摘要
该文采用涂覆的方式构建了一种用于灵敏检测抗坏血酸(AA)的电化学传感器。先将多壁碳纳米管(MWCNTs)和氧化石墨烯(GO)混合悬浮液修饰在玻碳电极(GCE)表面,修饰的GO可有效防止MWCNTs聚集,再将具有良好电催化性能的金铂核壳纳米粒子(Au@Pt NPs)修饰在GO/MWCNTs电极上,层层组装构建形成GO/MWCNTs/Au@Pt NPs/GCE三维新型抗坏血酸电化学传感器。该修饰电极在磷酸缓冲溶液中对AA显示了较宽的线性范围和极低的检出限,氧化峰电流与AA浓度在0.005~0.5μmol/L和0.5~1 000μmol/L范围内呈良好的线性关系,相关系数均为0.999,检出限(S/N=3)为4×10~(-9) mol/L,稀释人体血清样品的加标浓度为0.01、0.1、10μmol/L,回收率为90.9%~108%,相对标准偏差(RSD,n=3)为1.2%~2.8%。该修饰电极对AA具有良好的选择性,可有效排除多巴胺、尿酸、葡萄糖等生物小分子的干扰。方法简单、高效、灵敏,可用于临床实际检测。
An ultra-sensitive electrochemical sensor for detection of ascorbic acid(AA)was constructed by drop-casting method with electrochemical sensing interface.Multi-walled carbon nanotubes(MWCNTs) and graphene oxide(GO) preventing the aggregation of MWCNTs were first added to the surface of glassy carbon electrode(GCE) to form a film.Subsequently,gold platinum core-shell nanoparticles(Au@Pt NPs) were immobilized on the surface of GO/MWCNTs/GCE through layer by layer assembly,forming a GO/MWCNTs/Au@Pt NPs/GCE 3 D composite film.The as-prepared electrode was used in the electrochemical detection of AA in phosphate buffer solution by differential pulse voltammetry(DPV) with a wide linear range and very low detection limit.There were good linear relationships between the redox peak current and AA in ranges of 0.005-0.5 μmol/L and 0.5-1 000 μmol/L,respectively,with their correlation coefficients of 0.999 and their detection limits(S/N=3) of 4.0×10~(-9) mol/L.The recoveries for the real human serum sample at three spiked levels of 0.01,0.1 and 10 μmol/L were in the range of 90.9%-108%,with the relative standard deviations(RSD,n=3)of 1.2%-2.8%.With a good selectivity toward AA,the sensor could effectively eliminate any interferences from small biological molecules such as dopamine,uric acid and glucose,etc.Therefore,the sensor is simple,efficient and sensitive,and could be widely used in clinical detection.
引文
[1] Raveendran J,Krishnan R G,Nair B G,Babu T G S.Microchim.Acta,2017,184(3):1-7.
[2] Hei Y W,Li X Q,Zhou X,Liu J J,Hassan M,Zhang S Y,Yang Y,Bo X J,Wang H L,Zhou M.Anal.Chim.Acta,2018,1029:15-23.
[3] Numan A,Shahid M M,Omar F S,Ramesh K,Ramesh S.Sens.Actuators B,2017,238:1043-1051.
[4] Lin X Q,Gong J M.Anal.Chim.Acta,2004,507(2):255-261.
[5] Bai Z Y,Zhou C L,Xu H B,Wang G N,Pang H J,Ma H Y.Sens.Actuators B,2017,243:361-371.
[6] Tedim J,Gon?alves F,Pereira M F R,Figueiredo J L,Moura C,Freire C,Hillman A R.Electrochim.Acta,2008,53(23):6722-6731.
[7] Cumings J,Zettl A.Science,2000,289(5479):602-604.
[8] Treacy M M J,Ebbesen T W,Gibson J M.Nature,1996,381(6584):678-680.
[9] Noked M,Okashy S,Zimrin T,Aurbach D.Angew.Chem.Int.Ed.,2012,51(7):1568-1571.
[10] You B,Jiang J H,Fan S J.ACS Appl.Mater.Interfaces,2014,6(17):15302-15308.
[11] Kim J,Cote L J,Kim F,Yuan W,Shull K R,Huang J X.J.Am.Chem.Soc.,2010,132(23):8180-8186.
[12] Pei S F,Cheng H M.Carbon,2012,50(9):3210-3228.
