Abstract
In this study, two important biomarkers, namely glucose and uric acid, were detected in different biological fluids using a highly sensitive and selective chitosan-/nano-based electrochemical microfluidic paper-based analytical device (µPAD). A graphite/chitosan/polyethylene glycol (PEG) mixture was used as bare working electrode and counter electrode with silver ink being used as quasi-reference electrode. Graphene, multiwall carbon nanotubes, and Fe3O4 nanoparticles were used to improve sensitivity as well as selectivity of the working electrodes. The developed chitosan-/nano-based microfluidic analytical system showed apparent redox peaks, and all the three types of nanomaterials improved the performance of the bare graphite/chitosan/PEG electrode with the Fe3O4-modified electrode exhibiting the sharpest signals with the highest selectivity. The linear ranges of glucose and uric acid were 0.01–30 mM and 0.05–15 mM, respectively, where the limits of detection (LOD) were 5 µM and 20 µM for glucose and uric acid, respectively. In comparison with most of previous data reported on μPADs and due to high surface area/volume ratio of NPs and faster electron transfer promoted by chitosan and NPs, the better LODs were found in the current study. The fast, efficient, and low-cost µPADs were successfully applied to highly sensitive and selective detection of glucose and uric acid in serum and urine samples and noninvasive glucose detection in tear samples.
Graphic abstract
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Adkins J, Boehle K, Henry C (2015) Electrochemical paper-based microfluidic devices. Electrophoresis 36:1811–1824. https://doi.org/10.1002/elps.201500084
Ahmadi SH, Davar P, Manbohi A (2016) Adsorptive removal of reactive orange 122 from aqueous solutions by ionic liquid coated Fe3O4 magnetic nanoparticles as an efficient adsorbent. Iran J Chem Chem Eng 35:63–73. http://www.ijcce.ac.ir/article_18809_12c4a39f4ab80f0ee6f1ac883cb4a592.pdf
Ahmed MU, Hossain MM, Tamiya E (2008) Electrochemical biosensors for medical and food applications. Electroanalysis 20:616–626. https://doi.org/10.1002/elan.200704121
Akyazi T, Basabe-Desmonts L, Benito-Lopez F (2018) Review on microfluidic paper-based analytical devices towards commercialisation. Anal Chim Acta 1001:1–17. https://doi.org/10.1016/j.aca.2017.11.010
Baca J, Taormina C, Feingold E, Finegold D, Grabowski J, Asher S (2007) Mass spectral determination of fasting tear glucose concentrations in nondiabetic volunteers. Clin Chem 53:1370–1372. https://doi.org/10.1373/clinchem.2006.078543
Bandodkar A, Jia W, Ramírez J, Wang J (2015) Biocompatible enzymatic roller pens for direct writing of biocatalytic materials: “do-it-yourself” electrochemical biosensors. Adv Healthc Mater 4:1215–1224. https://doi.org/10.1002/adhm.201400808
Batchelor-McAuley C, Kätelhön E, Barnes E, Compton R, Laborda E, Molina A (2015) Recent advances in voltammetry. ChemistryOpen 4:224–260. https://doi.org/10.1002/open.201500042
Cánovas R, Parrilla M, Blondeau P, Andrade F (2017) A novel wireless paper-based potentiometric platform for monitoring glucose in blood. Lab Chip 17:2500–2507. https://doi.org/10.1039/C7LC00339K
Cate D, Adkins J, Mettakoonpitak J, Henry C (2015) Recent developments in paper-based microfluidic devices. Anal Chem 87:19–41. https://doi.org/10.1021/ac503968p
Cha KH, Jensen GC, Balijepalli AS, Cohan BE, Meyerhoff ME (2014) Evaluation of commercial glucometer test strips for potential measurement of glucose in tears. Anal Chem 86:1902–1908. https://doi.org/10.1021/ac4040168
Chen X, Chen J, Wang F, Xiang X, Luo M, Ji X, He Z (2012) Determination of glucose and uric acid with bienzyme colorimetry on microfluidic paper-based analysis devices. Biosens Bioelectron 35:363–368. https://doi.org/10.1016/j.bios.2012.03.018
