纤维素基固态荧光传感器的研究进展

杨青峰; 安聪聪; 张明; 李正辉; 施镭; 周凝宇

doi:10.13801/j.cnki.fhclxb.20230724.003

纤维素基固态荧光传感器的研究进展

doi: 10.13801/j.cnki.fhclxb.20230724.003

北华大学　材料科学与工程学院，吉林 132013

基金项目: 吉林省自然科学基金(YDZJ202201ZYTS441)；吉林省发改委产业创新专项资金项目(2023C038-2)；吉林市科技创新发展计划杰出青年人才培养专项(20200104083)；生物多糖纤维成形与生态纺织国家重点实验室(青岛大学)开放基金项目(KFKT202213)

详细信息

通讯作者:
张明，博士，副教授，硕士生导师，研究方向为生物质多元纳米复合材料仿生智能化研究　E-mail: mattzhming@163.com

中图分类号: TQ34；TQ340.7；TB332
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出版历程
- 收稿日期: 2023-05-08
- 修回日期: 2023-06-14
- 录用日期: 2023-07-01
- 网络出版日期: 2023-07-25
- 刊出日期: 2024-01-01

Research progress of cellulose-based solid-state fluorescence sensors

School of Materials Science and Engineering, Beihua University, Jilin 132013, China

Funds: Natural Science Foundation of Jilin Province (YDZJ202201ZYTS441); Jilin Provincial Development and Reform Commission Industrial Innovation Special Fund Project (2023C038-2); Science and Technology Innovation Development Plan of Jilin City (20200104083); State Key Laboratory of Bio-Fibers and Eco-Textile (Qingdao University) (KFKT202213)

摘要

摘要: 在“双碳”战略背景下，生物基荧光智能材料的研究进展及其多功能应用备受瞩目。纤维素是自然界储量最丰富的天然高分子材料，基于纤维素的固态荧光传感器不但具备绿色、成本低、可降解、亲水性好、生物相容性好、无毒等优点，相较于传统的荧光分子探针，还拥有更便携、高效、寿命长、稳定性高、适用场景广泛等优势。综述了近些年来利用化学改性制备纤维素基固态荧光传感器的研究进展，阐明了纤维素与不同荧光分子结合的机制，即通过共价交联或者引入官能团，将荧光分子引到纤维素表面进行改性。分类介绍了各种纤维素基固态荧光传感器的类型，包括阳离子型、阴离子型、pH型、硝基芳香型、气体型和双(多)重响应型等，以及在环境检测、生物成像、食品安全、荧光印刷及防伪等应用领域的优势。最后，详细探讨了纤维素基荧光智能传感器的相关研究，并对其发展机遇和未来挑战进行展望。
- 荧光 /
- 纤维素 /
- 智能响应 /
- 传感器 /
- 检测
Abstract: Under the background of the "dual carbon" strategy, the research progress of bio-based fluorescent intelligent materials and their multifunctional applications have attracted much attention. Cellulose is the most abundant natural polymer material in nature. Cellulose-based solid-state fluorescence sensors not only have the advantages of green, low cost, biodegradability, good hydrophilicity, good biocompatibility, and non-toxicity, but also have advantages such as portability, efficiency, long lifespan, high stability, and wide applicability compared to traditional fluorescent molecular probes. The research progress of cellulose-based solid-state fluorescent sensors prepared by chemical modification in recent years was reviewed. The mechanism of the combination of cellulose with different fluorescent molecules was clarified. Fluorescent molecules were introduced to the surface of cellulose by covalent crosslinking or introduction of functional groups. Various types of cellulose-based solid-state fluorescence sensors, including cationic, anionic, pH-type, nitroaromatic, gas-type and double (multi) re-responsive types, were introduced. The advantages of cellulose-based solid-state fluorescence sensors in environmental detection, bioimaging, food safety, fluorescence printing and anti-counterfeiting applications were also introduced. Finally, the relevant research on cellulose-based fluorescent smart sensors is discussed in detail, and their development opportunities and future challenges are prospected.
- fluorescence /
- cellulose /
- intelligent response /
- sensors /
- testing

HTML全文

图 1 纤维素的结构示意图^[23]

Figure 1. Schematic diagram of cellulose structure^[23]

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图 2 (a) 1, 10-邻菲罗啉-5-胺 (Phen)-4, 4' -亚甲基二苯基二异氰酸酯(MDI)-醋酸纤维素(CA)对Fe²⁺检测机制^[32]；(b) 纤维素纳米晶体(CNC)-琥珀酸酐(SA)-卟啉酯(COOC₆TPP)对Hg²⁺检测机制^[33]

Figure 2. (a) 1, 10-phenanthroline-5-amine (Phen)-4,4′-methylene diphenyl diisocyanate (MDI)-cellulose acetate (CA) detection mechanism for Fe²⁺^[32]; (b) Cellulose nanocrystal (CNC)-succinic anhydride (SA)-porphyrin ester (COOC₆TPP) detection mechanism for Hg²⁺^[33]

Ex—Excitation spectrum; Em—Emission spectrum

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图 3 自然光下(a)和紫外光下(b)的香豆素基荧光分子(CAM)照片；(c) 香豆素基荧光纤维素(CFC)复合膜材料制备及Hg²⁺检测示意图；自然光下 (d) 和紫外光下 (e) 抗聚集诱导猝灭(anti-ACQ)材料照片^[34]