[13] Chen W F,Yan L F,Bangal P R.Carbon,2010,48(4):1146-1152.
[14] Fan Z J,Wang K,Wei T,Yan J,Song L,Shao B.Carbon,2010,48(5):1686-1689.
[15] Acik M,Lee G,Mattevi C,Pirkle A,Wallace R M,Chhowalla M,Cho K,Chabal Y.J.Phys.Chem.C,2015,115(40):19761-19781.
[16] Gao F,Cai X L,Wang X,Gao C,Liu S L,Gao F,Wang Q X.Sens.Actuators B,2013,186(6):380-387.
[17] Weaver C L,Li H X,Luo X L,Cui X T.J.Phys.Chem.B,2014,2(32):5209-5219.
[18] Zhang Y H,Lei W,Xu Y J,Xia X F,Hao Q L.Nanomaterials,2016,6(10):178.
[19] Lin C Y,Lai Y H,Balamurugan A,Vittal R,Lin C W,Ho K C.Talanta,2010,82(1):340-347.
[20] Xia B Y,Wu H B,Wang X,Lou X W.Angew.Chem.Int.Ed.,2013,52(47):12337-12340.
[21] Sun X,Li D,Ding Y,Zhu W,Guo S,Wang Z L,Sun S.J.Am.Chem.Soc.,2014,136(15):7734-7739.
[22] Xia B Y,Wu H B,Yan Y,Lou X W,Wang X.J.Am.Chem.Soc.,2013,135(25):9480-9485.
[23] Wang B,Chen Y F,Wu Y Y,Weng B,Liu Y S,Lu Z S,Li C M,Yu C.Biosens.Bioelectron.,2016,78(3):4023-4030.
[24] Ning X,Zhou B B,Huang N B,Jiang M S,Zhang J B,Lin L.Biosens.Bioelectron.,2016,85:625-632.
[25] Priyadarshini E,Pradhan N.Sens.Actuators B,2017,238:888-902.
[26] Yu H,Jian X,Jin J,Wang F,Wang Y,Qi G C.J.Electroanal.Chem.,2013,700(7):47-53.
[27] Mani V,Chen S M,Lou B S.Int.J.Electrochem.Sci.,2013,8(10):11641-11660.
[28] Hummer W S,Offeman R E.J.Am.Chem.Soc.,1958,80:1339.
[29] Xia H B,Xiahou Y J,Zhang P N,Ding W C,Wang D Y.Langmuir,2016,32(23):5870-5880.
[30] Li Y J,Ding W C,Li M R,Xia H B,Wang D Y,Tao X T.J.Mater.Chem.A,2014,3(1):368-376.
[31] Xu Y Y,Dong Y N,Shi J,Xu M L,Zhang Z F,Yang X K.Catal.Commun.,2011,13(1):54-58.
[32] Li C C,Zhang W Y,Ang H X,Yu H,Xia B Y,Wang X,Yang Y H,Zhao Y,Hng H,Yan Q Y.J.Mater.Chem.A,2014,2(27):10676-10681.
[33] Keeley G P,O'Neill A,Mcevoy N,Peltekis N,Coleman J N,Duesberg G S.J.Mater.Chem.,2010,20(36):7864-7869.
[34] Pakapongpan S,Mensing J P,Phokharatkul D,Lomas T,Tuantranont A.Electrochim.Acta,2014,133:294-301.
[35] Zhang X,Yu S,He W Y,Uyama H,Xie Q J,Zhang L,Yang F C.Biosens.Bioelectron.,2014,55:446-451.
[36] Das T R,Jena S K,Madhuri R,Sharma P K.Appl.Surf.Sci.,2018,449:304-313.
[37] Chauhan N,Narang J,Pundir C S.Analyst,2011,136(9):1938-1945.
[38] Thangamuthu R,Senthil K S M,Chandrasekara K.Sens.Actuators.B,2007,120(2):745-753.
[39] Zhang H F,Huang F L,Xu S L,Xia Y,Huang W,Li Z L.Electrochem.Commun.,2013,30:46-50.
[40] Shi W T,Liu C X,Song Y L,Lin N S,Zhou S,Cai X X.Biosens.Bioelectron.,2012,38(1):100-106.
[41] Liu L,Zhai J F,Zhu C Z,Han L,Ren W,Dong S J.Anal.Chim.Acta,2017,981:34-40.