9-芴基甲氧基羰基-酪氨酸掺杂聚乙烯醇室温磷光薄膜性质研究

doi:10.6023/cjoc202409005

摘要/Abstract

室温磷光(Room Temperature Phosphorescence, RTP)材料在信息加密、光学传感、生物成像、信息存储等方面具有十分广阔的应用前景, 然而有机材料在室温条件下实现长寿命、高效率的磷光一直面临诸多挑战性, 这主要是由于环境条件下有机分子的磷光发射经常会被强烈的非辐射跃迁、低效的系间穿越、氧气等因素的淬灭所阻碍. 本研究主要使用掺杂聚合物基质这一策略实现了长寿命室温磷光发射, 所制备的两种9-芴基甲氧基羰基(Fmoc)-酪氨酸@PVA薄膜在275 nm的紫外光源照射后产生寿命大于4000 ms的磷光发射和持续时间长达41 s的蓝色余辉. 进一步在体系中掺杂染料分子罗丹明B, 通过Förster共振能量转移(Förster-resonance energy-transfer, FRET)过程实现对薄膜余辉发光颜色的调节.

关键词: 酪氨酸, 室温磷光, 聚乙烯醇, 共振能量转移

Room temperature phosphorescent (RTP) materials have broad application prospects in information encryption, optical sensing, biological imaging, information storage and so on. However, the realization of long-lived, high-efficiency phosphorescence in organic materials at room temperature represents a challenge, largely because the phosphorescence emission of organic molecules under ambient conditions is often hindered by intensive non-radiative transitions, inefficient intersystem crossing, and quenching of oxygen. In this study, the doped polymer matrix strategy was mainly used to achieve long-life room temperature phosphorescence emission. Two kinds of 9-fluorenyl methoxycarbonyl (Fmoc)-Tyrosine@PVA films prepared can produce phosphorescence emission with a lifetime of more than 4000 ms and blue afterglow with a long duration of 41 s after irradiation by 275 nm ultraviolet light source. Furthermore, Rhodamine B, a dye molecule, was doped in the system to adjust the color of the doped films by Förster-resonance energy transfer process.

Key words: tyrosine, room temperature phosphorescence, polyvinyl alcohol, resonance energy transfer

引用此文

高玉兰, 龙江琴, 王秋生. 9-芴基甲氧基羰基-酪氨酸掺杂聚乙烯醇室温磷光薄膜性质研究[J]. 有机化学, 2025, 45(4): 1261-1267.

Yulan Gao, Jiangqin Long, Qiusheng Wang. Properties Research of Poly(vinyl alcohol) Phosphorescent Films Doped with 9-Fluorenyl Methoxycarbonyl-Tyrosine at Room Temperature[J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1261-1267.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 8

图1. (a) Fmoc-酪氨酸的分子结构、(b) Fmoc-Tyr@PVA薄膜中的荧光、磷光发射光谱、(c) Fmoc-Tyr@PVA薄膜寿命衰减曲线

Figure 1. (a) Molecular structures of Fmoc-Tyrosine, (b) fluorescence/phosphorescence emission spectra, and (c) lifetime decay curves of Fmoc-Tyrs@PVA films

Compound	Fluorescence			Phosphorescence
Compound	λ_ex/nm	λ_em/nm	Ф_Fluo/%	λ_em/nm	τ/ms	Ф_Phos/%
Fmoc-D-Tyr	275	314	2.98	460	4248.33	15.37
Fmoc-L-Tyr	275	318	6.24	460	4256.54	16.89
Fmoc-D-Tyr/RhB	275	314/592	1.68	461/589	3387.85	18.56
Fmoc-L-Tyr/RhB	275	318/592	2.88	461/589	3127.54	22.66

表1. Fmoc-D-Tyr@PVA、Fmoc-L-Tyr@PVA、Fmoc-D-Tyr/RhB@PVA、Fmoc-L-Tyr/RhB@PVA薄膜光物理性质测试结果

Table 1. Test results of photophysical properties of Fmoc-D-Tyr@PVA, Fmoc-L-Tyr@PVA, Fmoc-D-Tyr/RhB@PVA, and Fmoc-L-Tyr/ RhB@PVA films

