基于 AuNPs@Cu-porphyrin MOF 纳米酶的人血清中 GSH 的比色和 SERS 双模检测。

Colorimetric and SERS dual-mode detection of GSH in human serum based on AuNPs@Cu-porphyrin MOF nanozyme.

机构信息

Key Laboratory of Electromagnetic Transformation and Detection of Henan Province, College of Physics and Electronic Information, Luoyang Normal University, Luoyang, 471934, China; CAS Key Laboratory of High Magnetic Field and Iron Beam Physical Biology, Institute of Intelligent Machines, Hefei Institute of Physical Sciences, Chinese Academy of Sciences, Hefei, 230031, China.

CAS Key Laboratory of High Magnetic Field and Iron Beam Physical Biology, Institute of Intelligent Machines, Hefei Institute of Physical Sciences, Chinese Academy of Sciences, Hefei, 230031, China; Science Island Branch of Graduate School, University of Science and Technology of China, Hefei, 230026, China.

出版信息

Anal Chim Acta. 2024 May 22;1304:342552. doi: 10.1016/j.aca.2024.342552. Epub 2024 Mar 27.

DOI:10.1016/j.aca.2024.342552

PMID:38637053

Abstract

BACKGROUND

Rapid and accurate detection of glutathione content in human blood plays an important role in real-time tracking of related diseases. Currently, surface-enhanced Raman scattering/spectroscopy (SERS) combined with nanozyme material has been proven to have excellent properties in the detection applications compared to many other methods because of it combines the advantages of trace detection capability of SERS and efficient catalytic activity of nanozymes. However, there are still existing problems in real sample detection, and to achieve quantitative detection is still challenging.

RESULTS

In this study, gold nanoparticles (AuNPs) were synthesized in situ on the surface of two-dimensional Cu-porphyrin metal-organic framework (MOF) nanosheets to produce the AuNPs@Cu-porphyrin MOF nanozyme, which exhibited both oxidase-like activity and SERS detection ability. On one hand, the intrinsic oxidase-like activity of the nanozyme could be inhibited due to the chelation of glutathione (GSH) and Cu, which thus led to the visual color change of the solution. On the other hand, the abundant Raman "hot spots" at the nanogap generated by Au NPs and the internal standard (IS) signal provided by Cu-meso-tetra (4-carboxyphenyl) porphine (Cu-TCPP) MOF improved the sensitivity and quantitative accuracy of detection.

SIGNIFICANCE AND NOVELTY

A dual-mode signal output sensor based on the nanozyme was thus established, which could be used in the trace detection of GSH. Such a dual-mode sensor possesses excellent detection performance, with the advantage of both wide detection range from 1 to 300 μM in the colorimetric detection mode and high sensitivity with LOD of 5 nM in the SERS detection mode, and can be applied to GSH detection in actual serum samples with reliable results.

摘要

背景

快速、准确地检测人血液中的谷胱甘肽含量在实时跟踪相关疾病方面发挥着重要作用。目前，表面增强拉曼散射/光谱（SERS）结合纳米酶材料在检测应用中已被证明具有优于许多其他方法的优异性能，因为它结合了 SERS 的痕量检测能力和纳米酶的高效催化活性的优点。然而，在实际样品检测中仍然存在问题，实现定量检测仍然具有挑战性。

结果

在这项研究中，在二维铜卟啉金属-有机骨架（MOF）纳米片的表面原位合成了金纳米粒子（AuNPs），产生了具有类氧化酶活性和 SERS 检测能力的 AuNPs@Cu-卟啉 MOF 纳米酶。一方面，由于谷胱甘肽（GSH）和 Cu 的螯合作用，纳米酶的固有类氧化酶活性会受到抑制，从而导致溶液的颜色发生变化。另一方面，Au NPs 产生的纳米间隙中的丰富拉曼“热点”和内部标准（IS）信号由 Cu-间四（4-羧基苯基）卟啉（Cu-TCPP）MOF 提供，提高了检测的灵敏度和定量准确性。