Conclusions
In summary, a free-standing MXene/CTS/Cu2O electrode was formed through electrostatic interaction of MXene and CTS with opposite charges, followed by the electrodeposition of Cu2O. Taking advantage of the synergistic function of MXene/CTS layers and Cu2O nanoparticles, this ternary electrode exhibits excellent sensing capabilities for glucose and cholesterol with preferable linear ranges that can cover the full concentration range in clinical diagnosis. For glucose sensing, the sensitivity was 60.295 µA·L/(mmol·cm2) with LOD being 52.4 µmol/L (SNR=3), while a sensitivity up to 215.71 µA·L/(mmol·cm2) and LOD low to 49.8 µmol/L (SNR=3) were achieved for cholesterol detection. Additionally, this biosensor possesses superior anti-interference ability and reproductivity, and thus exhibits great potential for genuine sample analysis. Accordingly, the as-prepared enzyme-free MXene/CTS/Cu2O electrode acts as a biomimetic electrocatalyst with excellent performance for analysis of multiple metabolites, and overcomes the disadvantages of an enzyme-based biosensor. This work has proposed a versatile strategy for designing and fabricating selfassembled nanocomposite materials with tuned structural and functional properties. It is a first attempt which could be easily integrated into portable electrochemical devices, facilitating effective routine monitoring of blood metabolites and paving the way for commercialization and point-of-care testing.
概要
目的
研制低成本、高精度的多种代谢物同时检测的生物传感器对医疗诊断具有重要意义。在本工作中,我们提出了一种基于MXene/壳聚糖(CTS)/Cu2O纳米复合材料的独立无酶电极,用于同时高精度测定葡萄糖和胆固醇。
创新点
1. 利用MXene、CTS和Cu2O的协同作用,通过电位分离,实现对葡萄糖和胆固醇的无酶同时检测;2. 优化检测范围,可用于检测人体血液样本。
方法
1. 通过MXene、CTS和Cu2O纳米材料的协同作用形成有效的界面结,促进反应过程中的电荷转移,进而提高与待测物质的接触面积;2. 分析电化学反应过程,构建电流信号与待测物浓度之间的关系,得到传感器的性能参数。
结论
1. MXene/CTS薄膜具有较高的比表面积,为离子的扩散提供了更多的通道,同时Cu2O纳米粒子可以提供丰富的金属活性边缘,促进了电荷转移,提高了反应活性。2. Cu2O纳米颗粒在胆固醇检测中发挥了重要作用,而同时作为导电基底和葡萄糖氧化剂的MXene,通过协同作用实现了在不同电位上同时无酶检测葡萄糖和胆固醇。3. 在优化的电位范围内(−0.80–0.40 V),该传感器对葡萄糖和胆固醇具有良好的线性响应,灵敏度分别为60.295和215.71 µA∙L/(mmol·cm2),而检出限分别为52.4和49.8 µmol/L。4. 通过对人血清样品的实时分析,验证了其良好的抗干扰能力和回收率(98.04%–102.94%),所以该传感器具有一定的临床应用前景。
References
Ahmad R, Khan M, Tripathy N, et al., 2020. Hydrothermally synthesized nickel oxide nanosheets for non-enzymatic electrochemical glucose detection. Journal of the Electrochemical Society, 167(10):107504. https://doi.org/10.1149/1945-7111/ab9757
Anasori B, Lukatskaya MR, Gogotsi Y, 2017. 2D metal carbides and nitrides (MXenes) for energy storage. Nature Reviews Materials, 2(2):16098. https://doi.org/10.1038/natrevmats.2016.98
Bairagi PK, Verma N, 2018. Electrochemically deposited dendritic poly (methyl orange) nanofilm on metal-carbonpolymer nanocomposite: a novel non-enzymatic electrochemical biosensor for cholesterol. Journal of Electroanalytical Chemistry, 814:134–143. https://doi.org/10.1016/j.jelechem.2018.02.011
Boota M, Pasini M, Galeotti F, et al., 2017. Interaction of polar and nonpolar polyfluorenes with layers of two-dimensional titanium carbide (MXene): intercalation and pseudocapacitance. Chemistry of Materials, 29(7): 2731–2738. https://doi.org/10.1021/acs.chemmater.6b03933
Dey RS, Raj CR, 2013. Redox-functionalized graphene oxide architecture for the development of amperometric biosensing platform. ACS Applied Materials & Interfaces, 5(11):4791–4798. https://doi.org/10.1021/am400280u