图2. (a) Fmoc-Tyr@PVA薄膜在激发波长为275 nm下拍摄的发光照片(紫外灯照射时间为5 s)、(b) Fmoc-Tyr@PVA薄膜CIE坐标图

Figure 2. (a) Luminescence photograph at an excitation wavelength of 275 nm (UV irradiation time is 5 s), and (b) CIE coordinate diagram of Fmoc-Tyrs@PVA films

图3. (a) Fmoc-L-Tyr@PVA薄膜激发-发射二维曲线、(b) Fmoc-L-Tyr@PVA薄膜激发依赖磷光发射图谱

Figure 3. (a) Phosphorescence-excitation mapping, and (b) excitation-dependent delayed phosphorescence spectra of Fmoc-L-Tyr@PVA films

图4. (a) 10 mg PVA, 5 mg Fmoc-L-Tyr, 5 mg Fmoc-L-Tyr＋10 mg PVA分别溶于0.55 mL DMSO-d6的核磁共振氢谱; (b) 10 mg PVA, 5 mg Fmoc-D-Tyr, 5 mg Fmoc-L-Tyr＋10 mg PVA分别溶于0.55 mL DMSO-d6的核磁共振氢谱

Figure 4. (a) 1H NMR spectra of 10 mg PVA, 5 mg Fmoc-L-Tyr and 5 mg Fmoc-L-Tyr＋10 mg PVA in 0.55 mL DMSO-d6; (b) 1H NMR spectra of 10 mg PVA, 5 mg Fmoc-D-Tyr and 5 mg Fmoc-D-Tyr＋10 mg PVA in 0.55 mL DMSO-d6

图5. PVA和Fmoc-Trys@PVA膜的XRD图

Figure 5. XRD patterns of PVA and Fmoc-Tyrs@PVA films

图6. (a)简化的Jablonski能级图用于解释TS-FRET过程; (b) Fmoc-Tyr@PVA薄膜磷光发射光谱与RhB水溶液紫外吸收光谱和荧光发射光谱

Figure 6. (a) Simplified Jablonski diagram to explain the phosphorescence energy transfer; (b) Phosphorescence emission spectra of Fmoc-Tyrs@PVA films and the UV absorption spectrum and fluorescence emission spectrum of RhB aqueous solution

图7. RhB共掺杂Fmoc-Tyr薄膜的(a)磷光发射光谱、(b)寿命衰减曲线、(c)在激发波长为275 nm下拍摄的发光照片(紫外灯照射时间为5 s)

Figure 7. (a) Phosphorescent emission spectra, (b) phosphorescent life decay curves, and (c) luminescent photograph of Fmoc- Tyr/RhB@PVA films at an excitation wavelength of 275 nm (UV irradiation time is 5 s)

