量子点室温磷光探针检测生物体液中的头孢哌酮钠舒巴坦钠

doi:10.7503/cjcu20160082

摘要/Abstract

摘要：

以水相合成的3-巯基丙酸包覆的Mn掺杂ZnS量子点(MPA-Mn/ZnS QDs)作为室温磷光探针, 基于头孢哌酮钠舒巴坦钠(CPZ-SBT)作为一种电子受体, 可通过电子转移有效猝灭Mn/ZnS QDs的室温磷光效应, 构建了一种测定痕量CPZ-SBT的方法. 当CPZ-SBT浓度为0.7~84 μg/L时, 其与MPA-Mn/ZnS QDs的磷光强度之间呈良好线性关系, 相关系数为0.99, 该方法的检出限为0.14 μg/L.

关键词: 量子点, 室温磷光探针, 检测, 头孢哌酮钠舒巴坦钠

Abstract:

A method for the determination of trace cefoperazone sodium-sulbactam sodium(CPZ-SBT) was established using water phase synthesized 3-mercaptopropionic acid-capped Mn-doped ZnS quantum dots(MPA-Mn/ZnS QDs) as a room temperature phosphorescence(RTP) probe, which based on the phenomenon that the electron acceptor acted by CPZ-SBT can effectively quench the RTP of MPA-Mn/ZnS QDs through electron transfer. There is a good relationship between CPZ-SBT and changes on the phosphorescence intensity of MPA-Mn/ZnS QDs when the concentration of CPZ-SBT is in the scope of 0.7—84 μg/L. The correlation coefficient and detection limit of this method are 0.99 and 0.14 μg/L, respectively. Additionally, this method is able to conduct analysis simply without deoxidizer, inducer or complex sample processing, which can effectively avoid the interference of background fluorescence and scattered light in biological fluids and can be successfully applied in trace determination of CPZ-SBT in biological fluids as well.

Key words: Quantum dots, Room temperature phosphorescence probe, Detection, Cefoperazone sodium-sulbactam sodium(CPZ-SBT)

中图分类号:

O657.3

TrendMD:

房晓星, 郑吉, 闫桂琴. 量子点室温磷光探针检测生物体液中的头孢哌酮钠舒巴坦钠. 高等学校化学学报, 2016, 37(8): 1435.

FANG Xiaoxing,ZHENG Ji,YAN Guiqin. Detection of Cefoperazone Sodium and Sulbactam Sodium in Biological Fluid by Quantum Dots Room Temperature Phosphorescence Probe^†. Chem. J. Chinese Universities, 2016, 37(8): 1435.

图/表 10

Fig.1 TEM image(A), XRD pattern(B), zeta potential diagram(C) and the excitation spectrum(a) with phosphorescence emission spectrum(b) of MPA-Mn/ZnS QDs(D) QDs: 40 mg/L; PBS buffer: 20 mmol/L; pH=6.0.

Fig.2 Effects of pH(A), time(B) and NaCl concentration(C) on the RTP intensity of QDs and QDs-CPZ-SBT

Fig.3 CPZ-SBT concentration-dependent RTP emission of the QDs(A) and the variation of ΔP(P0-P) as a function of CPZ-SBT QDs: 40 mg/L; CPZ-SBT: 84 μg/L; PBS: 20 mmol/L, pH=6.0.

Table 1 Different analytical techniques reported for detection of CPZ-SBT

Substance	Method	Detection range/(g·L^-1)	LOD/(μg·L^-1)	Reference
CPZ	HPLC	1.5×10^-2—2.7	0.408	[17]
SBT	HPLC	1.4×10^-2—2.7	1.96	[17]
CPZ	RP-HPLC	4.9×10^-2—0.49	1.0	[18]
SBT	RP-HPLC	2.4×10^-2—0.24	2.0	[18]
CPZ	UPLC	20.66—154.95	2.31	[19]
SBT	UPLC	20.96—152.18	6.22	[19]
CPZ-SBT	Fluorescence	8.0×10^-6—1.0×10^-4	0.10	[20]
CPZ-SBT	Phosphorescent	7.0×10^-7—8.4×10^-5	0.14	This method

Fig.4 Temperature-dependent response of P0/P to CPZ-SBT(A) and UV-Vis spectra of CPZ-SBT with emission spectra of QDs(B) QDs: 40 mg/L; CPZ-SBT: 84 μg/L. (B) a. CPZ-SBT; b. QDs.

Fig.5 Fluorescence(A), UV-Vis absorption(B), RLS of QDs-CPZ-SBT(C) spectra and changes of QDs-CPZ-SBT RLS after addition of NaCl(D)(QDs, 40 mg/L; CPZ-SBT, 84 μg/L) (A) a. CPZ-SBT; b. QDs; c. QDs-CPZ-SBT(QDs: 40 mg/L; CPZ-SBT: 84 μg/L); (B) a. CPZ-SBT; b. QDs; c. QDs-CPZ-SBT(QDs: 40 mg/L; CPZ-SBT: 42 μg/L); d. QDs-CPZ-SBT(QDs: 40 mg/L; CPZ-SBT: 84 μg/L); (C) QDs: 40 mg/L; concentration of CPZ-SBT/(μg·L-1): 0, 14, 28, 42, 56, 84; (D) QDs: 40 mg/L; CPZ-SBT: 84 μg/L; NaCl: 0.04, 0.10, 0.20, 0.30 mol/L.

Scheme 1 Mechanism of the RTP quenching process

Table 2 Tolerance of foreign substances

Co-existing substance	Tolerance ratio	Change of RTP intensity(%)	Co-existing substance	Tolerance ratio	Change of RTP intensity(%)
Na⁺	200	1.7	Serine	300	1.6
K⁺	200	-3.1	L-Gly	200	3.3
Ca²⁺	150	1.7	L-Cys	150	-1.9
Mg²⁺	100	-2.8	Glucose	100	2.6

Table 3 Detection of CPZ-SBT in real samples(n=3)

Sample	Added/(μg·L^-1)	Found/(μg·L^-1)	Recovery(%)	RSD(%)(n=3)
Human serum	5	4.6	95.3±2	2.78
	10	10.3	101.5±1	1.09
Human urine	5	5.2	103.7±4	1.96
	10	9.8	97.4±2	2.89

Fig.6 Phosphorescence and fluorescence spectra of urine(a, d) and serum(b, c)

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