含大体积侧基纤维素类衍生物的合成及其金属离子荧光识别性能研究  

Synthesis of Cellulose Derivative Bearing Bulky Substituents and Fluorescence Recognition Property for Metal Ions

作　　者：王宇清 王凡 代枭 王伟琪 沈军[1,3] Yu-qing Wang;Fan Wang;Xiao Dai;Wei-qi Wang;Jun Shen(College of Materials Science and Chemical Engineering,Harbin Engineering University,Harbin 150001;College of Mechanical Engineering,Tongling University,Tongling 244000;School of Civil and Resource Engineering,University of Science and Technology Beijing,Beijing 100083)

机构地区：[1]哈尔滨工程大学材料科学与化学工程学院,哈尔滨150001 [2]铜陵学院机械工程学院,铜陵244000 [3]北京科技大学土木与资源工程学院,北京100083

出　　处：《高分子学报》2024年第10期1335-1345,共11页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号51673052,21474024,51073046);黑龙江省自然科学基金重点项目(基金号ZD2021B001);黑龙江省自然科学基金联合引导项目(基金号LH2023E063);铜陵学院人才科研启动基金(基金号2023tlxyrc23)资助项目.

摘　　要：以微晶纤维素为基质,通过6-位保护法和氨基甲酸酯化反应,合成了一种6-位具有大体积咔唑侧基的区域选择性取代纤维素类衍生物,即纤维素-[2,3-(3,5-二甲基)-6-(4-(4-(3-(9-乙基-9H-咔唑-3)脲基)苄基))]苯基氨基甲酸酯(Cel-1).由核磁共振氢谱和元素分析结果表明所合成衍生物的结构规整,取代基本完全.基于12种金属离子对Cel-1的荧光识别性能进行了详细评价.结果表明,大体积纤维素衍生物Cel-1可在DMSO/H_(2)O体系中对Fe^(3+)和Cu^(2+)实现高灵敏度和高选择性的双模式检测,同时对其他10种金属离子均有极好的抗干扰能力.其中,在荧光模式和紫外可见光模式下,Cel-1对Fe^(3+)和Cu^(2+)的检测限均低于美国国家环境保护局(EPA)所规定的2种离子在饮用水中可接受的最高浓度.证明所合成的大体积纤维素类衍生物具有对Fe^(3+)和Cu^(2+)的高效特异性荧光识别性能,可作为化学传感器用于这2种金属离子的快速识别与检测.此外,基于Cel-1制备的荧光墨水在自然光下不显示,但在紫外光下则可观察到明亮的蓝色荧光,显示了其在防伪领域的应用潜能.A regioselectively substituted cellulose derivative with bulky pendants at the 6-position,that is the cellulose-[2,3-(3,5-dimethyl)-6-(4-(4-(3-(9-ethyl-9H-carbazole-3)ureido)benzyl))]phenylcarbamate(Cel-1),was successfully synthesized using cellulose as substrate by 6-position-protection method and carbamoylation.The 1H-NMR spectrum and elemental analysis data indicated that the cellulose derivative was structurally regular with almost complete substitution as expected.The fluorescent recognition property of Cel-1 was then evaluated in detail based on twelve metal ions.The results indicated that the bulky cellulose derivative(Cel-1)could realize excellent dual-mode recognition to both Fe^(3+)and Cu^(2+)with high sensitivity and high selectivity in the DMSO/H_(2)O system,together with high anti-counterfeiting ability to the other ten metal ions tested in the study.Especially,the limits of detection of Cel-1 for Fe^(3+)and Cu^(2+)in both fluorescence and UV-visible modes were lower than the maximum acceptable concentrations of the two ions in drinking water as defined by the United States Environmental Protection Agency(EPA).It demonstrated that the obtained bulky cellulose derivative possessed high-efficient and specific fluorescent recognition ability for Fe^(3+)and Cu^(2+),which could be used as chemosensors for the rapid recognition and detection of the two metal ions.In addition,the fluorescent ink prepared based on Cel-1 could not be observed under natural light,whereas emitted bright blue fluorescence under ultraviolet light,suggesting its potential in the anti-counterfeiting related field.

关 键 词：荧光传感 大体积侧基 纤维素类衍生物 金属离子识别 双模式检测 

分 类 号：TQ352.7[化学工程] O657.3[理学—分析化学]