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郑州大学于阿娟教授团队‖【Anal. Chem.】一种基于多发射MOF、功能化pH敏感染料的荧光传感器阵列用于PFASs的高灵敏检测与识别

  • 2026-04-16 06:02:20
郑州大学于阿娟教授团队‖【Anal. Chem.】一种基于多发射MOF、功能化pH敏感染料的荧光传感器阵列用于PFASs的高灵敏检测与识别

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介绍 /Introduction

全氟和多氟烷基物质(PFASs)因其大规模使用和持久性污染特性,已成为全球关注的环境和人体健康问题。因此,在水相体系中实现PFASs的灵敏传感与区分具有重要意义。本工作通过溶剂热法合成了两种具有开放金属位点的锆基金属有机框架(Zr-MOFs),即UiO-67-NH₂和PCN-999,并将其作为主体用于封装pH敏感的染料分子。通过原位封装策略,将尼罗红和异硫氰酸荧光素(FITC)嵌入UiO-67-NH₂的纳米笼中,同时将罗丹明6G衍生物(RGH)引入PCN-999的纳米空腔内。所得两种荧光复合材料FR@UiO-67-NH₂和RGH@PCN-999表现出优异的水稳定性和发光持久性,在单波长激发下分别呈现三发射和双发射通道。基于这两种Dye@MOFs构建的荧光传感器阵列,可根据差异化的荧光响应,用于六种PFASs的高灵敏检测与识别。
结合主成分分析(PCA)和层次聚类分析(HCA),该荧光传感器阵列能够准确区分浓度低至0.5 μM的六种PFASs,并成功实现了对它们多元混合物的区分,对单一PFASs的检测限低至21.8 nM。此外,该传感器阵列在复杂基质(包括自来水、湖水和消防防护服洗涤液)中表现出优异的PFASs区分能力和半定量检测性能。粉末X射线衍射(PXRD)、红外吸收光谱(FT-IR)和X射线光电子能谱(XPS)进一步证实,该荧光传感器阵列可能涉及静态荧光猝灭机制。
相关成果以 “ A Multiemission MOF-Based Fluorescent Sensor ArrayFunctionalized with pH-Sensitive Dyes for Highly Sensitive Detection and Identification of PFASs” 为题发表在《Anal. Chem.
全文速递.pdf郑州大学于阿娟教授团队‖Anal.Chem.一种基于多发射MOF功能化pH敏感染料的荧光传感器阵列用于PFASs的高灵敏检测与识别.pdf

研究图/Introduction

Scheme 1. (a) General Procedure for the Fabrication of Dye@MOFs Composites and (b) Fluorescence Screening and Discrimination Mechanism of the MOF-Based Sensor Array toward PFASs

Figure 1. SEM images of (a) UiO-67-NH2; (b) FR@UiO-67-NH2; (c) PCN-999; and (d) RGH@PCN-999.

Figure 2. (a) PXRD patterns and (b) FT-IR of H2BPDC-NH2, UiO-67-NH2, FR@UiO-67-NH2, and FR@UiO-67-NHin H2O; (c) fluorescence emission spectra of Nile Red, FITC, UiO-67-NH2, and FR@UiO-67-NH2; (d) PXRD patterns and (e) FT-IR of L12, PCN-999, RGH@PCN-999, and RGH@PCN-999 in H2O; and (f) fluorescence emission spectra of RGH, L12, PCN-999, and RGH@PCN-999.

Figure 3. Radar plots of fluorescence responses (I0/I) of (a) FR@UiO-67-NH2 and (b) RGH@PCN-999 toward six PFASs (10 μM) under different channels; (c) bar graphs of I0/I across five channels (where I0 and I represent the fluorescence intensities at a specific emission wavelength before and after the addition of PFASs, respectively; channels 1-5 correspond to λem = 470, 512, 640, 515, and 550 nm, respectively).
Figure 4. (a1,b1) Heat maps; (a2,b2) PCA score plots; and (a3,b3) HCA plots of the sensor array toward six PFASs at different concentrations (a1-a3: 1 μM; b1-b3: 2 μM).
Figure 5. (a1) Heat maps; (a2) PCA score plots of the sensor array toward PFOA at different concentrations; and (a3) plots of factor 1 as a function of the PFOA concentrations.
Figure 6. (a1) Heatmaps; (a2) HCA plots; (a3) PCA score plots of PFOA/PFOS binary mixtures at different molar ratios; (b1) heatmaps; (b2) HCA plots; and (b3) PCA score plots of multicomponent PFAS mixtures at different molar ratios.
Figure 7. PCA score plots of the sensor array for six PFASs in (a1) tap water, (a2) lake water, and (a3) washing liquor of the firefighting protective clothing; HCA plots of the sensor array for six PFASs in (b1) tap water, (b2) lake water, and (b3) washing liquor of the firefighting protective clothing.

