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Photo-stimulus-responsive dual-emitting fluorescence of spiropyran-encapsulated carbon dots-functionalized silicon dioxide for dynamic information encryption

基于碳点功能化的二氧化硅封装螺吡喃的光响应材料用于动态信息加密

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Abstract

Developing stimulus-responsive fluorescent materials plays a crucial role in solving emerging requirements for information security. Here, we propose a stimulus-responsive dual-emitting fluorescent material SP@SiO2-CDs (SP = spiropyran) that was acquired by encapsulating the SP compound in carbon dots (CDs)-functionalized silicon dioxide. This composite shows a blue emission at 470 nm from the CDs and a red emission at approximately 620 nm from SP. With continuous ultraviolet (UV) light irradiation (365 nm), SP molecules undergo the ring-closing to ring-opening process, and significant fluorescence resonance energy transfer can be achieved between SiO2-CDs and isomeric merocyanine. The SP@SiO2-CDs powders can show not only photo-chromism from yellow to pink under UV stimulation but also double-emission fluorescence conversion from blue-white to orange-red. When exposed to white light, this dynamic fluorescence behavior can be completely restored to the initial state. Taking full advantage of the time dependence of fluorescence, we have successfully developed a dynamic anticounterfeiting pattern and multiple codes. In addition, by doping with polydimethylsiloxane, we obtained an independent film with high flexibility and mechanical strength and demonstrated its application in time-dependent information encryption. This work provides a novel approach to improve the security of information encryption related to offline portable information encryption.

摘要

开发刺激响应荧光材料对于解决信息安全的新兴需求至关重要. 本文中, 我们提出了一种刺激响应双发射荧光材料SP@SiO2-CDs (SP: 螺吡喃), 该材料是通过将螺吡喃化合物封装到碳点功能化的二氧化硅中得到的. 这种复合材料显示碳点在470 nm处发射蓝色光, 螺吡喃在620 nm处发射红色光. 在连续紫外光(365 nm)照射下, 螺吡喃分子经历从闭环到开环的过程, SiO2-CDs和异构部花青之间可以实现显著的荧光能量共振转移. SP@SiO2-CDs复合物粉末不仅可以在紫外光刺激下光致变色从黄色到粉色, 而且可以实现从淡蓝色到橙红色的双发射荧光转换. 当暴露在白光下时, 这种动态荧光行为可以完全恢复到初始状态. 基于荧光的时间依赖性, 本文成功开发了动态防伪图案和多重编码. 此外, 通过掺杂聚二甲基硅氧烷, 获得了具有高柔韧性和机械强度的薄膜, 并展示了其在高级信息加密中的应用. 该工作为提高离线便携式信息加密的安全性提供了一种新方法.

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Acknowledgements

This work was supported by Zhejiang Sci-Tech University Shengzhou Innovation Research Institute (SYY2.023C000005).

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Author notes

  1. These authors contributed equally to this work

Authors and Affiliations

  1. School of Materials Science and Engineering, Zhejiang Sci-Tech University, Hangzhou, 310018, China

    Jiangkun Zhu  (朱姜昆), Huimin Zhao  (赵慧敏), Yuhui Yang  (杨玉慧), Wei Wu  (吴伟), Leilei Hu  (胡磊磊), Youhao Wei  (卫尤豪) & Yangyang Gao  (高阳旸)

  2. Department of Polymer Materials, Zhejiang Sci-Tech University, Hangzhou, 310018, China

    Yuhui Yang  (杨玉慧)

  3. Institute of Smart Biomedical Materials, Zhejiang Sci-Tech University, Hangzhou, 310018, China

    Yuhui Yang  (杨玉慧)

  4. Zhejiang Sci-Tech University Shengzhou Innovation Research Institute, Shengzhou, 312451, China

    Yuhui Yang  (杨玉慧)

Authors
  1. Jiangkun Zhu  (朱姜昆)
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Contributions

Author contributions Yang Y conceived the idea and supervised this work. Zhu J and Zhao H conducted the experiments, analyzed the data and prepared the manuscript with support from Yang Y. Wu W, Hu L, Wei Y and Gao Y revised the manuscript. All authors contributed to the general discussion.

Corresponding author

Correspondence to Yuhui Yang  (杨玉慧).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Supplementary information Experimental details and supporting data are available in the online version of the paper.

Jiangkun Zhu is a Master’s student under the guidance of Yuhui Yang at Zhejiang Sci-Tech University. His current research focuses on the preparation of dynamic photo-chromic materials.

Huimin Zhao received her Master’s degree from Zhejiang Sci-Tech University in June, 2023. During her Master’s degree, her research focused on the preparation of photochromic materials based on SiO2@SP complexes.

Yuhui Yang is an associate professor at the School of Materials and Engineering, Zhejiang Sci-Tech University. In 2016, she obtained a doctorate degree in organic chemistry from the Institute of Physical and Chemical Technology, Chinese Academy of Sciences. Her main research areas include organic photochromic materials, anticounterfeiting materials, and smart fibers.

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40843_2023_2728_MOESM1_ESM.pdf

Photo-stimulus-responsive dual-emitting fluorescence of spiropyran-encapsulated carbon dots-functionalized silicon dioxide for dynamic information encryption

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Zhu, J., Zhao, H., Yang, Y. et al. Photo-stimulus-responsive dual-emitting fluorescence of spiropyran-encapsulated carbon dots-functionalized silicon dioxide for dynamic information encryption. Sci. China Mater. 67, 680–689 (2024). https://doi.org/10.1007/s40843-023-2728-9

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