Dong XW, Zhang YD, Ding B, et al., 2018. Layer-by-layer self-assembled two-dimensional MXene/layered double hydroxide composites as cathode for alkaline hybrid batteries. Journal of Power Sources, 390:208–214. https://doi.org/10.1016/j.jpowsour.2018.04.058
Fan Y, Liu JT, Wang Y, et al., 2017. A wireless point-of-care testing system for the detection of neuron-specific enolase with microfluidic paper-based analytical devices. Biosensors and Bioelectronics, 95:60–66. https://doi.org/10.1016/j.bios.2017.04.003
Gao J, Huang WZ, Chen ZP, et al., 2019. Simultaneous detection of glucose, uric acid and cholesterol using flexible microneedle electrode array-based biosensor and multichannel portable electrochemical analyzer. Sensors and Actuators B: Chemical, 287:102–110. https://doi.org/10.1016/j.snb.2019.02.020
Grozdanov I, 1994. Electroless chemical deposition technique for Cu2O thin films. Materials Letters, 19(5–6):281–285. https://doi.org/10.1016/0167-577X(94)90171-6
Henry P, Thomas F, Benetos A, et al., 2002. Impaired fasting glucose, blood pressure and cardiovascular disease mortality. Hypertension, 40(4):458–463. https://doi.org/10.1161/01.HYP.0000032853.95690.26
Huang QL, An YR, Tang LL, et al., 2011. A dual enzymatic-biosensor for simultaneous determination of glucose and cholesterol in serum and peritoneal macrophages of diabetic mice: evaluation of the diabetes-accelerated atherosclerosis risk. Analytica Chimica Acta, 707(1–2):135–141. https://doi.org/10.1016/j.aca.2011.09.003
Jaime J, Rangel G, Muñoz-Bonilla A, et al., 2017. Magnetite as a platform material in the detection of glucose, ethanol and cholesterol. Sensors and Actuators B: Chemical, 238:693–701. https://doi.org/10.1016/j.snb.2016.07.059
Ji R, Wang LL, Wang GF, et al., 2014. Synthesize thickness copper (I) sulfide nanoplates on copper rod and it’s application as nonenzymatic cholesterol sensor. Electrochimica Acta, 130:239–244. https://doi.org/10.1016/j.electacta.2014.02.155
Khaliq N, Rasheed MA, Cha G, et al., 2020. Development of non-enzymatic cholesterol bio-sensor based on TiO2 nanotubes decorated with Cu2O nanoparticles. Sensors and Actuators B: Chemical, 302:127200. https://doi.org/10.1016/j.snb.2019.127200
Khazaei M, Arai M, Sasaki T, et al., 2013. Novel electronic and magnetic properties of two-dimensional transition metal carbides and nitrides. Advanced Functional Materials, 23(17):2185–2192. https://doi.org/10.1002/adfm.201202502
Lee JH, Shoeman DW, Kim SS, et al., 1997. The effect of superoxide anion in the production of seven major cholesterol oxidation products in aptoric and protic conditions. International Journal of Food Sciences and Nutrition, 48(2):151–159. https://doi.org/10.3109/09637489709006975
Li G, Liao JM, Hu GQ, et al., 2005. Study of carbon nanotube modified biosensor for monitoring total cholesterol in blood. Biosensors and Bioelectronics, 20(10): 2140–2144. https://doi.org/10.1016/j.bios.2004.09.005
Li X, Ren KB, Zhang M, et al., 2019. Cobalt functionalized MoS2/carbon nanotubes scaffold for enzyme-free glucose detection with extremely low detection limit. Sensors and Actuators B: Chemical, 293:122–128. https://doi.org/10.1016/j.snb.2019.04.137
Li ZJ, Qiao KJ, Shi WC, et al., 2016. Biosynthesis of poly (glycolate-co-lactate-co-3-hydroxybutyrate) from glucose by metabolically engineered Escherichia coli. Metabolic Engineering, 35:1–8. https://doi.org/10.1016/j.ymben.2016.01.004
