Zinc oxide nanocomb biosensor for glucose detection

J. X. Wang, X. W. Sun, A. Wei, Y. Lei, X. P. Cai et al. Citation: Appl. Phys. Lett. 88, 233106 (2006); doi: 10.1063/1.2210078 View online: http://dx.doi.org/10.1063/1.2210078 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v88/i23 Published by the American Institute of Physics.

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JEM-2010F .3. L. electronic mail: exwsun@ntu. The detection limit measured was 0.02 mM. W.APPLIED PHYSICS LETTERS 88.12. Hitachi S-5200 . argon and oxygen were introduced through the tube at a flow rate of 100 SCCM denotes cubic centimeter per minute at STP and 1 SCCM. The pressure of the tube was maintained at about 8 10−1 Torr by a rotary pump. The electrochemical experiment was performed at room temperature utilizing an electrochemical workstation Bio-logic SA VMP2 with a conventional three-electrode configuration. These M results demonstrate that zinc oxide nanostructures have potential applications in biosensors.sg nace.1063/1. X.6 nanorings. X. a 5 l 0. biosensors made of 1D ZnO nanostructures are rare. Redistribution subject to AIP license or copyright.99% and graphite powder were mixed thoroughly and loaded into a small quartz boat. Singapore Y. Firstly. Following the evaporation of water.12 In this letter. and dried by high purity nitrogen gas. electrochemical activity. 233106 2006 Zinc oxide nanocomb biosensor for glucose detection J. After the reaction was terminated. and selected area electron diffraction SAED were employed in characterization. 0. respectively. Recently. and high electron communication features.5% weight Nafion solution was dropped onto the GOx / ZnO / gold electrode and dried overnight at 4 ° C to form a film. The as-prepared ZnO/Gold electrode was then wetted by 0. Singapore 639798. the electrode was polished with 1. 233106-1 Downloaded 28 Dec 2011 to 202. Nanyang Technological University. subsequently. Nanyang Technological University.01M PBS.2 One-dimensional 1D zinc oxide nanostructures have attracted great interest in the past few years.0 ml. and pyroelectric properties. we shall report a biosensor for glucose detection using ZnO nanocombs fabricated in large quantity using a vapor phase transport method. x-ray diffraction XRD. Singapore Received 5 December 2005. The enzyme used for glucose detection.0. Lei. Scanning electron microscopy SEM. was immobilized on ZnO nanocombs first in our design. sensors. high purity ZnO 99.65. Cai. The immobilized GOx shows high affinity for glucose. A glucose biosensor was constructed using these nanocombs as supporting materials for glucose oxidase GOx loading. and actuators due to its semiconducting. Nanyang Avenue.a and A. Li School of Chemical and Biomedical Engineering. Dong School of Materials Science and Engineering. M.4.0 mg GOx in 1. To fabricate the glucose biosensor. A 5 l GOx 40 U / mg solution was dropped onto the surface of the ZnO/Gold electrode. nontoxicity. they are promising for biosensor applications. ZnO is a biocompatible material with a high isoelectric point IEP of about 9. It has profound applications in optics.5 nanotubes.8 gas sensor.edu.aip. high-resolution transmission electron microscopy HRTEM. and the ZnO nanocomb biosensor showed high sensitivity without the presence of an electron mediator.7 etc. The Nafion/ GOx / ZnO / gold electrodes were stored in PBS and kept at 4 ° C in a refrigerator when not in use. chemical stability. On the other hand.3. the as-prepared ZnO nanocombs were firstly transferred from the silicon substrate to a standard gold electrode commonly used in electrochemistry.12. piezoelectric.33 A / cm2 mM for glucose detection and high affinity of GOx to glucose the apparent Michaelis-Menten constant Kapp = 2. Graphite powder was used to reduce ZnO at this temperature so as to generate Zn and ZnOx x 1 vapor.01M phosphate buffer solution PBS with pH = 7. which is critical to attach GOx / ZnO nanocombs tightly on the surface of the gold electrode. see http://apl.00 88. Siemens D5005 with Cu K radiation. Wang. The zinc oxide nanocomb glucose biosensor showed a high sensitivity 15. Nanyang Avenue.1. as the protein immobilization is primarily