高等学校化学学报 ›› 2020, Vol. 41 ›› Issue (2): 268.doi: 10.7503/cjcu20190448
收稿日期:
2019-08-09
出版日期:
2020-02-10
发布日期:
2019-11-14
通讯作者:
曹忠
E-mail:zhongcao2004@163.com
基金资助:
PENG Yuyu,WANG Yu,YU Xinyao,ZENG Julan,XIAO Zhongliang,CAO Zhong()
Received:
2019-08-09
Online:
2020-02-10
Published:
2019-11-14
Contact:
Zhong CAO
E-mail:zhongcao2004@163.com
Supported by:
摘要:
将单(6-巯基-6-去氧)-β-环糊精(HS-β-CD)通过金硫键自组装在金电极(GE)表面, 构建了一种简单、 快速、 灵敏的超分子识别L-半胱氨酸(L-Cys)的电位型电化学传感器. 通过循环伏安法和交流阻抗法研究了膜表面的电化学行为; 通过扫描电子显微镜(SEM)和X射线光电子能谱(XPS)表征了电极表面的膜组装效果, 其作用机制是固定在金电极表面的HS-β-CD空穴可通过分子间作用力吸附结合带负电的L-Cys, 使电极表面的膜电位发生改变, 导致对L-Cys的超分子选择性识别作用, 从而实现对L-Cys的定量分析. 在优化的实验条件下, 该电极在pH=6.0的磷酸盐缓冲溶液中对L-Cys有良好的电位响应性能, 线性范围为1.0×10 -7~1.0×10 -4 mol/L, 斜率为(-65.29±1.0) mV/pc(25 ℃), 检测下限达到6.0×10 -8 mol/L; 电极响应速度快、 稳定性和重现性好、 抗干扰能力强. 将该电极用于实际猪血清和猪尿液样品中L-Cys含量的测定, 回收率为95.0%~104.7%, 表明该新型电极在生命科学等领域具有良好的应用前景.
TrendMD:
彭与煜,王煜,于鑫垚,曾巨澜,肖忠良,曹忠. 基于单(6-巯基-6-去氧)-β-环糊精修饰金电极对L-半胱氨酸的快速灵敏检测. 高等学校化学学报, 2020, 41(2): 268.
PENG Yuyu,WANG Yu,YU Xinyao,ZENG Julan,XIAO Zhongliang,CAO Zhong. Rapid and Sensitive Detection of L-Cysteine Based on Mono(6-mercapto-6-deoxy)-β-cyclodextrin Modified Gold Electrode †. Chem. J. Chinese Universities, 2020, 41(2): 268.
Fig.4 Cyclic voltammetry(A) and impedance(B) curves of bare GE(a), HS-β-CD/GE(b), and L-Cys/HS-β-CD/GE(c) electrodes in the media solution of containing 5.0 mmol/L K3Fe(CN)6/K4Fe(CN)6 and 0.5 mol/L Na2SO4
Fig.6 Typical potential response curves to L-Cys at different modification time(A) and effect of electrode sensitivity on modification time(B) (A) Modification time/h: a. 4; b. 8; c. 12; d. 24; d. 36; f. 48.
Fig.7 Effect of electrode sensitivity on pH(A) and corresponding potential response curves for L-Cys at different pH values(B) (B) pH value: a. 3; b. 4; c. 5; d. 5.5; e. 6; f. 6.5; g. 7; h. 8 ; i. 9.
Fig.8 Potential response curve of HS-β-CD/GE to L-Cys in PBS(pH=6.0) with various concentrations The red lines are the fitted curves of potential change vs. logarithmic concentration of L-Cys.
Fig.9 Dynamic curve of HS-β-CD/GE responding to various concentration of L-Cys in PBS(pH=6.0)(A) and enlarged plot of stage G for 1.0×10-4 mol/L of L-Cys(B) c(L-Cys)/( mol·L-1): a. 1.0×10-8; b. 5.0×10-8; c. 1.0×10-7; d. 5.0×10-7; e. 1.0×10-6; f. 1.0×10-5; g. 1.0×10-4.
