A Bifunctional Triphenylamine-Based Fluorescent Dye for Anti-counterfeiting and Latent Fingerprint Detection

doi:10.6023/cjoc202507001

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (3): 1095-1104.DOI: 10.6023/cjoc202507001 Previous Articles Next Articles

ARTICLES

一种用于防伪和潜指纹检测的双功能三苯胺基荧光染料

陈春琳^†, 谭杰^†, 张帮翠, 董官茞, 杨艳华^*(), 李湘广^*(), 高树林^*()

昆明学院化学化工学院云南省金属有机分子材料与器件重点实验室云南省金属有机分子材料与器件重点实验室昆明 650214

收稿日期:2025-10-18 修回日期:2025-11-03 发布日期:2025-11-12
作者简介:
†共同第一作者
基金资助:
国家大学生创新创业训练计划(202411393015); 云南省“兴滇英才支持计划”青年人才专项(ZX20230278); 云南省教育厅科学研究基金(2025Y1050); 国家自然科学基金(22065019); 昆明学院科学研究基金(XPZJ2205); 昆明学院科学研究基金(XPZJ2205-2); 昆明“春城计划”青年拔尖人才(C202014001); 云南省中青年学术和技术带头人储备人才(202105AC160043)

A Bifunctional Triphenylamine-Based Fluorescent Dye for Anti-counterfeiting and Latent Fingerprint Detection

Chunlin Chen, Jie Tan, Bangcui Zhang, Guanchen Dong, Yanhua Yang^*(), Xiangguang Li^*(), Shulin Gao^*()

Yunnan Key Laboratory of Metal-Organic Molecular Materials and Device, School of Chemistry and Chemical Engineering, Kunming University, Kunming 650214

Received:2025-10-18 Revised:2025-11-03 Published:2025-11-12
Contact: *E-mail: yh_yangkmu@126.com; lixiangguang@iccas.ac.cn; 778144294@qq.com
About author:
†These authors contributed equally to this work.
Supported by:
National College Students’ Platform for Innovation and Entrepreneurship Training Program(202411393015); Yunnan Provincial “Xingdian Talent Supporting Plan” Youth Talent Special Project(ZX20230278); Scientific Research Funds Project of Yunnan Education Department(2025Y1050); National Natural Science Foundation of China(22065019); Scientific Research Funds of Kunming University(XPZJ2205); Scientific Research Funds of Kunming University(XPZJ2205-2); Kunming “Spring City Program” for Youth Top-Notch Talents(C202014001); Program for Young and Middle-Aged Academic and Technical Leaders Reserve Talents of Yunnan Province(202105AC160043)

1. .pdf(10649KB)

Abstract

To explore the application of multifunctional fluorescent dye, a triphenylamine-based difluoroboron compound with an electron donor-acceptor molecular conformation was designed and successfully synthesized. It is found that it not only has the intramolecular charge transfer characteristics and solvatochromism, but also exhibits aggregation-induced emission performance. These photophysical properties can be well explained by theoretical calculation results. Furthermore, it displays reversible mechanofluorochromism behavior, which originates from phase transition between crystalline and amorphous states, confirmed by powder X-ray diffraction analysis. Leveraging this mechanofluorochromism behavior, the prepared safety paper exhibits anti-counterfeiting characteristics, demonstrating a repeatedly rewritable ink-free writing capability. A developer prepared from a dimethyl sulfoxide (DMSO)/H₂O mixture [water content of 60% (ϕ), c=1×10^－5 mol/L] could visualize latent fingerprint on both non-porous and porous substrates. Further analysis revealed that it could detect the ridge details of fingerprint containing sweat pore from photographs of imaging, which could be applied to personal identification. And latent fingerprint imaging originates from the interaction between oleic acid in sweat secretions and the dye.

Key words: difluoroboron fluorescent dye, mechanofluorochromism, aggregation-induced emission, anti-counterfeiting, latent fingerprint detection

Cite this article

Chunlin Chen, Jie Tan, Bangcui Zhang, Guanchen Dong, Yanhua Yang, Xiangguang Li, Shulin Gao. A Bifunctional Triphenylamine-Based Fluorescent Dye for Anti-counterfeiting and Latent Fingerprint Detection[J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 1095-1104.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 10

Scheme 1. Synthetic routes of the TPA-based difluoroboron compound TPA-2

Figure 1. (a) Normalized absorption spectra and (b) normalized emission spectra of compound TPA-2 in different organic solvents (c=1×10－5 mol/L, excited at 390 nm), and (c) the corresponding Lippert-Mataga fitting curves Inset: photos of fluorescence in different organic solvents.