Chen S et al (2013) Carbon nanodots as a matrix for the analysis of low-molecular-weight molecules in both positive- and negative-ion matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and quantification of glucose and uric acid in real samples. Anal Chem 85:6646–6652. https://doi.org/10.1021/ac401601r
Chen X, Wu G, Cai Z, Oyama M, Chen X (2014) Advances in enzyme-free electrochemical sensors for hydrogen peroxide, glucose, and uric acid. Microchim Acta 181:689–705. https://doi.org/10.1007/s00604-013-1098-0
Delaney JL, Hogan CF, Tian J, Shen W (2011) Electrogenerated chemiluminescence detection in paper-based microfluidic sensors. Anal Chem 83:1300–1306. https://doi.org/10.1021/ac102392t
Doughan S, Uddayasankar U, Peri A, Krull UJ (2017) A paper-based multiplexed resonance energy transfer nucleic acid hybridization assay using a single form of upconversion nanoparticle as donor and three quantum dots as acceptors. Anal Chim Acta 962:88–96. https://doi.org/10.1016/j.aca.2017.01.025
Dungchai W, Chailapakul O, Henry CS (2009) Electrochemical detection for paper-based microfluidics. Anal Chem 81:5821–5826
Ensafi AA, Taei M, Khayamian T (2010) Simultaneous determination of ascorbic acid, dopamine, and uric acid by differential pulse voltammetry using tiron modified glassy carbon electrode. Int J Electrochem Sci 5:116–130
Eshghi A, Kheirmand M (2018) Surface modification of glassy carbon electrode by Ni–Cu nanoparticles as a competitive electrode for ethanol electro-oxidation. Iran J Chem Chem Eng 37:1–8
Evans E, Gabriel EFM, Benavidez TE, Coltro WKT, Garcia CD (2014) Modification of microfluidic paper-based devices with silica nanoparticles. Analyst 139:5560–5567. https://doi.org/10.1039/C4AN01147C
Ferreira I, Ferreira M (1997) Simultaneous determination of sugars, uric and orotic acids in infant formulae by HPLC-UV/RI. J Liq Chromatogr Relat Technol 20:3419–3429. https://doi.org/10.1080/10826079708005841
Figueredo F, Garcia P, Cortón E, Coltro WKT (2016) Enhanced analytical performance of paper microfluidic devices by using Fe3O4 nanoparticles, MWCNT, and graphene oxide. ACS Appl Mater Interfaces 8:11–15. https://doi.org/10.1021/acsami.5b10027
Frebel H, Chemnitius GC, Cammann K, Kakerow R, Rospert M, Mokwa W (1997) Multianalyte sensor for the simultaneous determination of glucose, l-lactate and uric acid based on a microelectrode array. Sens Actuators B Chem 43:87–93. https://doi.org/10.1016/S0925-4005(97)00133-0
Fu L, Wang Y (2018) Detection methods and applications of microfluidic paper-based analytical devices. Trends Anal Chem 107:196–211. https://doi.org/10.1016/j.trac.2018.08.018
Gabriel EFM, Garcia PT, Cardoso TMG, Lopes FM, Martins FT, Coltro WKT (2016) Highly sensitive colorimetric detection of glucose and uric acid in biological fluids using chitosan-modified paper microfluidic devices. Analyst 141:4749–4756. https://doi.org/10.1039/C6AN00430J
Garcia PDT, Cardoso TMG, Garcia CD, Carrilho E, Coltro WKT (2014) A handheld stamping process to fabricate microfluidic paper-based analytical devices with chemically modified surface for clinical assays. RSC Adv 4:37637–37644. https://doi.org/10.1039/C4RA07112C
Ge L, Wang S, Song X, Ge S, Yu J (2012a) 3D Origami-based multifunction-integrated immunodevice: low-cost and multiplexed sandwich chemiluminescence immunoassay on microfluidic paper-based analytical device. Lab Chip 12:3150–3158. https://doi.org/10.1039/c2lc40325k
Ge L, Yan J, Song X, Yan M, Ge S, Yu J (2012b) Three-dimensional paper-based electrochemiluminescence immunodevice for multiplexed measurement of biomarkers and point-of-care testing. Biomaterials 33:1024–1031. https://doi.org/10.1016/j.biomaterials.2011.10.065
