光电化学技术应用于抗氧化分析的研究进展

doi:10.7503/cjcu20190651

摘要/Abstract

摘要：

在新陈代谢过程中, 机体会产生大量以自由基为主要形式的氧化活性物质, 而抗氧化剂可以通过电子转移的方式捕获并中和自由基, 从而有效抵御自由基引起的细胞损害, 以保障和维护人体健康. 食品作为人体外源性抗氧化剂的重要来源可以有效补充因体内代谢及体液排出而损失的抗氧化物质, 因此对食品中抗氧化物质消除自由基的能力即抗氧化能力的测定和评价具有重要意义. 光电化学技术作为一种简单快捷、低成本、低背景且高灵敏度的测定方法, 能够有效克服光学法、色谱法和电化学法等传统测试手段在抗氧化容量分析中的不足. 本文综述了基于半导体及其复合材料的光电化学传感平台的构建及食品体系抗氧化容量分析的研究进展, 评论了多种检测体系的特点并对其研究前景进行了展望.

关键词: 抗氧化, 光电化学, 传感器, 食品分析

Abstract:

In the process of metabolism, the body will produce a large number of oxidation active substances with free radicals as the main formation, and antioxidants can capture and neutralize free radicals in the form of electron transfer, so as to protect the cell from damage, prevent and retard the oxidative deterioration of food. Therefore, it is of great significance for the determination and evaluation of antioxidants capacitance in foods. As a low-cost, simple, quick and sensitive method, photoelectrochemical(PEC) technology can overcome the shortcomings of conventional methods, such as optical method, chromatographic method and electrochemical method. The design of photocatalysis materials is the key of the PEC platform. The review concludes with the progress of the photoelectrochemical platform based on semiconductor materials applied in the analysis of antioxidant capacity in food and the characteristics of various detection systems. In addition, the future research directions are also proposed.

Key words: Antioxidant, Photoelectrochemistry, Sensor, Food analysis

中图分类号:

O657

韩方杰, 代梦娇, 梁芷珊, 宋忠乾, 韩冬雪, 牛利. 光电化学技术应用于抗氧化分析的研究进展[J]. 高等学校化学学报, 2020, 41(4): 591-603.

HAN Fangjie, DAI Mengjiao, LIANG Zhishan, SONG Zhongqian, HAN Dongxue, NIU Li. Research Progress of Photoelectrochemical Technology Applied in Antioxidant Analysis ^†[J]. Chemical Journal of Chinese Universities, 2020, 41(4): 591-603.

图/表 16

Fig.1 Process and principle of photoelectrochemical analysis

Fig.2 Band positions and potential applications of some typical photocatalysts in aqueous solutions(pH=7)

Fig.3 Photocurrent responses of the g-C3N4/ITO electrode to different concentrations of AA(A) and corresponding calibration curve(B) in 0.1 mol/L PBS(pH=7.4)[62](A) c(AA)/(μmol·L-1): a. 0; b. 0.25; c. 0.5; d. 1; e. 3; f. 5; g. 10; h. 15; i. 25; j. 35; k. 55; l. 75; m. 100; n. 125; o. 175; p. 225; q. 325; r. 425; s. 525; t. 775; u. 1275. Inset of (B) shows better illustration of linear part in calibration curve. Error bars correspond to the standard deviations from three independent measurements with RSD equal to 5.2%.Copyright 2018, Elsevier.

Fig.4 Photocurrent responses of TiO2(a0, a1), rGO-TiO2(b0, b1) and PANI-rGO-TiO2(c0, c1) modified ITO without(a0—c0) and with(a1—c1) 166.8 mmol/L GA(A); photocurrent responses of PANI-rGO-TiO2 modified ITO with different concentrations of GA(B); photocurrent response of a PANI-rGO-TiO2 modified ITO electrode upon the addition of 166.8 mmol/L each of AA, GA, 33.36 mmol/L each of GSH, CYs, L-citric acid, L-malic acid, 0.167 mol/L each of ethanol, methanol, glucose, L-glycine in 0.1 mol/L PBS(pH=7.4) at 0 V under 420 nm light excitation(C) and illustration of photoelectro-chemical process for GA oxidation at PANI-rGO-TiO2 modified ITO(D)[39](B) The photoelectrochemical sensors were applied at 0 V under 420 nm light excitation in 0.1 mol/L PBS(pH=7.4). Inset in (B) is the linear calibration curve. ^Copyright 2013, Royal Society of Chemistry.

Fig.5 Schematic illustration of the surface contact region between Bi2MoO6 and Bi2S3, TDOS and LDOS of the Bi2MoO6/Bi2S3 heterostructures, the energy levels for valence and conduction bands of Bi2MoO6/Bi2S3(A); photocurrents of GA, EC, CT, CHA, CA and MT on Bi2MoO6/Bi2S3(B) and photocurrent responses of Bi2MoO6/Bi2S3 modified ITO electrode upon different concentrations of GA(C)[42]Inset of (C) is the corresponding liner calibration. The photoelectrochemical sensor was applied at 0 V under 470 nm irradiation in 0.1 mol/L PBS(pH=7.4). Copyright 2017, Elsevier.

Fig.6 Photocurrents of 12 μmol/L PG, TBHQ, BHA, BHT and VE on MoS2/ZnO heterostructures(A); photocurrent responses of MoS2/ZnO heterostructures modified ITO electrodes upon different concentrations of PG(B) and chemical structures of five antioxidants and proposed mechanism of the MoS2/ZnO-based photoelectrochemical sensor for the detection of PG(C)[66] (B) The inset is the corresponding linear calibration. The preceding photoelectrochemical experiments were applied at 0 V(vs. Ag/AgCl) under 470 nm irradiation in 0.1 mol/L PBS(pH=7.4). Copyright 2019, American Chemical Society.