Figure 2. (a) Absorption spectra, (b) emission spectra, and (c) change plots of emission intensity with fw of compound TPA-2 in DMSO/water mixtures (λex=370 nm, c=1×10－5 mol/L) Inset: photos in different fw under 365 nm UV lamp irradiation.

Figure 3. (a) Normalized emission spectra and (b) XRD patterns of compound TPA-2 in different solid states (λex=480 nm). Inset: Photos of luminescence colors in different solid states under a 365 nm UV lamp.

Figure 4. (a) Calculated frontier molecular orbital, (b) optimized structural of compound TPA-2 by density functional theory calculations, and (c) ESP surfaces and dipole moments in the ground and excited states, respectively

Figure 5. Photos of ink-free writing on prepared safety paper of compound TPA-2 (a) under a 365 nm UV lamp and (b) natural light, respectively

Figure 6. Fluorescence images of LPF on different substrates developed by compound TPA-2 dissolving in DMSO/H2O mixture (a) under a 365 nm UV lamp and (b) the original LFP without using developers under natural light, respectively

Figure 7. Fluorescence images of LPF on tinfoil after being processed with compound TPA-2 and enlarged regional images with specific features

Figure 8. Photographs of LFP undergoing different aging times on the surface of tinfoil under 365 nm UV lamp

Figure 9. (a) Fluorescence emission spectra (λex=360 nm) in DMSO/H2O mixture (fw=60%) containing compound TPA-2 (c=1× 10－4 mol/L) and in the presence of different components (c=1×10－3 mol/L) of fingerprint and (b) fluorescence photographs under 365 nm UV lamp