Goleij M, Fakhraee H (2017) Response surface methodology optimization of cobalt (II) and lead (II) removal from aqueous solution using MWCNT-Fe3O4 nanocomposite. Iran J Chem Chem Eng 36:129–141
Han D, Han T, Shan C, Ivaska A, Niu L (2010) Simultaneous determination of ascorbic acid, dopamine and uric acid with chitosan-graphene modified electrode. Electroanalysis 22:2001–2008. https://doi.org/10.1002/elan.201000094
Hu J, Wang S, Wang L, Li F, Pingguan-Murphy B, Lu TJ, Xu F (2014) Advances in paper-based point-of-care diagnostics. Biosens Bioelectron 54:585–597. https://doi.org/10.1016/j.bios.2013.10.075
Hu S-W, Qiao S, Xu B-Y, Peng X, Xu J-J, Chen H-Y (2017) Dual-functional carbon dots pattern on paper chips for Fe3+ and ferritin analysis in whole blood. Anal Chem 89:2131–2137. https://doi.org/10.1021/acs.analchem.6b04891
Huang J, Zhu X-L, Wang Y-M, Ge J-H, Liu J-W, Jiang J-H (2018) A multiplex paper-based nanobiocatalytic system for simultaneous determination of glucose and uric acid in whole blood. Analyst 143:4422–4428. https://doi.org/10.1039/C8AN00866C
Javadnia N, Farrokhnia A (2019) The thermodynamic and kinetics study of removal of Cd(II) by nanoparticles of cobalt oxide in aqueous solution. Iran J Chem Chem Eng 38:127–139
Jiang Y, Hao Z, He Q, Chen H (2016) A simple method for fabrication of microfluidic paper-based analytical devices and on-device fluid control with a portable corona generator. RSC Adv 6:2888–2894. https://doi.org/10.1039/C5RA23470K
Ko Y, Kwon M, Bae WK, Lee B, Lee SW, Cho J (2017) Flexible supercapacitor electrodes based on real metal-like cellulose papers. Nat Commun 8:536. https://doi.org/10.1038/s41467-017-00550-3
Kutzing MK, Firestein BL (2008) Altered uric acid levels and disease states. J Pharmacol Exp Ther 324:1–7. https://doi.org/10.1124/jpet.107.129031
Lakshmi D, Whitcombe MJ, Davis F, Sharma PS, Prasad BB (2011) Electrochemical detection of uric acid in mixed and clinical samples: a review. Electroanalysis 23:305–320. https://doi.org/10.1002/elan.201000525
Lam T, Devadhasan JP, Howse R, Kim J (2017) A chemically patterned microfluidic paper-based analytical device (C-µPAD) for point-of-care diagnostics. Sci Rep 7:1188. https://doi.org/10.1038/s41598-017-01343-w
Lan W-J et al (2014) Paper-based potentiometric ion sensing. Anal Chem 86:9548–9553. https://doi.org/10.1021/ac5018088
Lane JD, Krumholz DM, Sack RA, Morris C (2006) Tear glucose dynamics in diabetes mellitus. Curr Eye Res 31:895–901. https://doi.org/10.1080/02713680600976552
Magner E (1998) Trends in electrochemical biosensors†. Analyst 123:1967–1970. https://doi.org/10.1039/a803314e
Makaram P, Owens D, Aceros J (2014) Trends in nanomaterial-based non-invasive diabetes sensing technologies. Diagnostics 4:27–46
Manbohi A, Ahmadi SH (2015) In-tube magnetic solid phase microextraction of some fluoroquinolones based on the use of sodium dodecyl sulfate coated Fe3O4 nanoparticles packed tube. Anal Chim Acta 885:114–121. https://doi.org/10.1016/j.aca.2015.05.030
Manbohi A, Ahmadi SH (2019) Sensitive and selective detection of dopamine using electrochemical microfluidic paper-based analytical nanosensor. Sens Bio-Sens Res 23:100270. https://doi.org/10.1016/j.sbsr.2019.100270
Manbohi A, Ahmadi SH, Jabbari V (2015) On-line microextraction of moxifloxacin using Fe3O4 nanoparticle-packed in-tube SPME. RSC Adv 5:57930–57936. https://doi.org/10.1039/c5ra07049j
Meredith NA, Quinn C, Cate DM, Reilly TH, Volckens J, Henry CS (2016) Paper-based analytical devices for environmental analysis. Analyst 141:1874–1887. https://doi.org/10.1039/C5AN02572A
Nakashima K, Hayashida N, Kawaguchi S, Akiyama S, Tsukamoto Y, Imai K (1991) Flow-injection analysis with chemiluminescence detection of glucose and uric acid using immobilized enzyme reactor. Anal Sci 7:715–718. https://doi.org/10.2116/analsci.7.715