Fig.7 Schematic illustration of photoelectrochemical process for antioxidant capacity sensor designed with GO-TiO2 composites as source of OH radicals and DNA as a molecular probe(A) and agarose gel electrophoresis of different types of DNA(B) [40] Lane a: DNA markers; lanes b and c: DNA illuminated for 20 and 30 min with GOB-TiO2; lane d: after addition of gallic acid, DNA was illuminated 30 min with GOB-TiO2; lane e: DNA was illuminated 30 min without GOB-TiO2. Copyright 2013, Royal Society of Chemistry.

Table 1 Detection of antioxidant capacity by three different methods[40]

Sample	DNA sensor for GA/(mg·g^-1)	F-C method for GA/(mg·g^-1)	DPPH method for trolox/(mg·g^-1)
B1	47.45	60.29	141.20
B2	66.61	62.94	201.10
B3	41.86	78.40	191.50
B4	24.34	18.55	49.90
B5	38.39	39.82	86.30

Fig.9 Photocurrent responses of SGE-TiO2 modified ITO electrode upon different concentrations of GA(A), CT(B), CA(C), EGC(D), EGCG(E) and ECG(F), respectively [37]Inset in each graph is the corresponding liner calibration curve. The photoelectrochemical sensors were applied at 0 V under 420 nm light excitation in 0.1 mol/L PBS(pH=7.4).Copyright 2014, American Chemistry Society.

Fig.10 Mechanism of the photoelectrochemical sensor for the detection of the antioxidant capacity[38]AO: antioxidant; Ex(eV): the redox potential of the antioxidants with respect to a vacuum; E(V): the redox potential of the antioxidants(vs. Ag/AgCl); IP(kJ/mol): ionization potential of the antioxidants; AC: antioxidant capacity obtained from the slope of the standard calibration curve of each antioxidant. Copyright 2014, Royal Society of Chemistry.

Fig.11 Photograph of the thin layer photoelectrochemical flow cell(A), concentration-dependent photocurrent of CA(B), CT(C) and AA(D)[38]Insets in (B)—(D) are the linear curves of CA, CT and AA, respectively. Copyright 2014, Royal Society of Chemistry.

Fig.12 Photograph of the integrated PEC platform(A) and photocurrent responses of the BiMo0.015V0.985O4 modified ITO electrode in the PEC platform without(blank: PBS solution) and with a certain volume of juice into 4 mL PBS(0.1 mol/L, pH=7.4)(B)[35]Copyright 2015, Royal Society of Chemistry.

Table 2 Antioxidant capacities of fresh fruits detected by different methods(n=3)[35]

Practical sample	Antioxidant capacity/(mg·L^-1)
Practical sample	PEC sensor	F-C method	DPPH method
Mango	356.38±6.80	369.73±2.63	267.61±1.46
Grape	229.40±1.13	247.71±0.61	172.73±2.92
Apple	257.45±4.95	252.01±2.43	176.86±2.53
Mangosteen	265.54±6.63	308.44±5.27	182.01±3.86
Pitaye	104.18±3.14	129.27±0.38	83.76±0.73
Orange	445.59±9.12	468.67±1.52	281.66±1.82
Leechee	540.48±1.01	564.39±3.04	325.50±3.16
Kiwi fruit	601.12±5.38	611.73±4.56	344.83±11.38

Table 3 Antioxidant capacities of commercial teas(T, mg/g) and drinks(D, mg/L) detected by different methods(n=3)[35]

Practical sample	Antioxidant capacity/(mg·g^-1 or mg·L^-1)
Practical sample	PEC sensor	F-C method	DPPH method
T1	18.78±0.80	35.82±0.25	54.84±0.24
T2	73.33±1.72	106.56±0.53	144.03±0.42
T3	108.63±1.91	120.87±0.70	161.18±0.85
T4	52.11±1.51	71.60±0.23	106.90±0.73
D1	387.19±0.62	420.30±1.07	203.64±2.39
D2	345.31±1.24	386.24±6.77	193.31±2.30
D3	396.16±4.34	437.52±1.32	318.36±7.59
D4	429.88±4.24	459.78±2.97	325.78±2.39
D5	316.78±0.98	337.46±2.21	185.21±1.53
D6	393.10±0.98	435.85±1.14	250.63±4.08
D7	457.50±3.01	492.08±1.14	566.88±3.28
D8	712.10±13.04	770.78±1.02	731.51±1.55
D9	641.11±9.59	701.33±3.70	728.08±1.37
D10	436.60±4.37	487.50±0.41	522.16±4.07
D11	296.41±0.76	310.27±1.70	164.06±2.06
D12	352.02±5.05	388.18±0.62	198.06±2.06
D13	391.22±1.42	432.17±1.03	232.09±4.07
Practical sample	Antioxidant capacity/(mg·g^-1 or mg·L^-1)
Practical sample	PEC sensor	F-C method	DPPH method
D14	176.01±0.76	137.02±0.52	45.29±1.63
D15	58.07±0.36	34.43±0.19	27.96±0.73
D16	59.29±0.27	40.32±0.18	31.07±0.48

Fig.13 Inside(A), the whole instrument(B), one part of the two-EPCS(C), scheme of microfluidic chip(D) and profile of concentration vs. photocurrent of GA on the microfluidic chip(E)[41](1) The counter electrode(d=8.5 mm); (2) the working electrode(d=10.0 mm); (3) the inlet; (4) the outlet; (5) the lead wire of counter electrode; (6) the lead wire of working electrode. Copyright 2015, Elsevier.

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