References 37

[1]	Zhou, H.; Gao, S.; Weng, Z.; Yuna L.; Li, W.; Lei, P.; Li, X.; Yang, Y.; Yang, M. Spectrochim. Acta A 2025, 333, 125900. doi: 10.1016/j.saa.2025.125900
[2]	Qian, H.; Tian, J.; Jiang, X.; Zhang, B.; Li, X.; Yang, Y.; Gao, S.; Shao, L.; Li, F. Luminescence 2024, 39, e4729. doi: 10.1002/bio.4729 pmid: 38548706
[3]	Qian, W.; Zuo, M.; Song, Y.; Hu, X-Y.; Wang, L. Mater. Today Chem. 2022, 26, 101115.
[4]	Sun, H.; Li, S.; Liu, Q.; Zuo, M.; Tian, X.; Wang, K.; Hu, X-Y. Chin. Chem. Lett. 2024, 36, 109999. doi: 10.1016/j.cclet.2024.109999
[5]	Feng, Y.; Das, P. J.; Young, R. M.; Brown, P. J.; Hornick, J. E.; Weber, J. A.; Seale, J. S. W.; Stern, C. L.; Wasielewski, M. R.; Stoddart, J. F. J. Am. Chem. Soc. 2022, 144, 16841. doi: 10.1021/jacs.2c04906
[6]	Cao, Y.; Wang, X.; Shi, X.; Clee, S. M.; McGeer, P. L.; Wolf, M. O.; Orvig, C. Angew. Chem., Int. Ed. 2017, 56, 15603. doi: 10.1002/anie.v56.49
[7]	Feng, X.; Zhou, N.; Zhou, H.; Song, F.; Fu, S.; Zhang, W.; Liu, X.; Xu, D. New J. Chem. 2022, 46, 15657. doi: 10.1039/D2NJ02532A
[8]	Jia, M.; Hu, H.; Xiong, X.; Lyu, L.; Zhao, H.; Zhang, S.; Hou, J. Dyes Pigm. 2021, 190, 109343. doi: 10.1016/j.dyepig.2021.109343
[9]	Gac, A. L.; Mallet-Ladeira, S.; Roger, J.; Hierso, J.-C.; Miqueu, K.; Bouhadir, G.; Bourissou, D. Angew. Chem., Int. Ed. 2025, 64, e202501178. doi: 10.1002/anie.v64.19
[10]	Yin, Y.; Guan, Q.; Chen, Z.; Deng, D.-D.; Liu, S.; Sun, Y.; Liu, S. L. Sci. Adv. 2024, 10, adk5444.
[11]	Wang, Q.; Li, D.; Zhang, Z.; Shen, L.; Xu, H.; Wang, Z.; Redshaw, C.; Zhang, Q. Spectrochim. Acta A 2025, 330, 125694. doi: 10.1016/j.saa.2024.125694
[12]	Xu, M.; Tian, J.; Yang, Y.; Gou, G.; Li, F.; Shao, L.; Chi, K. Chin. J. Org. Chem. 2023, 43, 1824 (in Chinese).
	(徐茂财, 田佳壮, 杨艳华, 苟高章, 李福敏, 邵林, 池可心, 有机化学, 2023, 43, 1824.) doi: 10.6023/cjoc202211030
[13]	Zhu, H.; Weng, S.; Zhang, H.; Yu, H.; Kong, L.; Zhong, Y.; Tian, Y.; Yang, J. CrystEngComm 2018, 20, 2772. doi: 10.1039/C8CE00025E
[14]	Yang, S.; Tan, S.; Chen, Y.; Tian, J.; Yang, Y.; Li, X.; Gao, S. Dyes Pigm. 2023, 220, 111736. doi: 10.1016/j.dyepig.2023.111736
[15]	Yang, R.; Li, L.; Gao, S.; Weng, Z.; Li, W.; Wang, Z.; Li, X.; Yang, Y.; Jiang, W. J. Org. Chem. 2025, 90, 6044. doi: 10.1021/acs.joc.5c00508
[16]	Zhang, C.; Gao, X.; Ma, D.; Zou, D.; Zhang, N.; Yan, J. Dyes Pigm. 2024, 227, 112180. doi: 10.1016/j.dyepig.2024.112180
[17]	Sun, J.; Qian, C.; Xu, S.; Jia, X.; Zhai, L.; Zhao, J.; Lu, R. Org. Biomol. Chem. 2018, 16, 7438. doi: 10.1039/C8OB01596A
[18]	Luo, H.; Chen, C.; Li, S.; Zhang, B.; Chen, F.; Tian, J.; Gao S.; Wang, J.; Li, X.; Yang, Y. New J. Chem. 2025, 49, 7414. doi: 10.1039/D5NJ00511F
[19]	Choi, N.-E.; Kim, E.-J.; Lee, J. RSC Adv. 2022, 12, 33180. doi: 10.1039/D2RA06728E
[20]	Song, Y.; Sun, J.; Sun, M.; Simalou, O.; Gao, H.; Peng, J.; Shu, Y.; Zhai, L.; Lu, R. Opt. Mater. 2021, 115, 111006. doi: 10.1016/j.optmat.2021.111006
[21]	Tian, R.; Yu, Q.; Mei, L.-J.; Zhu, F.-Y.; Qin, Q.; Ma, R.; Wang, Y.-L.; Li, C.; Zhu, M.-Q. Sens. Actuators, B 2023, 396, 134634. doi: 10.1016/j.snb.2023.134634