Liang X, Garsuch A, Nazar LF, 2015. Sulfur cathodes based on conductive MXene nanosheets for high-performance lithium-sulfur batteries. Angewandte Chemie International Edition, 54(13):3907–3911. https://doi.org/10.1002/anie.201410174
Ling Z, Ren CE, Zhao MQ, et al., 2014. Flexible and conductive MXene films and nanocomposites with high capacitance. Proceedings of the National Academy of Sciences of the United States of America, 111(47): 16676–16681. https://doi.org/10.1073/pnas.1414215111
Lorencova L, Bertok T, Dosekova E, et al., 2017. Electrochemical performance of Ti3C2Tx MXene in aqueous media: towards ultrasensitive H2O2 sensing. Electrochimica Acta, 235:471–479. https://doi.org/10.1016/j.electacta.2017.03.073
Lu X, Tao L, Song DD, et al., 2018. Bimetallic Pd@Au nanorods based ultrasensitive acetylcholinesterase biosensor for determination of organophosphate pesticides. Sensors and Actuators B: Chemical, 255:2575–2581. https://doi.org/10.1016/j.snb.2017.09.063
Mashtalir O, Naguib M, Mochalin VN, et al., 2013. Intercalation and delamination of layered carbides and carbonitrides. Nature Communications, 4:1716. https://doi.org/10.1038/ncomms2664
Naguib M, Kurtoglu M, Presser V, et al., 2011. Two-dimensional nanocrystals produced by exfoliation of Ti3AlC2. Advanced Materials, 23(37):4248–4253. https://doi.org/10.1002/adma.201102306
Oh JK, Lee DI, Park JM, 2009. Biopolymer-based microgels/nanogels for drug delivery applications. Progress in Polymer Science, 34(12):1261–1282. https://doi.org/10.1016/j.progpolymsci.2009.08.001
Pagare PK, Torane AP, 2016. Band gap varied cuprous oxide (Cu2O) thin films as a tool for glucose sensing. Microchimica Acta, 183(11):2983–2989. https://doi.org/10.1007/s00604-016-1949-6
Patil SB, Dheeman DS, Al-Rawhani MA, et al., 2018. An integrated portable system for single chip simultaneous measurement of multiple disease associated metabolites. Biosensors and Bioelectronics, 122:88–94. https://doi.org/10.1016/j.bios.2018.09.013
Phetsang S, Jakmunee J, Mungkornasawakul P, et al., 2019. Sensitive amperometric biosensors for detection of glucose and cholesterol using a platinum/reduced graphene oxide/poly(3-aminobenzoic acid) film-modified screen-printed carbon electrode. Bioelectrochemistry, 127: 125–135. https://doi.org/10.1016/j.bioelechem.2019.01.008
Pletcher D, 1984. Electrocatalysis: present and future. Journal of Applie Electrochemistry, 14(4):403–415. https://doi.org/10.1007/BF00610805
Raj V, Johnson T, Joseph K, 2014. Cholesterol aided etching of tomatine gold nanoparticles: a non-enzymatic blood cholesterol monitor. Biosensors an Bioelectronics, 60: 191–194. https://doi.org/10.1016/j.bios.2014.03.062
Rengaraj A, Haldorai Y, Kwak CH, et al., 2015. Electrodeposition of flower-like nickel oxide on CVD-grown graphene to develop an electrochemical non-enzymatic biosensor. Journal of Materials Chemistry B, 3(30): 6301–6309. https://doi.org/10.1039/c5tb00908a
Shih WC, Yang MC, Lin MS, 2009. Development of disposable lipid biosensor for the determination of total cholesterol. Biosensors an Bioelectronics, 24(6):1679–1684. https://doi.org/10.1016/j.bios.2008.08.055
Shumyantseva V, Deluca G, Bulko T, et al., 2004. Cholesterol amperometric biosensor based on cytochrome P450scc. Biosensors an Bioelectronics, 19(9):971–976. https://doi.org/10.1016/j.bios.2003.09.001