Navaei T, Zare K, Taleshi F, Yousefi M (2019) Removal of Cd2+ from aqueous solution by nickel oxide/CNT nanocomposites. Iran J Chem Chem Eng 38:141–154
Nie Z, Deiss F, Liu X, Akbulut O, Whitesides GM (2010a) Integration of paper-based microfluidic devices with commercial electrochemical readers. Lab Chip 10:3163–3169. https://doi.org/10.1039/C0LC00237B
Nie Z et al (2010b) Electrochemical sensing in paper-based microfluidic devices. Lab Chip 10:477–483. https://doi.org/10.1039/B917150A
Noiphung J, Songjaroen T, Dungchai W, Henry CS, Chailapakul O, Laiwattanapaisal W (2013) Electrochemical detection of glucose from whole blood using paper-based microfluidic devices. Anal Chim Acta 788:39–45. https://doi.org/10.1016/j.aca.2013.06.021
Odo J, Shinmoto E, Shiozaki A, Hatae Y, Katayama S, Jiao G (2004) Spectrofluorometric determination of uric acid and glucose by use of Fe(III)-thiacalix[4]arenetetrasulfonate as a peroxidase mimic. J Health Sci 50:594–599
Phypers B, Pierce JMT (2006) Lactate physiology in health and disease. Contin Educ Anaesth Crit Care Pain 6:128–132. https://doi.org/10.1093/bjaceaccp/mkl018
Quyen TTB, Su W-N, Chen K-J, Pan C-J, Rick J, Chang C-C, Hwang B-J (2013) Au@SiO2 core/shell nanoparticle assemblage used for highly sensitive SERS-based determination of glucose and uric acid. J Raman Spectrosc 44:1671–1677. https://doi.org/10.1002/jrs.4400
Rossi LM, Quach AD, Rosenzweig Z (2004) Glucose oxidase–magnetite nanoparticle bioconjugate for glucose sensing. Anal Bioanal Chem 380:606–613. https://doi.org/10.1007/s00216-004-2770-3
Said MI, Rageh AH, Abdel-aal FAM (2018) Fabrication of novel electrochemical sensors based on modification with different polymorphs of MnO2 nanoparticles. Application to furosemide analysis in pharmaceutical and urine samples. RSC Adv 8:18698–18713. https://doi.org/10.1039/C8RA02978D
Sarwar N et al (2010) Diabetes mellitus, fasting blood glucose concentration, and risk of vascular disease: a collaborative meta-analysis of 102 prospective studies. Lancet 375:2215–2222. https://doi.org/10.1016/s0140-6736(10)60484-9
Shukla SK, Mishra AK, Arotiba OA, Mamba BB (2013) Chitosan-based nanomaterials: a state-of-the-art review. Int J Biol Macromol 59:46–58. https://doi.org/10.1016/j.ijbiomac.2013.04.043
Songjaroen T, Dungchai W, Chailapakul O, Laiwattanapaisal W (2011) Novel, simple and low-cost alternative method for fabrication of paper-based microfluidics by wax dipping. Talanta 85:2587–2593. https://doi.org/10.1016/j.talanta.2011.08.024
Sriram G et al (2017) Paper-based microfluidic analytical devices for colorimetric detection of toxic ions: a review. Trends Anal Chem 93:212–227. https://doi.org/10.1016/j.trac.2017.06.005
Srivastava M, Nirala NR, Srivastava SK, Prakash R (2018) A comparative study of aptasensor vs immunosensor for label-free PSA cancer detection on GQDs-AuNRs modified screen-printed electrodes. Sci Rep 8:1923. https://doi.org/10.1038/s41598-018-19733-z
Tabata M, Fukunaga C, Ohyabu M, Murachi T (1984) Highly sensitive flow injection analysis of glucose and uric acid in serum using an immobilized enzyme column and chemiluminescence. J Appl Biochem 6:251–258
Tietz NW (1995) Clinical guide to laboratory tests (ELISA), 3rd edn. W.B. Saunders Co., Philadelphia
Vosmanská V, Kolářová K, Rimpelová S, Kolská Z, Švorčík V (2015) Antibacterial wound dressing: plasma treatment effect on chitosan impregnation and in situ synthesis of silver chloride on cellulose surface. RSC Adv 5:17690–17699. https://doi.org/10.1039/C4RA16296J
Wang J, Chatrathi MP, Tian B, Polsky R (2000) Microfabricated electrophoresis chips for simultaneous bioassays of glucose, uric acid, ascorbic acid, and acetaminophen. Anal Chem 72:2514–2518. https://doi.org/10.1021/ac991489l