[22]	Duan, L.; Zheng, Q.; Tu, T. Adv. Mater. 2022, 34, 2202540. doi: 10.1002/adma.v34.35
[23]	Liu, D.; Wang, M.; Han, J.; Zhang, Z.; Wang, X. Sens. Actuators, B 2024, 401, 135045. doi: 10.1016/j.snb.2023.135045
[24]	Chen, C.; Tian, J.; Li, S.; Gao, S.; Yang, Y.; Li, X.; Zhang, J. J. Photochem. Photobiol., A 2025, 460, 116125. doi: 10.1016/j.jphotochem.2024.116125
[25]	Tan, S.; Tian, J.; Yang, S.; Zhang, B.; Yang, Y.; Li, X.; Gao, S. J. Lumin. 2024, 275, 120730. doi: 10.1016/j.jlumin.2024.120730
[26]	Zhang, B.; Chen, C.; Tian, J.; Gao, S.; Yang, Y.; Li, X.; Zhang, J. New J. Chem. 2024, 48, 20399. doi: 10.1039/D4NJ03860F
[27]	Tian, J.; Su, Z.; Jiang, X.; Zhang, B.; Yang, Y.; Li, X.; Gou, G. Spectrochim. Acta A 2024, 319, 124568. doi: 10.1016/j.saa.2024.124568
[28]	Chen, Y.; Zhou, Y.; Wang, Z.; Wang, M.; Gao, W.; Zhou, Y.; Liu, M.; Huang, X.; Wu, H. CrystEngComm 2019, 21, 4258. doi: 10.1039/C9CE00348G
[29]	Zhou, L.; Xu, D.; Gao, H.; Han, A.; Yang, Y.; Zhang, C.; Liu, X.; Zhao, F. RSC Adv. 2016, 6, 69560. doi: 10.1039/C6RA14595G
[30]	Li, S.; Wang, L.; Ma, Y.; Zhu, L.; Lin, W. Sens. Actuators, B 2022, 371, 132595. doi: 10.1016/j.snb.2022.132595
[38]	Tian, J.; Du, Y.; Chen, C.; Li, X.; Gao, S.; Yang, Y.; Jiang, S. Forensic Chem. 2025, 42, 100643. doi: 10.1016/j.forc.2025.100643
[39]	Luo, Y. Guidance for Criminal Science and Technology Experiments, China People’s Public Security University Press, Beijing, 2017, pp. 63-64 (in Chinese).
	(罗亚平, 刑事科学技术实验指导, 中国人民公安大学出版社, 北京, 2017, pp. 63-64.)
[40]	Liu, L.; Wang, J.; Wang, X.; Wang, H.; Li, M.; Wu, T.; Gao, G.; Zheng, X.; Liu, G.; Fan, L.; Shen, W.; Ru, G.; Zhao, Z.; Tang, B. Z. Chin. J. Chem. 2023, 41, 1465. doi: 10.1002/cjoc.v41.12
[41]	Zhang, M.; Zhang, J.; Zhang, Z.; Kwok, R. T.K.; Lam, J. W. Y.; Jia, G.; Tang, B. Z. Adv. Opt. Mater. 2024, 12, 2302781. doi: 10.1002/adom.v12.13
[42]	Du, Y.; Tian, J.; Jiang, X.; Chen, C.; Yang, Y.; Gao, S. ChemistrySelect 2024, 9, e202402064. doi: 10.1002/slct.v9.30
[31]	Mei, J.; Hong, Y.; Lam, J. W. Y.; Qin, A.; Tang, Y.; Tang, B. Z. Adv. Mater. 2014, 26, 5429. doi: 10.1002/adma.v26.31
[32]	Gao, B.; Wang, H.; Hao, Y.; Fu, L.; Fang, H.; Jiang, Y.; Wang, L.; Chen, Q.; Xia, H.; Pan, L.; Ma, Y.; Sun, H. J. Phys. Chem. B 2010, 114, 128. doi: 10.1021/jp909063d
[33]	Yu, C.; Hao, E.; Fang, X.; Wu, Q.; Wang, L.; Li, J.; Xu, L.; Jiao, L.; Wong, W. J. Mater. Chem. C 2019, 7, 3269. doi: 10.1039/C9TC00316A
[34]	Huang, G.; Xia, Q.; Huang, W.; Tian, J.; He, Z.; Li, B. S.; Tang, B. Z. Angew. Chem., Int. Ed. 2019, 58, 17814. doi: 10.1002/anie.v58.49
[35]	Liu, M.; Han, Y.; Yuan, W.; Guo, C.; Shi, S.; Liu, X.; Chen, Y. Dalton Trans. 2019, 48, 14626. doi: 10.1039/C9DT02852H
[36]	Jin, X.; Xin, R.; Wang, S.; Yin, W.; Xu, T.; Jiang, Y.; Ji, X.; Chen, L.; Liu, J. Sens. Actuators, B 2017, 244, 777. doi: 10.1016/j.snb.2017.01.080
[37]	Jiang, Q.; Tian, J.; Peng, Z.; Gao, S.; Wang, J.; Li, X.; Yang, Y. ChemistrySelect 2025, 10, e202500742. doi: 10.1002/slct.v10.17