Sinha A, Dhanjai, Zhao HM, et al., 2018. MXene: an emerging material for sensing and biosensing. TrAC Trends in Analytical Chemistry, 105:424–435. https://doi.org/10.1016/j.trac.2018.05.021
Song PA, Wang H, 2020. High-performance polymeric materials through hydrogen-bond cross-linking. Advanced Materials, 32(18):1901244. https://doi.org/10.1002/adma.201901244
Wang XF, Kajiyama S, Iinuma H, et al., 2015. Pseudocapacitance of MXene nanosheets for high-power sodium-ion hybrid capacitors. Nature Communications, 6:6544. https://doi.org/10.1038/ncomms7544
Wang Y, Dou H, Wang J, et al., 2016. Three-dimensional porous MXene/layered double hydroxide composite for high performance supercapacitors. Journal of Power Sources, 327:221–228. https://doi.org/10.1016/j.jpowsour.2016.07.062
Wu Q, He L, Jiang ZW, et al., 2019. CuO nanoparticles derived from metal-organic gel with excellent electrocatalytic and peroxidase-mimicking activities for glucose and cholesterol detection. Biosensors an Bioelectronics, 145:111704. https://doi.org/10.1016/j.bios.2019.111704
Yang J, Lee H, Cho M, et al., 2012. Nonenzymatic cholesterol sensor based on spontaneous deposition of platinum nanoparticles on layer-by-layer assembled CNT thin film. Sensors an Actuators B: Chemical, 171–172:374–379. https://doi.org/10.1016/j.snb.2012.04.070
Acknowledgments
This work is supported by the National Key Scientific Instrument and Equipment Development Project of China (No. 51627808), the National Natural Science Foundation of China (No. 51605088), the Natural Science Foundation of Jiangsu Province (Nos. BK20170667 and BK20201278), the Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. SJCX20_0026), and the Zhishan Youth Scholar Program of Southeast University (SEU), China.
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Tao HU designed the research. Man ZHANG processed the corresponding data. Hui DONG and Tong LI participated in the methodology and discussion. **ao-bei ZANG provided the original technique of experiments and reviewing. Man ZHANG wrote the first draft of the manuscript. Zhong-hua NI and **ao LI helped to organize the manuscript. Man ZHANG and **ao LI revised and edited the final version.
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Tao HU, Man ZHANG, Hui DONG, Tong LI, **ao-bei ZANG, **ao LI, and Zhong-hua NI declare that they have no conflict of interest.
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All procedures were in accordance with the ethical standards of the Responsible Committee on Human Experimentation (Institute of Process Engineering, Chinese Academy of Sciences, China) and with the Helsinki Declaration of 1975, as revised in 2008(5). Informed consent was obtained from all patients for being included in the study.
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Free-standing MXene/chitosan/Cu2O electrode: an enzyme-free and efficient biosensor for simultaneous determination of glucose and cholesterol
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Hu, T., Zhang, M., Dong, H. et al. Free-standing MXene/chitosan/Cu2O electrode: an enzyme-free and efficient biosensor for simultaneous determination of glucose and cholesterol. J. Zhejiang Univ. Sci. A 23, 579–586 (2022). https://doi.org/10.1631/jzus.A2100584
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DOI: https://doi.org/10.1631/jzus.A2100584