Li Yan-Feng, Zhang Xian, Lu Qian, Cao Jing-Zhen, Gao Sheng, Liu Qin-Ze, Cai Xiao-Xia, Zhao Hui
School of Materials Science and Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan, 250353, China.
School of Materials Science and Engineering, Qilu University of Technology (Shandong Academy of Sciences), Jinan, 250353, China.
Anal Chim Acta. 2024 Oct 2;1324:343102. doi: 10.1016/j.aca.2024.343102. Epub 2024 Aug 13.
Hexavalent chromium (Cr (VI)) is highly carcinogenic to humans. Ascorbic acid (AA) deficiency can be hazardous to health. And the dual-effect fluorescence detection of them is an important research topic. Carbon dots (CDs) based on cellulose are excellent candidates for the fluorescence probes due to their low cost and environmental friendliness. But most of them exhibit shortwave emission, small Stokes shift and poor fluorescence performance, all of which limit their use. Therefore, there is an urgent need for cellulose CDs with longer emission wavelengths and larger Stokes shifts in dual-effect fluorescence detection of Cr (VI) and AA.
Under optimal conditions (180 °C, 12 h), we prepared cellulose-based nitrogen-doped carbon dots (N-CDs) by a simple one-step hydrothermal process, which display longer emission wavelengths (ex: 370 nm, em: 510 nm), larger Stokes shifts (140 nm) and high fluorescence quantum yield (QY: 19.27 %). The continuous "turn-off" and "turn-off-on" fluorescence detection platforms were constructed based on the internal filtering effect (IFE) between Cr and N-CDs, and Cr reduced to Cr by AA at pH = 6. The platform has been successfully simultaneous detect Cr (VI) and AA with a wide range of 0.01-40 μM and 0.1-100 μM. And the lowest limits of detection (LOD) are 0.0303 μM and 0.072 μM, respectively. In the presence of some other metals, non-metal ions and water-soluble acids in the fruits, this fluorescent platform can demonstrate a high level of interference immunity.
This represents the first yellow-green cellulose-based N-CDs with large Stokes shift for dual-effect detection of Cr (VI) and AA in real water samples and fresh fruits. The fluorescence detection platform has the advantage of low volume detection. Less than 2 mL of sample is required for testing and results are available in <5 min. This method is rare and supply a novel idea for the quantitative monitoring of Cr (VI) and AA.
六价铬(Cr(VI))对人类具有高度致癌性。抗坏血酸(AA)缺乏会对健康造成危害。对它们进行双效荧光检测是一个重要的研究课题。基于纤维素的碳点(CDs)因其低成本和环境友好性,是荧光探针的极佳候选材料。但大多数此类碳点表现出短波发射、小斯托克斯位移和较差的荧光性能,所有这些都限制了它们的应用。因此,在对Cr(VI)和AA进行双效荧光检测时,迫切需要发射波长更长、斯托克斯位移更大的纤维素碳点。
在最佳条件(180°C,12小时)下,我们通过简单的一步水热法制备了基于纤维素的氮掺杂碳点(N-CDs),其发射波长更长(激发波长:370nm,发射波长:510nm)、斯托克斯位移更大(140nm)且荧光量子产率高(QY:19.27%)。基于Cr与N-CDs之间的内滤效应(IFE)构建了连续的“关断”和“关断-开启”荧光检测平台,在pH = 6时,Cr被AA还原为Cr。该平台已成功同时检测浓度范围为0.01 - 40μM和0.1 - 100μM的Cr(VI)和AA。最低检测限(LOD)分别为0.0303μM和0.072μM。在水果中存在一些其他金属、非金属离子和水溶性酸的情况下,该荧光平台能表现出高水平的抗干扰能力。
这代表了首个用于实际水样和新鲜水果中Cr(VI)和AA双效检测的具有大斯托克斯位移的黄绿色纤维素基N-CDs。该荧光检测平台具有检测体积小的优势。测试所需样品量少于2mL,且在<5分钟内即可获得结果。此方法较为罕见,为Cr(VI)和AA的定量监测提供了新思路。