driven by electrostatic interaction. ZnO nanodevices. Singapore 639798. ZnO nanostructures have unique advantages including the high specific surface area. However.5. Sun.10 and field emitter. such as room temperature laser.4 Extensive efforts have been made to synthesize ZnO nanostructures. At the same time. X. Hence.103. The quartz tube was then heated to 900 ° C and kept for 30 min. glucose oxidase GOx . © 2006 American Institute of Physics.3 nanobelts. because nanostructural morphology is one of the important factors determining the properties. These devices show higher performance compared to those fabricated from bulk and thin film forms of ZnO. accepted 12 April 2006. Nanyang Technological University. The ZnO nanocombs were prepared by a vapor phase transport method. Prior to the experiment. Singapore Z.19 mM . Nanyang Avenue. P. such as nanowires. the furnace was cooled down to room temperature and the white products on silicon substrate were collected for characterization and fabrication of glucose sensor. optoelectronics.. which make it suitable for absorption of proteins with low IEPs. The GOx solution was prepared by dissolving 5.9 transistor. 0.13 Moreover. and C. published online 6 June 2006 Single crystal zinc oxide nanocombs were synthesized in bulk quantity by vapor phase transport. The modified gold electrode with a diameter of 1 mm was used as the working electrode.11 have been studied extensively. Singapore 639798. DOI: 10.2210078 Zinc oxide ZnO is an important member in II-VI group semiconductors. Then the small quartz boat was pushed into a large quartz tube mounted horizontally inside a fura Author to whom correspondence should be addressed.org/about/rights_and_permissions . Wei School of Electrical and Electronic Engineering. A slice of silicon wafer was placed downstream from the quartz boat as the collector. and © 2006 American Institute of Physics 0003-6951/2006/88 23 /233106/3/$23.

1. These two peaks should be related to oxidation and reduction of ZnO itself. which match well the standard XRD data file JCPDS 792205 . Phys. This peak can be attributed to H2O2 generated during glucose oxidation by GOx. It can be seen that there is an increase in current from 0. corresponds to the interspacing ¯ of 0001 and 0111 planes of wurtzite ZnO. Lett. Cyclic voltammograms CV of Nafion/gold electrode and Nafion/ZnO/gold electrode are shown in Fig. Figure 1 e shows the TEM image of an individual ZnO nanocomb. were detected. Figure 1 f is a HRTEM image taken near the edge along the stem of the nanocomb in Fig. Figure 2 b shows the CV curves of Nafion/ GOx / ZnO / gold electrode in PBS with 0 and 3 mM glucose. where all the diffraction peaks can be indexed to the hexagonal wurtzite phase of ZnO with lattice constants of a = 0. Inset is the CV curves recorded at various scan rates of 20. the length of the main stems reaches several tens of micrometers. respectively. 1 a . and 100 mV/ s sequentially increasing along the arrow direction of Nafion/ GOx / ZnO / gold electrode in the same buffer solution containing 3 mM glucose.05 m aluminum slurries sequentially. 233106 2006 FIG. The distance between two adjacent nanorods is about 500 nm. 40. c medium.520 nm. 80. Appl. No other crystalline forms. is ¯1 indexed to be 21¯ 0 The performance of the GOx / ZnO biosensor was measured at room temperature. The branching nanorods grow on one side of nanoribbon with a diameter of about 200 nm.aip. The corresponding SAED pattern is shown in the inset in Fig. FIG.103. and high magnifications. Downloaded 28 Dec 2011 to 202.65. e TEM image of a ZnO nanocomb and f HRTEM image and the corresponding SAED pattern insert of a ZnO nanocomb. respectively. 1 e .4 PBS buffer at scan rate of 50 mV/ s. 1 f . 40. respectively. a XRD pattern of ZnO nanocombs and SEM images of ZnO nanocombs with b low. Redistribution subject to AIP license or copyright.16 The inset shows the CV curves of Nafion/ GOx / ZnO / gold electrode in PBS containing 3 mM glucose obtained at various scan rates of 20. 0. 