参考文献 22

[1]	Becquerel, E. C. R. Acad. Sci. 1866, 62, 999.
[2]	(a) Hirata, S.; Totani, K.; Kaji, H.; Vacha, M.; Watanabe, T.; Adachi, C. Adv. Opt. Mater. 2013, 1, 438.
	(b) Jian, M. Y.; Song, Z. C.; Chen, X. J.; Zhao, J. C.; Xu, B. J.; Chi, Z. G. Chem. Eng. J. 2022, 429, 132346.
[3]	Jiang, X; Wu, M. L.; Zhang, L; Wang, J. Y.; Cui, M. Y.; Wang, J. H.; Pang, X. K.; Song, B.; He, Y. Anal. Chem. 2022, 94, 7264. doi: 10.1021/acs.analchem.2c00510 pmid: 35427126
[4]	(a) Yang, J.; Zhen, X.; Wang, B.; Gao, X. M.; Ren, Z. A.; Wang, J. Q.; Xie, Y. J.; Li, J. R.; Peng, Q.; Pu, K. Y.; Li, Z. Nat. Commun. 2018, 9, 840. doi: 10.1038/s41467-018-03236-6 pmid: 29483501
	(b) Zhang, Y. H.; Li, H. R.; Yang, M. D.; Dai, W. B.; Shi, J. B.; Tong, B.; Cai, Z. X.; Wang, Z. Y.; Dong, W. P.; Yu, X. Q. Chem. Commun. 2023, 59, 5329. pmid: 29483501
[5]	Li, F. Y.; Du, Y.; Liu, J. A.; Sun, H.; Wang, J.; Li, R. Q.; Kim, D.; Hyeon, T.; Ling, D. S. Adv. Mater. 2018, 30, 1802808.
[6]	(a) Su, Y.; Phua, S. Z. F.; Li, Y. B.; Zhou, X. J.; Jana, D.; Li, G. F.; Lim, W. Q.; Ong, W. K.; Yang, C. L. Sci. Adv. 2018, 4, eaas9732.
	(b) Gao, L.; Huang, J. Y.; Qu, L. J.; Chen, X. H.; Zhu, Y.; Li, C.; Tian, Q. C.; Zhao, Y. L.; Yang, C. L. Nat. Commun. 2023, 14, 7252.
[7]	(a) Zhao, W. J.; He, Z. K.; Tang, B. Z. Nat. Rev. Mater. 2020, 5, 869.
	(b) Ma, X.; Wang, J.; Tian, H. Acc. Chem. Res. 2019, 52, 738.
	(c) Ma, X. K.; Liu, Y. Acc. Chem. Res. 2021, 54, 3403.
	(d) Guo, J. J.; Yang, C. L.; Zhao, Y. L. Acc. Chem. Res. 2022, 55, 1160.
[8]	Liang, Y. H.; Xu, C.; Zhang, H. Q.; Wu, S. Y.; Li, J. A.; Yang, Y. F.; Mao, Z.; Luo, S. L.; Liu, C.; Shi, G.; Sun, F. Q.; Chi, Z. G.; Xu, B. L. Angew. Chem., Int. Ed. 2023, 135, e202217616.
[9]	(a) Chen, X. F.; Xu, C.; Wang, T.; Zhou, C.; Du, J. J.; Wang, Z. P.; Xu, H. X.; Xie, T. Q.; Bi, G. Q.; Jiang, J.; Zhang, X. P.; Demas, J. N.; Trindle, C.; Luo, Y.; Zhang, G. Q. Angew. Chem., Int. Ed. 2016, 55, 9872. pmid: 21336325
	(b) Shi, H. F.; Song, L. L.; Ma, H. L.; Sun, C.; Huang, K. Y.; Lv, A. Q.; Ye, Y. P.; Wang, H.; Cai, S. Z.; Yao, W.; Zhang, Y. J.; Zheng, R. L.; An, Z. F.; Huang, W. J. Phys. Chem. Lett. 2019, 10, 595. pmid: 21336325
	(c) Mu, Y.; Wang, J. Q.; Han, S. D.; Pan, J.; Li, J. H.; Wang, G. M. Inorg. Chem. 2020, 59, 972. pmid: 21336325
	(d) Bolton, O.; Lee, K.; Kim, H. J.; Lin, K. Y.; Kim, J. Nat. Chem. 2011, 3, 205. doi: 10.1038/nchem.984 pmid: 21336325
[10]	An, Z. F.; Zheng, C.; Tao, Y.; Chen, R. F.; Shi, H. F.; Chen, T.; Wang, Z. F.; Li, H. H.; Deng, R. R.; Liu, X. G.; Huang, W. Nat. Mater. 2015, 14, 685.
[11]	(a) Yang, Z.; Xu, C.; Li, W.; Mao, Z.; Ge, X. Y.; Huang, Q. Y.; Deng, H. J.; Zhao, J.; Gu, F.; Zhang, Y.; Chi, Z. G. Angew. Chem., Int. Ed. 2020, 59, 17451. pmid: 38020368
