自组装协同催化高选择性合成卤代芳烃
史时辉, 李皓瑜, 韩少杰, 姚一凡, 刘思齐
【大学化学】doi: 10.3866/PKU.DXHX202312002
卤代芳烃是非常重要的合成砌块,广泛应用于农用化学品、材料和药物等的合成。芳烃的亲电取代卤化反应是制备芳基卤化物最简单的方法,但是富电子芳烃的卤化反应存在区域选择性差的挑战。本实验采用自组装协同催化策略,以环己基苯溴化反应为模型反应,高选择性合成溴代芳烃,进而应用于卤代芳烃的高选择性合成。在加深学生芳烃亲电取代卤化反应的同时,也向学生传授自组装、协同催化和路易斯酸碱催化等重要知识,加深学生对亲电取代反应机理和离子型中间体的了解。实验主要由卤代芳烃的合成、机理探究及实验普适性三部分组成,包含多种有机实验基本操作,涉及反应监测、分离纯化、产物表征等多个重要环节,实验整体时长7小时,安全性高,可操作性强,适合本科实验教学开设。本实验秉持科研反哺教学的理念,将新的科研成果转化为人才培养内容,有助于提高学生的科研创新与实践能力。
关键词: 卤代芳烃, 区域选择性, 亲电取代卤化反应, 协同催化
Dual-ligand-modified copper nanoclusters: Synthesis and application in ornidazole detection
Rui TIAN, Duo LI, Yuan REN, Jiamin CHAI, Xuehua SUN, Haoyu LI, Yuecheng ZHANG
【无机化学学报】doi: 10.11862/CJIC.20240389
Bovine serum albumin (BSA) and glycine (Gly) dual-ligand-modified copper nanoclusters (BSA-Gly CuNCs) with high fluorescence intensity were synthesized by a one-pot strategy. Based on the competitive fluorescence quenching and dynamic quenching effects of ornidazole (ONZ) on BSA-Gly CuNCs, a simple and sensitive detection method for ONZ was successfully developed. The experimental results demonstrate that the addition of the small molecule Gly can more effectively protect CuNCs, and thus enhance its fluorescence intensity and stability. The proposed assay allowed for the detection of ONZ in a linear range of 0.28 to 52.60 μmol·L-1 and a detection limit of 0.069 μmol·L-1. Compared with the single-ligand-modified CuNCs, dual-ligand-modified BSA-Gly CuNCs had higher fluorescence intensity, stability, and sensing ability and were successfully applied to evaluate ONZ in actual ONZ tablets.
关键词: copper nanocluster, ornidazole, dual-ligand-modified, fluorescence detection
B掺杂长余辉室温磷光碳量子点在信息加密与湿度检测中的应用
张越诚, 杨帆, 张诗雨, 马程骏, 田锐, 孙雪花, 李皓瑜, 孙凌波, 马红燕
【无机化学学报】doi: 10.11862/CJIC.20240415
以硼酸与苯甲酸(BZA)为原材料,通过一步热解法合成了B掺杂的长余辉室温磷光碳量子点(B-CQDs-BZA)。采用透射电子显微镜(TEM)、X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、紫外可见(UV-Vis)吸收光谱与荧光/磷光发射光谱对B-CQDs- BZA的形貌、结构及发光性能进行表征。结果显示,合成的B-CQDs-BZA主要是由无定形碳构成的尺寸介于2.0~4.5 nm之间的零维碳量子点。B-CQDs-BZA经254与302 nm的紫外光照射后,可呈现出长达20 s的蓝色室温磷光,经测试其磷光寿命长达2.09 s。该方法简单、快速且具有普遍适用性,使用多种原材料均可合成长余辉室温磷光CQDs。基于B-CQDs-BZA卓越的室温磷光发光寿命,我们将B-CQDs-BZA成功应用于时间分辨防伪技术。另外,根据水分子对B-CQDs-BZA的猝灭效应,将其制作成湿度试纸,用来检测环境空气的湿度。
关键词: 室温磷光, 碳量子点, 信息加密, 湿度
Chitosan/silica-coated copper nanoclusters: Synthesis and application in cefixime detection
Rui TIAN, Jiamin CHAI, Junyu CHEN, Yuan REN, Xuehua SUN, Haoyu LI, Yuecheng ZHANG
【无机化学学报】doi: 10.11862/CJIC.20250026
Herein, copper nanoclusters (Cu NCs) were synthesized in aqueous solution through a chemical reduction method using polyethyleneimine as reducing agent and protective ligand, with Cu(NO3)2 as copper source. Subsequently, composite fluorescent nanoparticles, chitosan-functionalized silica nanoparticles (CSNPs)-coated Cu NCs (Cu NCs/CSNPs), were synthesized via a reverse microemulsion method. Compared with Cu NCs, the composite Cu NCs/CSNPs exhibited an increased quantum yield and enhanced fluorescence sensing performance. Based on the composite Cu NCs/CSNPs, a fluorescence method for the detection of cefixime fluorescence quenching was established. The technique was simple, sensitive, and selective for detecting cefixime. The fluorescence quenching efficiency of Cu NCs/CSNPs was linearly related to the concentration of cefixime in the range of 3.98-38.5 μmol·L-1 (1.81-17.46 mg·L-1), with a limit of detection of 0.045 5 μmol·L-1 (20.6 μg·L-1).
关键词: copper nanoclusters, fluorescence detection, cefixime

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