2. b Cyclic voltammograms of Nafion/ GOx / ZnO / gold electrode in the same buffer solution in the absence red and presence blue of 3 mM glucose. The origin of these two peaks will be studied in detail in a separate paper. see http://apl. The detailed structure of individual ZnO nanocomb is studied by SAED and TEM.4 to 0. The HRTEM image confirms the good quality of the single crystal ZnO nanocombs.14 the stems of nanocombs are ribbons with a thickness of about 50 nm. indicating different thicknesses for the stem and the nanorods. medium.6 V on the CV curve for Nafion/ GOx / ZnO / gold electrode in PBS with 3 mM glucose. It can be seen that the product consists of numerous comblike nanostructures with single morphology nanocomb and uniform size in the area examined. 0.233106-2 Wang et al. 2 a .1 V were observed in the CV curve of Nafion/ZnO/gold electrode. Unlike the nanocombs reported previously. The XRD pattern of the as-prepared product by vapor phase transport is shown in Fig.6 V in PBS with 3 mM glucose compared to PBS without glucose. as reported previously. 60.246 nm. and then sonicated in de-ionized water. The spacing of the lattice planes. two peaks at 0.3 and 0.325 nm and c = 0. Different from pure Nafion/gold electrode. 88. respectively. which is vertical to the ribbon stem of the nanocomb.520 and 0. 60. showing a typical diffusioncontrolled electrochemical behavior. such as Zn or other Zn compounds. and d high magnifications. indicating the response of Nafion/ GOx / ZnO / gold electrode to glucose. 80.12. respectively. A weak shoulder peak appeared at about 0. It can be found that the peak current is proportional to the square root of scan rate.01M. Figures 1 b –1 d show typical SEM images of the ZnO product in low.15. The ribbon stem and the nanorods of ZnO nanocomb show different contrast. The direction of electron beam. Color online a Cyclic voltammograms of Nafion/gold electrode red and Nafion/ZnO/gold electrode blue in 0. and the width of the stems decreases gradually along the growth direction to form sharp tips. and 100 mV s−1 sequentially increase along the arrow direction in the inset .org/about/rights_and_permissions . The growth direction of the ¯ stem and branching nanorods can be determined to be 0110 and 0001 . pH 7. respectively.

Heo. 3 Y. Redistribution subject to AIP license or copyright. Appl. J. L. Mater. Chim. 72. Q. see http://apl. D. The corresponding calibration curve solid square of the glucose biosensor is shown in Fig. Deng. L. Fan and J.22 indicating the high affinity of the ZnO glucose biosensor. The Lineweaver-Burk plot open circle of 1 / i vs 1 / C is shown in Fig. Xu. Ivill. Biosens. Electroanalysis 13. 5. Chara. Lett. and S. 1981 2004 .8 V vs Ag/ AgCl reference was applied on the working electrode in the measurement.01M. Q. M. Ma. 83. Gao. as a traditional transparent conductor. Y. Phys. and M. are gratefully acknowledged. Y. Yang. 999 2003 . R. Chim. Shen. Phys. P. Anal. 401 2003 . Lett. Niu. Yang. and N.103. 13. 12 F. L. 13 Z. Dong. Acta 525. L. 1561 2005 . Z. W.02 to 4. F. X. J. Zuo. B. Lett. Lu. X. at working buffer pH. Sun. D. C. H. Q. Appl. A. Wang. W. Liu. the ZnO nanocombs with ribbonlike stem possess high specific surface area and good biocompatible properties. Zhao. Wang. Phys. and H. Lao. Appl. It could be calculated according to the Lineweaver-Burk equation 1 / i = Kapp / imax 1 / C + 1 / imax. Bioelectrochemistry 67. 3806 2003 . Yang. Z. L. Anal. According to the Lineweaver-Burk plot. b The calibration curve solid square of ZnO / GOx biosensor and the Lineweaver-Burk plot open circle . a Amperometric responses of Nafion/ GOx / ZnO / gold electrodes with the successive addition of 20 M glucose to the 0. the response current increases and saturates at a high glucose concentration of 13 mM. Ai. Xu. Z. Y. J. J. Sun. J. 85. H. Phys. and Z. Zhu. 87. M. M. Appl. F. 185502 2003 . and A. nanocombs are distributed irregularly on the surface of the gold electrode forming a three-dimensional porous network. D. Yu. Chem. The results showed that the ZnO nanocombs formed an attractive matrix for GOx immobilization. Acta 519. R. 67 1998 . The sensitivity is significantly higher than that of glucose biosensor reported previously. Anal. ZnO nanocombs are positively charged whereas GOx is negatively charged. Kong. Q. the ZnO Downloaded 28 Dec 2011 to 202. 