	(b) Kongasseri, A. A.; Garain, S.; Ansari, S. N.; Garain, B. C.; Wagalgave, S. M.; Singh, U.; Pati, S. K.; George, S. J. Chem. Mater. 2023, 35, 7781. pmid: 38020368
	(c) Kongasseri, A. A.; Ansari, S. N.; Garain, S.; Wagalgave, S. M.; George, S. J. Chem. Sci. 2023, 14, 12548. doi: 10.1039/d3sc04001a pmid: 38020368
	(d) Song, J.; Ma, R. Chin. J. Org. Chem. 2021, 41, 4519 (in Chinese). pmid: 38020368
	(宋金明, 马骧, 有机化学, 2021, 41, 4519.) doi: 10.6023/cjoc202100082 pmid: 38020368
	(e) Yuan, W. Z.; Shen, X. Y.; Zhao, H.; Lam, J. W.; Tang, L.; Lu, P.; Wang, C.; Liu, Y.; Wang, Z.; Zheng, Q.; Sun, J. Z.; Ma, Y.; Tang, B. Z. J. Phys. Chem. C 2010, 114, 6090. pmid: 38020368
[12]	(a) Mieno, H.; Kabe, R.; Notsuka, N.; Allendorf, M. D.; Adachi, C. Adv. Opt. Mater. 2016, 4, 1015.
	(b) Lu, Y. L.; Wang, Y. J.; Zhu, L. L.; Yue, B. B. Chin. J. Org. Chem. 2022, 42, 3549 (in Chinese).
	(路云乐, 王彦杰, 朱亮亮, 岳兵兵, 有机化学, 2022, 42, 3549.) doi: 10.6023/cjoc202204063
[13]	(a) Xu, L. T.; Li, G. P.; Xu, T.; Zhang, W. D.; Zhang, S. K.; Yin, S. W.; An, Z. F.; He, G. Chem. Commun. 2018, 54, 9226.
	(b) Yang, Z. Y.; Mao, Z.; Zhang, X. P.; Ou, D. P.; Mu, Y. X.; Zhang, Y.; Zhao, C. Y.; Liu, S. W.; Chi, Z. G.; Xu, J. R.; Wu, Y. C.; Lu, P. Y.; Lien, A.; Bryce, M. R. Angew. Chem., Int. Ed. 2016, 55, 2181.
[14]	(a) Feng, R. C.; Wang, M. X.; Zhang, Z. Y.; Hu, P. T.; Wu, Z. Q.; Shi, G. Y.; Xu, B. J.; Li, H.; Ma, L. J. ACS Appl. Mater. 2023, 15, 30717.
	(b) Wan, K. L.; Zhai, Y. X.; Liu, S. X.; Li, J.; Li, S. J.; Strehmel, B.; Chen, Z. J.; James, T. D. Angew. Chem., Int. Ed. 2022, 61, e202202760.
	(c) Zhou, Q.; Yang, C. L.; Zhao, Y. L. Chem 2023, 9, 2446.
[15]	Dai, X. Y.; Huo, M.; Liu, Y. Nat. Rev. Chem. 2023, 7, 854.
[16]	Ma, X.; Xu, C.; Wang, J.; Tian, H. Angew. Chem., Int. Ed. 2018, 57, 10854.
[17]	Zhang, Y. F.; Su, Y.; Wu, H. W.; Wang, Z. H.; Wang, C.; Zheng, Y.; Zheng, X.; Gao L.; Zhou, Q.; Yang, Y.; Chen, X. H.; Yang, C. L.; Zhao, Y. L. J. Am. Chem. Soc. 2021, 143, 13675.
[18]	Lin, F. X.; Wang, H. Y.; Cao, Y. F.; Yu, R. J.; Liang, G. D.; Huang, H. H.; Mu, Y. X.; Yang, Z. Y.; Chi, Z. G. Adv. Mater. 2022, 34, 2108333.
[19]	Peng, H.; Xie, G. Z.; Cao, Y.; Zhang, L. Y.; Yan, X.; Zhang, X.; Miao, S. H.; Tao, Y.; Li, H. H.; Zheng, C.; Huang, W.; Chen, R. F. Sci. Adv. 2022, 8, eabk2925.
[20]	Zhang, Y. F.; Zhang, S. G.; Liu, G. Y.; Sun, Q. K.; Xue, S. F.; Yang, W. J. Chem. Sci. 2023, 14, 5177.
[21]	Liang, Y. H.; Hu, P.; Zhang, H. Q.; Yang, Q. C.; Wei, H. S.; Chen, R. T.; Yu, J. H.; Liu, C.; Wang, Y. H.; Luo, S. L.; Shi, G.; Chi, Z. G.; Xu, B. G. Angew. Chem., Int. Ed. 2024, 136, e202318516.
[22]	Zhen, J. S.; Long, J. Q.; Guo, X.; Wang, Q. S.; Zeng, X. Chem.-Eur. J. 2024, 30, e202304137.