基于金@二氧化锰纳米片超级纳米粒子从比色到单颗粒光谱检测谷胱甘肽

doi:10.7503/cjcu20190686

摘要/Abstract

摘要：

合成了由金纳米球和二氧化锰薄片组成的金@二氧化锰纳米片超级纳米粒子(AMNS-SPs), 将其作为探针, 利用比色和单颗粒光谱2种分析方法进行了谷胱甘肽的传感检测. 该传感检测基于选择性刻蚀探针AMNS-SPs中的二氧化锰纳米片, 使得该探针的局域表面等离子共振波长蓝移. 实验结果表明, 比色法和单颗粒光谱法检测谷胱甘肽的检出限分别为0.018 μmol/L和23.2 fmol/L, 且后者是目前检测谷胱甘肽灵敏度最高的传感方法之一. 该传感方法的优异性能主要源于非常薄的二氧化锰纳米片.

关键词: 谷胱甘肽, 比色, 裸眼检测, 单颗粒光谱

Abstract:

We herein study glutathione(GSH) sensing by two kinds of assay modes, namely colorimetry and single particle spectroscopy, using the as-prepared hybrid supraparticles made of gold nanoparticles and MnO₂ nanosheets(denoted as AMNS-SPs) as probes. The sensing is based on the selective etching of decorated MnO₂ nanosheets, which causes a substantial blue shift of the localized surface plasmon resonance of the AMNS-SPs. In terms of the two sensing systems, the detection limits are 0.018 μmol/L and 23.2 fmol/L, respectively. To our knowledge, the latter is one of the highest sensitivity for GSH sensing. This favorable performance is attributed to a rather thin thickness of the decorated MnO₂ nanosheets.

Key words: Glutathione, Colorimetric, Naked eye detection, Single particle spectroscopy

中图分类号:

O657.3

TrendMD:

凌云云,李莉,梁修蓉,夏云生. 基于金@二氧化锰纳米片超级纳米粒子从比色到单颗粒光谱检测谷胱甘肽. 高等学校化学学报, 2020, 41(4): 623.

LING Yunyun,LI Li,LIANG Xiurong,XIA Yunsheng. Glutathione Sensing: from Colorimetry to Single Particle Spectroscopy Based on Gold NP@MnO₂ Nanosheets Supraparticles. Chem. J. Chinese Universities, 2020, 41(4): 623.

图/表 6

Fig.1 Characterizations of the AMNS-SPs^SEM(A), TEM(B), HRTEM(C) and AFM(D, E) images of the AMNS-SPs. The curves a and b in Fig.1(E) represents the height profiles along the red and blue lines in Fig.1(D), respectively. (F) UV-Vis absorption spectra of AuNPs(a) and AMNS-SPs(b), and the insets are the corresponding photo images.

Fig.2 XPS spectra of the AMNS-SPs(A) Survey spectrum; (B) Au4f; (C) Mn2p; (D) O1s.

Fig.3 GSH sensing in bulk solution with AMNS-SPsTime-dependent absorption spectra of the AMNS-SPs in 10 (A), 50 (B), 100 (C) μmol/L of GSH, respectively. Time of curves a—p: 0—15 min. (D) Etching dynamics of the AMNS-SPs by 10(a), 50(b) and 100(c) μmol/L GSH. (E) c(GSH)/(μmol·L-1): a. 0; b. 0.2; c. 0.5; d. 1; e. 5; f. 10; g. 20; h. 50; i. 100; j. 200; k. 300. Absorption spectra of the AMNS-SPs in the presence of various concentrations of GSH. Dynamic range[0—300 μmol/L, (F)] and linear range [0.2—100 μmol/L, (G)] of the LSPR peak shift(Δλ) in different concentrations of GSH, respectively. (H) Linear range(0.2—100μmol/L) of ΔA380 in different concentrations of GSH. (I) a. PBS(pH=7.0); b. PBS(pH=7.4); c. Tris(pH=7.0); d. Tris(pH=7.4); e. KCl; f. K2CO3; g. NaCl; h. Na2SO4; i. MgSO4; j. MnSO4; k. alanine; l. arginine; m. lysine; n. serin; o. threonin; p. valine; q. histidine; r. glycine; s. leucine; t. glutamic acid; u. tyrosine; v. aspartic acid; w. tryptophan; x. cysteine; y. BSA; z. HSA; z1. fructose; z2 maltose; z3 glucose; z4 AA; z5 GSH. The responses of the AMNS-SPs to various biomolecules[the concentrations of various electrolytes(columns a—j) are 10 mmol/L. The concentrations of various amino acids(columns k—x) are 10, 10, 1.0, 10, 10, 10, 10, 10, 10, 0.25, 0.25, 0.25, 0.25 and 0.025 mmol/L, respectively. Both the concentrations of bovine serum albumin(BSA) and human serum albumin(HSA) are 1 mg/mL. The concentrations of fructose, maltose, glucose, AA and GSH(columns z1—z5) are 10, 10, 10, 0.025, and 0.025 mmol/L, respectively. (J) Photos of the AMNS-SPs etched by GSH. From left to right, the concentrations of GSH are 0, 0.5, 1, 5, 10, 20, 50, 100, 200, 300 μmol/L, respectively. The reaction time is 15 min.

Fig.4 Etching process of the AMNS-SPs by GSH molecules(0.3 μmol/L)Dark-field images of the AMNS-SPs before(A) and after(B) the etching process, respectively. (C) Scattering spectra of a single AMNS-SP before(a) and after(b) the etching process. (D) Time-dependent dark-field images of the AMNS-SPs. (E) TEM images of the AMNS-SPs during the etching process.

Fig.5 GSH sensing with single particle dark-field spectral imagingTypical single particle spectral images before(A) and after(B) adding GSH. (C) Distribution of λs-max after adding 0 pmol/L(C1), 1 pmol/L(C2), 10 pmol/L(C3), 100 pmol/L(C4), 1 nmol/L(C5), 10 nmol/L(C6), 100 nmol/L(C7) and 1 μmol/L(C8) GSH. 100 of the SPs are counted in each case. (D) Δλs-max vs. GSH concentration.

Fig.6 Characterizations of the TAMNS-SPs and their etching process by GSH molecules(0.3 μmol/L)TEM(A), HRTEM(B) and AFM(C, D) images of the TAMNS-SPs. The curves a and b in Fig.6(D) represents the height profiles along the red and blue lines in Fig.6(C), respectively. The time-dependent dark-field images of the TAMNS-SPs, time/min: (E) 0; (F) 5; (G) 10; (H) 15; (I) 20.

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