86. 213 2004 . Z. Li.233106-3 Wang et al. Mai. Z. X. These reasons contribute to the high sensitivity and high affinity of the biosensor constructed by ZnO nanocombs. 3. and J.20. Feng. Castillo. Bioelectron. L. 155 2004 . 1 Figure 3 a displays a typical amperometric response of the ZnO biosensor after addition of successive aliquots of 20 M glucose in PBS under stirring. Xian. 86. 1700 2005 . thus enhancing the direct electron transfer between the active sites of enzyme and the electrode. E. where i is the current.aip. It can be seen from the plot that the biosensor shows a rapid and sensitive response to the change of glucose concentration. 3 b . F. and R. Lu. Zhang. Lu. and R. The sponsorships from Research Grant Manpower Fund RGM 21/04 of Nanyang Technological University and Science and Engineering Research Council grant 0421010010 from Agency for Science. P. 52. 14 Z. Zhang. Chen. Sun. J. Chen and S.33 A / cm2 mM and a limit of detection LOD of 0. 34 2004 . C. Following the increase of the glucose concentration. B. Kwok.19 mM. Lett. W. Jpn. Meng. B. M. Li. Yang. Sun and H. and J. Chem. Electrochim. M. Zhu. Pan. Yu. Liu. Anal. and K. 1196 1980 . H. the Kapp is calculated to be 2. 22 Q. Zhou. L. Phys. Technology and Research A*STAR . L. Rajagopalan. and Z. Q. Vidal. The straight line is the linear fit to the calibration curve. Y. L. S. Luo. 1947 2001 . 8 X. W. Kong. Jin. Wan.20 Au nanoparticle. Y. Zhang. G. H. D. single crystalline ZnO nanostructures have good conductivity. Yu. Garcia. Lett. L. Sun.19 The apparent Michaelis-Menten constant Kapp is generally used to evaluate M the biological activity of immobilized enzyme. Yu. Steiner. and C is the glucose concentration.4 PBS buffer under stirring. P. 19 J. 18 J. W.. pH 7. The linear range of the calibration curve is from 0. Shen. S. 1065 2005 . 2011 2000 . G. which provide many transport channels in nanoscale. S. Acta 49. Electroanalysis 17. and fast response for glucose detection. 15 2005 . W. X. 093110 2005 . Biosens. Liu. G.65. Zhao. H. G. N. and Z. Ye. Additionally. L. high sensitivity. Z. Phys. Yu. Zhang. X. H. Fan and J. Yamamoto. M. X. Z. 88. F. 3878 2004 . Yang. 3 b . X. This simple method of fabricating ZnO / GOx biosensor can also be extended to immobilize other enzymes and other bioactive molecules on various 1D metal oxide nanostructures.12.5 mM correction coefficient R = 0. Ding. Liu. Today 7. Appl. Different enzymes immobilized on the porous metal oxide matrix have been reported. Appl. F. Chisholm. Phillipp. Wang. Y. H. W. Dong. 11 C. A potential of +0. Dai. we reported a biosensor by immobilized GOx on the single crystalline ZnO nanocombs for glucose detection. 7 P. Norton. B. 18. Liu. and C. J. R. Hughes. 10 Z. W. Nanosci. Heller. S. and F. Bioelectron. W. Pearton.22–24 In our case. 91. J. Lett. In summary. Y. Y. Hu.18 and the LOD is lower compared to the glucose sensor based on titanium dioxide sol-gel matrix reported previously. Phys. J. Metal oxides have unique advantages in immobilized enzyme. Moreover. 76. 17 T.21 and nanopore-TiO2 film electrodes. 21 S. 66. Part 2 42. imax is M the maximum current. S. Kamln and G. X. Li. and Y. W. T. Anal. which provides a favorable microenvironment for GOx loading with large quantity. Sun. Science 309. L. H. Y. J. Z. Liu. Appl. Q. W. 2451 1994 . Wang. 123510 2005 . which exhibits a high affinity. which is lower than M previously reported data using native enzyme GOx. Zhang. L. Y. 4707 2000 . Q. Lett. L. 413 2001 . M. The response time for the electrode is less than 10 s. Y. 16 Y. L. 5 Z. L1229 2003 . 24 Z.org/about/rights_and_permissions . Phys. F. Rev. S. Xu. Q. L. Science 291. Xu. 23 Y. M. S. J. 19.999 with a sensitivity of 15.17. Wilson. G. G. 408 1999 . 6 W. He. Nanotechnol.02 mM. Bioelectron. D. 4 C. Ju. G. Singapore. and J. C. Yang. 233106 2006 FIG. 9 Z. Biosens. indicating a good electrocatalytic property of Nafion/ GOx / ZnO / gold electrode. 15 X. A. Meanwhile. which favors the electrostatic attraction of GOx and ZnO nanocombs. and T. Yuen. F. Xu and X. and form versatile electrodes for biosensor studies. P. J. 2 X. Y. Phys. 20 R. Chem. C. Appl. H. Yu. Wang.

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