No. | Potential/mV | No. | Potential/mV | ||
---|---|---|---|---|---|
1.0×10-5 mol/L | 1.0×10-6 mol/L | 1.0×10-5 mol/L | 1.0×10-6 mol/L | ||
1 | -141 | -82 | 6 | -140 | -80 |
2 | -142 | -81 | AV | -140.8 | -80.2 |
3 | -140 | -79 | SD | ±0.75 | ±1.05 |
4 | -141 | -80 | RSD(%) | 0.54 | 1.31 |
5 | -141 | -81 |
Table 1 Reproducibility of HS-β-CD/GE responding to L-Cys in PBS(pH=6.0)*
No. | Potential/mV | No. | Potential/mV | ||
---|---|---|---|---|---|
1.0×10-5 mol/L | 1.0×10-6 mol/L | 1.0×10-5 mol/L | 1.0×10-6 mol/L | ||
1 | -141 | -82 | 6 | -140 | -80 |
2 | -142 | -81 | AV | -140.8 | -80.2 |
3 | -140 | -79 | SD | ±0.75 | ±1.05 |
4 | -141 | -80 | RSD(%) | 0.54 | 1.31 |
5 | -141 | -81 |
Fig.10 Effects of interfering substance on HS-β-CD/GE The concentration of L-Cys is 1.0×10-6 mol/L, and the concentrations of other coexisting substances are 1.0×10-4 mol/L. a. L-Cys; b. L-Cys+L-Val; c. L-Cys+L-Trp; d. L-Cys+L-Phe; e. L-Cys+L-Leu; f. L-Cys+L-Thr; g. L-Cys+L-Ala; h. L-Cys+L-Ile; i. L-Cys+L-Gly; j. L-Cys+L-Arg; k. L-Cys+L-Pro; l. L-Cys+L-Cyn; m. L-Cys+L-Met; n. L-Cys+L-His; o. L-Cys+L-Lys; p. L-Cys+Na+; q. L-Cys+K+; r. L-Cys+Ca2+; s. L-Cys+UA; t. L-Cys+GLC.
Sample | c(L-Cys)a/ (μmol·L-1) | c(L-Cys)b/ (μmol·L-1) | Spiked/ (μmol·L-1) | Found/ (μmol·L-1) | Recovery(%) | RSD(%) |
---|---|---|---|---|---|---|
Serum 1 | 0.3213 | 0.3265 | 0.1056 | 0.4371 | 104.7 | 4.2 |
Serum 2 | 0.4127 | 0.4261 | 0.6065 | 1.0290 | 99.4 | 1.1 |
Serum 3 | 0.7634 | 0.7528 | 1.0980 | 1.9010 | 104.5 | 1.8 |
Serum 4 | 0.6516 | 0.6602 | 4.9850 | 5.7010 | 101.1 | 2.5 |
Serum 5 | 0.1528 | 0.1573 | 9.8870 | 9.8990 | 98.5 | 0.77 |
Serum 6 | 0.1472 | 0.1396 | 50.12 | 48.58 | 96.6 | 2.9 |
Urine 1 | —— | —— | 0.1056 | 0.1073 | 101.6 | 5.7 |
Urine 2 | —— | —— | 0.6065 | 0.6056 | 99.8 | 2.1 |
Urine 3 | —— | —— | 1.098 | 1.043 | 95.0 | 5.2 |
Urine 4 | —— | —— | 4.985 | 4.983 | 99.9 | 2.1 |
Urine 5 | —— | —— | 9.887 | 9.997 | 101.1 | 0.54 |
Urine 6 | —— | —— | 50.12 | 49.34 | 98.4 | 1.7 |
Table 2 Recovery of the proposed HS-β-CD/GE for determination of L-Cys in pig serum and urine samples
Sample | c(L-Cys)a/ (μmol·L-1) | c(L-Cys)b/ (μmol·L-1) | Spiked/ (μmol·L-1) | Found/ (μmol·L-1) | Recovery(%) | RSD(%) |
---|---|---|---|---|---|---|
Serum 1 | 0.3213 | 0.3265 | 0.1056 | 0.4371 | 104.7 | 4.2 |
Serum 2 | 0.4127 | 0.4261 | 0.6065 | 1.0290 | 99.4 | 1.1 |
Serum 3 | 0.7634 | 0.7528 | 1.0980 | 1.9010 | 104.5 | 1.8 |
Serum 4 | 0.6516 | 0.6602 | 4.9850 | 5.7010 | 101.1 | 2.5 |
Serum 5 | 0.1528 | 0.1573 | 9.8870 | 9.8990 | 98.5 | 0.77 |
Serum 6 | 0.1472 | 0.1396 | 50.12 | 48.58 | 96.6 | 2.9 |
Urine 1 | —— | —— | 0.1056 | 0.1073 | 101.6 | 5.7 |
Urine 2 | —— | —— | 0.6065 | 0.6056 | 99.8 | 2.1 |
Urine 3 | —— | —— | 1.098 | 1.043 | 95.0 | 5.2 |
Urine 4 | —— | —— | 4.985 | 4.983 | 99.9 | 2.1 |
Urine 5 | —— | —— | 9.887 | 9.997 | 101.1 | 0.54 |
Urine 6 | —— | —— | 50.12 | 49.34 | 98.4 | 1.7 |
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