结论 /Conclusion

总之,通过原位封装策略,将pH敏感染料(FITC和尼罗红)分别嵌入UiO-67-NH₂的纳米空腔中,同时将RGH嵌入PCN-999的孔道内,得到了两种具有优异水稳定性和多发射通道的荧光复合材料FR@UiO-67-NH₂和RGH@PCN-999。在单一激发波长下,由这两种Dye@MOFs组合构建的荧光传感器阵列具有五个发射通道,可用于浓度低至0.5 μM的六种PFASs的高灵敏检测与识别。同时,将pH响应性染料嵌入MOFs/MOCs的空腔中,不仅能拓宽复合材料的荧光发射通道、提高检测效率,还能与弱电离的PFASs发生质子交换,并诱导被选择性捕获的PFASs进入MOFs的纳米笼空腔,从而显著提高了复杂基质中PFASs检测的抗干扰能力和灵敏度。结合多元统计技术,成功实现了PFASs多元混合体系的区分,对单一PFASs的定量检测限低至21.8 nM。此外,该传感器阵列在复杂基质中PFASs的准确识别和半定量检测方面也取得了成功应用。通过XRD、FT-IR和XPS表征,该荧光传感器阵列的传感机制可能是由于PFASs吸附到Dye@MOFs上而引起的静态荧光猝灭。此类荧光传感器的合成策略拓展了基于LMOFs阵列的传感技术的应用范围,并为区分和半定量检测PFASs这类环境污染物提供了新颖的研究范式。

文献直通车 /Literature information

A Multiemission MOF-Based Fluorescent Sensor Array Functionalized with pH-Sensitive Dyes for Highly Sensitive Detection and Identification of PFASsJiayi Fan, Xinwen Jia, Mengyun Lu, Quanming Yin, Fenghua Dai,and Ajuan Yu*

原文链接:https://doi.org/10.1021/acs.analchem.5c06375

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  1. CONNECT:[ UseTime:0.000393s ] mysql:host=127.0.0.1;port=3306;dbname=i460;charset=utf8mb4
  2. SHOW FULL COLUMNS FROM `fenlei` [ RunTime:0.000580s ]
  3. SELECT * FROM `fenlei` WHERE `fid` = 0 [ RunTime:0.023390s ]
  4. SELECT * FROM `fenlei` WHERE `fid` = 63 [ RunTime:0.000906s ]
  5. SHOW FULL COLUMNS FROM `set` [ RunTime:0.000795s ]
  6. SELECT * FROM `set` [ RunTime:0.000943s ]
  7. SHOW FULL COLUMNS FROM `article` [ RunTime:0.000586s ]
  8. SELECT * FROM `article` WHERE `id` = 513213 LIMIT 1 [ RunTime:0.003497s ]
  9. UPDATE `article` SET `lasttime` = 1777443895 WHERE `id` = 513213 [ RunTime:0.004533s ]
  10. SELECT * FROM `fenlei` WHERE `id` = 64 LIMIT 1 [ RunTime:0.000280s ]
  11. SELECT * FROM `article` WHERE `id` < 513213 ORDER BY `id` DESC LIMIT 1 [ RunTime:0.002158s ]
  12. SELECT * FROM `article` WHERE `id` > 513213 ORDER BY `id` ASC LIMIT 1 [ RunTime:0.000525s ]
  13. SELECT * FROM `article` WHERE `id` < 513213 ORDER BY `id` DESC LIMIT 10 [ RunTime:0.000980s ]
  14. SELECT * FROM `article` WHERE `id` < 513213 ORDER BY `id` DESC LIMIT 10,10 [ RunTime:0.008288s ]
  15. SELECT * FROM `article` WHERE `id` < 513213 ORDER BY `id` DESC LIMIT 20,10 [ RunTime:0.002327s ]
0.130146s