Qiu Changjing, Liu Hongchen, Wang Xijun, Tao Shenming, Mo Jilong, Chen Pinhong, Xiao He, Qi Haisong
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510641, China.
State Key Laboratory of Pulp and Paper Engineering, South China University of Technology, Guangzhou 510641, China; College of Textiles, Zhongyuan University of Technology, Zhengzhou 450007, China; National Forestry and Grassland Administration Key Laboratory of Plant Fiber Functional Materials, Fujian Agriculture and Forestry University, Fuzhou 350108, China.
Carbohydr Polym. 2024 Dec 15;346:122620. doi: 10.1016/j.carbpol.2024.122620. Epub 2024 Aug 16.
Polymer-based sensors, particularly those derived from renewable polymers, are gaining attention for their superior properties compared to organic small molecules. However, their complex preparation and poor, uncontrollable sensitivity have hindered further development. Herein, cellulose-based polymer photoluminescence (PL) chemosensors were fabricated using a straightforward and adjustable strategy. Specifically, water-soluble cellulose acetoacetate (CAA) was used as the substance for the in-situ synthesis of 1,4-dihydropyridine (DHPs) fluorescent rings on cellulose chains via a catalyst-free, room-temperature Hantzsch reaction. Benefiting from the synergetic through-space conjugation of DHPs rings and semi-rigid cellulose chains with heteroatoms, the sensors exhibit bright and stable PL properties. Based on this performance, the cellulose-based sensor excels in the specific recognition of Fe in aqueous systems, showing exceptional selectivity, stability, and anti-interference performance due to the synergy between the inner filter effect (IFE) and intramolecular charge transfer (ICT). Theoretical calculations confirm the role of the extended π-conjugated structure at the DHPs-4 position in modulating the sensor sensitivity, achieving a low limit of detection (LOD) of 0.48 μM. Furthermore, the versatility of the Hantzsch reaction shows the potential of this strategy for developing a new generation of biomass-based polymer portable sensors for real-time and on-site detection.
基于聚合物的传感器，尤其是那些源自可再生聚合物的传感器，因其相较于有机小分子的优越性能而受到关注。然而，其复杂的制备过程以及较差且不可控的灵敏度阻碍了其进一步发展。在此，采用一种直接且可调节的策略制备了基于纤维素的聚合物光致发光（PL）化学传感器。具体而言，水溶性乙酰乙酸纤维素（CAA）被用作通过无催化剂的室温汉斯奇反应在纤维素链上原位合成1,4 - 二氢吡啶（DHP）荧光环的物质。得益于DHP环与含杂原子的半刚性纤维素链的协同空间共轭，该传感器展现出明亮且稳定的PL性能。基于此性能，基于纤维素的传感器在水体系中对铁具有出色的特异性识别能力，由于内滤光效应（IFE）和分子内电荷转移（ICT）之间的协同作用，表现出卓越的选择性、稳定性和抗干扰性能。理论计算证实了DHP - 4位扩展的π共轭结构在调节传感器灵敏度方面的作用，实现了0.48 μM的低检测限（LOD）。此外，汉斯奇反应的通用性显示了该策略在开发新一代用于实时和现场检测的基于生物质的聚合物便携式传感器方面的潜力。