Wang X, Li F, Cai Z, Liu K, Li J, Zhang B, He J (2018) Sensitive colorimetric assay for uric acid and glucose detection based on multilayer-modified paper with smartphone as signal readout. Anal Bioanal Chem 410:2647–2655. https://doi.org/10.1007/s00216-018-0939-4
Wei F et al (2009) Electrochemical sensor for multiplex biomarkers detection. Clin Cancer Res 15:4446–4452. https://doi.org/10.1158/1078-0432.ccr-09-0050
Weng X, Neethirajan S (2017) Rapid detection of norovirus using paper-based microfluidic device. bioRxiv. https://doi.org/10.1101/162396
WHO (2018) Diabetes. WHO. http://www.who.int/news-room/fact-sheets/detail/diabetes
Xue Y-Y et al (2017) Development of a paper-based microfluidic analytical device by a more facile hydrophobic substrate generation strategy. Anal Biochem 525:100–106. https://doi.org/10.1016/j.ab.2017.03.001
Yan Q, Peng B, Su G, Cohan BE, Major TC, Meyerhoff ME (2011) Measurement of tear glucose levels with amperometric glucose biosensor/capillary tube configuration. Anal Chem 83:8341–8346. https://doi.org/10.1021/ac201700c
Yijun J, Jinhua J, Qiuming G, Meiling R, Himei Y, Lingjun Q (2008) A novel nanoscale catalyst system composed of nanosized Pd catalysts immobilized on Fe3O4@SiO2-PAMAM. Nanotechnology 19:075714
Yu J, Ge L, Huang J, Wang S, Ge S (2011) Microfluidic paper-based chemiluminescence biosensor for simultaneous determination of glucose and uric acid. Lab Chip 11:1286–1291. https://doi.org/10.1039/C0LC00524J
Yuwono RA, Izdiharruddin MF, Wahyuono RA (2016) Integrated ZnO nanoparticles on paper-based microfluidic: toward efficient analytical device for glucose detection based on impedance and FTIR measurement. In: Second international seminar on photonics, optics, and its applications. SPIE, p 6
Zhao C, Meng Y, Shao C, Wan L, Jiao K (2008) Unadulterated glucose biosensor based on direct electron transfer of glucose oxidase encapsulated chitosan modified glassy carbon electrode. Electroanalysis 20:520–526. https://doi.org/10.1002/elan.200704086
Zhao C, Thuo MM, Liu X (2013) A microfluidic paper-based electrochemical biosensor array for multiplexed detection of metabolic biomarkers. Sci Technol Adv Mater 14:054402. https://doi.org/10.1088/1468-6996/14/5/054402
Zhao C, Thuo MM, Liu X (2015) Corrigendum: A microfluidic paper-based electrochemical biosensor array for multiplexed detection of metabolic biomarkers (2013 Sci. Technol. Adv. Mater. 14 054402). Sci Technol Adv Mater 16:049501. https://doi.org/10.1088/1468-6996/16/4/049501
Zhu X, Huang J, Liu J, Zhang H, Jiang J, Yu R (2017) A dual enzyme–inorganic hybrid nanoflower incorporated microfluidic paper-based analytic device (μPAD) biosensor for sensitive visualized detection of glucose. Nanoscale 9:5658–5663. https://doi.org/10.1039/c7nr00958e
Acknowledgements
We gratefully acknowledge the Iran National Science Foundation (Grant no. 54372049) for supporting this project. We also would like to thank Chemistry and Chemical Engineering Research Center of Iran (CCERCI) and Iranian National Institute for Oceanography and Atmospheric Science (INIOAS). We also would like to thank Bushehr University of Medical Sciences for providing real samples. Lastly, the authors would like to thank Vahid Jabbari at chemistry department of Southern Methodist University (SMU), Texas, USA, for scientific support and assisting us in editing language of the paper.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Manbohi, A., Ahmadi, S.H. Chitosan–Fe3O4 nanoparticle enzymatic electrodes on paper as an efficient assay for glucose and uric acid detection in biological fluids. Chem. Pap. 74, 2675–2687 (2020). https://doi.org/10.1007/s11696-020-01105-5
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11696-020-01105-5