Figure 3. Photographs of coumarin-based probe molecule (CAM) under daylight (a) and ultraviolet light (b); (c) Schematic diagram of coumarin-based fluorescent cellulose (CFC) composite membrane material preparation and Hg²⁺ detection and removal; Photographs of anti-aggregation-caused quenching (anti-ACQ) materials under daylight (d) and ultraviolet light (e)^[34]

CMC—Carboxymethyl cellulose

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图 4 (a) 柠檬酸/半胱氨酸改性纤维素基复合材料的防伪、Cl⁻检测和紫外屏蔽性能^[39]；(b) 四丁基铵盐和HSO₄⁻浓度对纸条颜色的影响^[40]；(c) 纸带浸入HSO₄⁻与NaOH溶液及两次重复使用后的紫外-可见吸收光谱^[40]

Figure 4. (a) Anti-counterfeiting, Cl⁻ detection, and UV shielding properties of citric acid/cysteine modified cellulose based composites^[39]; (b) Effect of tetrabutylammonium salt and HSO₄⁻ concentration on the color of paper strips^[40]; (c) Paper tape was immersed in HSO₄⁻ solution and NaOH solution, and refreshed in the UV visible absorption spectra after two repeated uses^[40]

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图 5 2, 4, 6-三硝基甲苯(TNT)检测荧光滤纸的制备及其作用机制图^[46]

Figure 5. Preparation of 2, 4, 6-trinitrotoluene (TNT) detection fluorescent filter paper and its mechanism diagram^[46]

NACs—Nitroaromatic compound pollutants; Poly(HEMA-co-PyMA)—Poly(2-hydroxyethyl methacrylate-co-pyrene-butyric acid hema

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图 6 纤维素基荧光传感器作用机制及其不同pH下颜色和荧光变化^[53]

Figure 6. Mechanism of cellulose based fluorescence sensors and their color and fluorescence changes under different pH values^[53]

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表 1 纤维素基固态荧光传感器的类型、性能优势及其应用领域

类型	检测物质	性能优势	应用领域	参考文献
阳离子型	Fe²⁺	高选择性、灵敏、易操作、形态多样等	图案印刷、化学传感、防伪等	^[32]
	Hg²⁺	灵敏、选择性高、便携、易规模化等	重金属吸附、检测等	^{[33, 34]}
	Pb²⁺	简单、灵敏、成本低、抗干扰等	重金属吸附、生物成像等	^[35-37]
	Cu²⁺	灵敏、高选择性等	重金属吸附、检测等	^{[1, 38]}
阴离子型	Cl^-	形态多样、抗紫外、高选择性等	化学传感、紫外屏蔽和防伪等	^[33]
	HSO₄^-	灵敏、高选择性、抗干扰、强荧光等	环境检测等	^[39]
	CN^-	高选择性、高亲/保水性等	环境检测等	^[40-43]
	ClO^-/SCN^-	响应可逆、循环使用性好等	环境检测、指纹信息提取等	^[44]
其他	硝基芳烃	高选择性、适用场景灵活等	水体与固体检测、生物监测传感等	^{[2, 45-48]}
	pH	灵敏、机械性能好、绿色、溶剂稳定等	酸碱指示、检测等	^{[49, 50]}
	气体	高选择性、适用场景灵活等	生物医学、食品安全等	^{[17, 51]}
	双(多)重	灵敏、检测物质多样、适用场景灵活等	多模式监测、环境检测等	^[52-55]
	其他	生物相容性、低细胞毒性等	生物成像、安全印刷、防伪等	^[58-60]

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表 1 纤维素基固态荧光传感器的类型、性能优势及其应用领域

Table 1. Types, performance advantages and applications of cellulose based solid-state fluorescence sensors

类型	检测物质	性能优势	应用领域	参考文献
阳离子型	Fe²⁺	高选择性、灵敏、易操作、形态多样等	图案印刷、化学传感、防伪等	[32]
	Hg²⁺	灵敏、选择性高、便携、易规模化等	重金属吸附、检测等	[33-34]
	Pb²⁺	简单、灵敏、成本低、抗干扰等	重金属吸附、生物成像等	[35-37]
	Cu²⁺	灵敏、高选择性等	重金属吸附、检测等	[1, 38]
阴离子型	Cl⁻	形态多样、抗紫外、高选择性等	化学传感、紫外屏蔽和防伪等	[39]
	HSO₄⁻	灵敏、高选择性、抗干扰、强荧光等	环境检测等	[40]
	CN⁻	高选择性、高亲/保水性等	环境检测等	[41-44]
	ClO⁻/SCN⁻	响应可逆、循环使用性好等	环境检测、指纹信息提取等	[45]
其他	硝基芳烃	高选择性、适用场景灵活等	水体与固体检测、生物监测传感等	[2, 46-49]
	pH	灵敏、力学性能好、绿色、溶剂稳定等	酸碱指示、检测等	[50-51]
	气体	高选择性、适用场景灵活等	生物医学、食品安全等	[17, 52]
	双(多)重	灵敏、检测物质多样、适用场景灵活等	多模式监测、环境检测等	[53-57]
	其他	生物相容性、低细胞毒性等	生物成像、安全印刷、防伪等	[59-61]

下载: 导出CSV

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