemistry, 2025, 44(4): 100515-100515. doi: 10.1016/j.cjsc.2025.100515

Get Citation

PDF

XML

Metrics

PDF Downloads(1)
Abstract views(79)
HTML views(16)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142