一种用于防伪和潜指纹检测的双功能三苯胺基荧光染料

A Bifunctional Triphenylamine-Based Fluorescent Dye for Anti-counterfeiting and Latent Fingerprint Detection

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 10

References 37

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Jidong Zhang, Hao Wang, Xiaoxin Quan, Shenghai Zhang, Wei She. Synthesis of Aggregation-Induced Emission (AIE) Organic Polymorphs Based on Tetraphenylethene Structure: Research on Molecular Conformation and Detection Performance of Cys [J]. Chinese Journal of Organic Chemistry, 2026, 46(3): 934-940.
[2]	Pengze Yan, Shuli Gao, Tianrui Li, Jinling Miao, Xuchuan Jiang, Yong Nie. Progress in the Synthesis of Carborane Compounds with Aggregation-Induced Emission [J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2677-2697.
[3]	Hongyu Dai, Honghong Sun, Peifa Wei, Weijiang Guan. Strategies for the Synthesis of High-Efficiency Aggregation-Induced Emission Photosensitizers [J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 4128-4142.
[4]	Bingyan Chen, Jie Sun, Linghong Xiong, Xuewen He. Fluorescence Light-Up Detection and Imaging of Atypical Nucleic Acid Structures [J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 4082-4107.
[5]	Yixuan Chen, Zheng Zhao. Aggregation-Induced Emission Photosensitizers for Photodynamic Antimicrobial Therapy [J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 3998-4012.
[6]	Fafen Chen, Chunlin Chen, Zhi Peng, Bangcui Zhang, Haiyan Luo, Shan Li, Shulin Gao, Jianfei Wang, Xiangguang Li, Yanhua Yang. Triphenylamine-Based Schiff Base Compounds for the Latent Fingerprints Visualization [J]. Chinese Journal of Organic Chemistry, 2025, 45(11): 4185-4194.
[7]	Zixuan Dong, Junjun Su, Hongfei Pan, Xiangkui Ren, Zhijian Chen. Near-Infrared Aggregation-Induced Emission (AIE) Molecules Based on Coupling of Triarylamine-Modified Benzothiadiazole Units [J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 205-211.
[8]	Ziran Tang, Hao Sun, Liangliang Zhu. Research Progress of Photoresponsive Photoluminescent Materials with Aggregation-Induced Emission Characteristics [J]. Chinese Journal of Organic Chemistry, 2024, 44(8): 2393-2412.
[9]	Jie Zhang, Nan Li, Na Zhao. Recent Progress of Aggregation-Induced Emission Molecule Nanozyme Composites [J]. Chinese Journal of Organic Chemistry, 2024, 44(8): 2469-2478.
[10]	Qingbao Gong, Xiang Lü, Changjiang Yu, Wanwan Li, Quansheng Zhao, Lijuan Jiao, Erhong Hao. Aggregation-Induced Emission (AIE) Active Fluoroboronated Pyridylhydrazinyl Aldehyde Hydrozone Dyes: Synthesis, Crystal Structure and Optical Properties [J]. Chinese Journal of Organic Chemistry, 2024, 44(8): 2545-2553.
[11]	Yuanhao Wang, Yukai Sun, Yuhang Liu, Zhaoming Zhang, Xuzhou Yan. Construction and Properties of Flexible Light-Emitting Materials Based on Tetraphenylethylene [J]. Chinese Journal of Organic Chemistry, 2024, 44(8): 2538-2544.
[12]	Hanyu Jia, Yuewen Yu, Guangxue Feng, BenZhong Tang. Construction of Type I Aggregation-Induced Emission Photosensitizers for Photodynamic Therapy via Photoinduced Electron Transfer Mechanism [J]. Chinese Journal of Organic Chemistry, 2024, 44(8): 2530-2537.
[13]	Yizhuo Shen, Kangwei Luo, Qingyang Xu, Jianyu Zhang, JingZhi Sun, Haoke Zhang, BenZhong Tang. Weak Interaction-Based Organic Luminescent Materials [J]. Chinese Journal of Organic Chemistry, 2024, 44(8): 2453-2468.
[14]	Junchu He, Junqi Wu, Jianghui Wang, Jingwen Xu, BenZhong Tang, Zujin Zhao. Blue Aggregation-Induced Delayed Fluorescence Materials with 5,10-Dihydrodibenzo[b,e][1,4]azasiline as Donor [J]. Chinese Journal of Organic Chemistry, 2024, 44(8): 2513-2522.
[15]	Zhixin Xie, Shaoling Li, Wei Liu, Kai Yan, Tao Jiang, Yiwei Liu, Md. Monarul Islam, Xing Feng. An Efficient Approach to Narrow the Emission Band of Pyrene-Based Emitters [J]. Chinese Journal of Organic Chemistry, 2024, 44(8): 2504-2512.