Abstract
The article describes the preparation of chitosan-coated hemoglobin (Hb-CS) microcapsules by (a) preparing a CaCO3 precipitate containing Hb, (b) crosslinking Hb with glutaraldehye, (c) coating the particles with chitosan, and (d) preparing Hb-CS microcapsules by removing the CaCO3 template with a solution of disodium EDTA. The morphology and electrochemical properties of the Hb-CS microcapsules were investigated by scanning electron microscopy, cyclic voltammetry and electrochemical impedance spectroscopy. An oxygen sensor was obtained by immobilizing the Hb-CS microcapsules on the surface of a glassy carbon electrode (GCE) first modified with gold nanoparticles. The application of Hb-CS microcapsules facilitates electron transfer on the surface of GCE and warrants the integrity and biological activity of Hb. The oxygen sensor, operated best at a working voltage of −0.335 V (vs. SCE), displays a low limit of detection (30 nM). The Hb-CS microcapsules also are shown to release loaded oxygen to an anaerobic aqueous environment within 300 min.
Similar content being viewed by others
References
Spencer JA, Ferraro F, Roussakis E, Klein A, Wu J, Runnels JM, Zaher W, Mortensen LJ, Alt C, Turcotte R, Yusuf R, Côté D, Vinogradov SA, Scadden DT, Lin CP (2014) Direct measurement of local oxygen concentration in the bone marrow of live animals. Nature 508:269–273
Tong LY, Chuang CC, SY W, Zuo L (2015) Reactive oxygen species in redox cancer therapy. Cancer Lett 367:18–25
Aicha A, Freundlicha M, Vekilova PG (2015) The free heme concentration in healthy human erythrocytes. Blood Cell Mol Dis 55:402–4094
Fei HL, Ye RQ, Ye GL, Gong YJ, Peng ZW, Fan XJ, Samuel ELG, Ajayan PM, Tour JM (2014) Boron- and nitrogen-doped graphene quantum dots/graphene hybrid nanoplatelets as efficient electrocatalysts for oxygen reduction. ACS Nano 8:10837–10843
Lv XH, Ma HM, Wu D, Yan T, Ji L, Liu YX, Pang XH, Du B, Wei Q (2016) Novel gold nanocluster electrochemiluminescence immunosensors based on nanoporous NiGd-Ni2O3-Gd2O3 alloys. Biosens Bioelectron 75:142–147
Li YX, Liu ZC, Xie JP, Li LL, MQ F, Zhou J (2015) A nanocomposite with core-shell structure for site-specific oxygen sensing: Synthesis, characterization, photophysical feature and sensing performance. Sens Actuators B Chem 221:312–319
Pita M, Sanchez CG, Toscano MD, Shleev S, Lacey ALD (2013) Oxygen biosensor based on bilirubin oxidase immobilized on a nanostructured gold electrode. Bioelectrochem 94:69–74
Zheng J, Guo CZ, Chen CY, Fan MZ, Gong JP, Zhang YF, Zhao TX, Sun YL, Xu XF, Li MM, Wang R, Luo ZL, Chen CG (2015) High content of pyridinic- and pyrrolic-nitrogen-modified carbon nanotubes derived from blood biomass for the electrocatalysis of oxygen reduction reaction in alkaline medium. Electrochim Acta 168:386–393
Rezende EL (2013) Better oxygen delivery, vol 340. Science, pp. 1293–1294
Saadati S, Salimi A, Hallaj R, Rostami A (2014) Direct electron transfer and electrocatalytic properties of immobilized hemoglobin onto glassy carbon electrode modified with ionic-liquid/titanium-nitride nanoparticles: application to nitrite detection. Sens Actuators B Chem 191:625–633
Ahn KS, Lee JH, Park JM, Choi HN, Lee WY (2016) Luminol chemiluminescence biosensor for glycated hemoglobin (HbA1c) in human blood samples. Biosens Bioelectron 75:82–87
Bai J, LP W, Wang XJ, Zhang HM (2015) Hemoglobin-graphene modified carbon fiber microelectrode for direct electrochemistry and electrochemical H2O2 sensing. Electrochim Acta 185:142–147
Liu Y, Gong J, Wu W, Fang Y, Wang Q, Gu H (2016) A novel bio-nanocomposite based on hemoglobin and carboxy grapheme for enhancing the ability of carrying oxygen. Sens Actuators B Chem 222:588–597
Zhan T, Wang X, Li X, Song Y, Hou W (2016) Hemoglobin immobilized in exfoliated Co2Al LDH-graphene nanocomposite film: Direct electrochemistry and electrocatalysis toward trichloroacetic acid. Sens Actuators B Chem 228:101–108
Suprun EV, Shumyantseva VV, Archakov AI (2014) Protein electrochemistry: Application in Medicine A Review. Electrochim Acta 140:72–82
Hu Y, Sun H, Hu NF (2007) Assembly of layer-by-layer films of electroactive hemoglobin and surfactant didodecyldimethylammonium bromide. J Colloid Interface Sci 314:131–140
Koder RL, Ross Anderson JL, Solomon LA, Reddy KS, Moser CC, Leslie Dutto P (2009) Design and engineering of an O2 transport protein. Nature 458:305–309
RF X, Zhang JW, Zhou PH, Yang R, Feng XY, Xu LX (2015) A novel artificial red blood cell substitute: grafted starch-encapsulated hemoglobin. RSC Adv 5:43845–43853
Squires J E (2002) Artificial blood. Science 295:1002–1005
Wang YH, Guo JW, Gu HY (2010) A novel nano-sized bionic function interface for enhancing the ability of red blood cells to carry oxygen. Microchim Acta 171:179–186
Duan L, Yan X, Wang A, Jia Y, Li JB (2012) Highly loaded hemoglobin spheres as promising artificial oxygen carriers. ACS Nano 6:6897–6904
Liu Y, She P, Gong J, Wu WP, Xu SM, Li JG, Zhao K, Deng AP (2015) A novel sensor based on electrodeposited Au-Pt bimetallic nano-clusters decorated on graphene oxide (GO)-electrochemically reduced GO for sensitive detection of dopamine and uric acid. Sensors Actuators B Chem 221:1542–1553
Liu Y, Zhou J, Gong J, WP W, Pan ZQ, Gu HY (2013) The investigation of electrochemical properties for Fe3O4@Pt nanocomposites and an enhancement sensing for nitrite. Electrochim Acta 111:876–887
Kamin RA, Wilson GS (1980) Rotating ring-disk enzyme electrode for biocatalysis kinetic studies and characterization of the immobilized enzyme layer. Anal Chem 52:1198–1205
Liu Y, Han T, Chen C, Bao N, Yu CM, Gu HY (2011) A novel platform of hemoglobin on core-shell structurally Fe3O4@Au nanoparticles and its direct electrochemistry. Electrochim Acta 56:3248–3257
Taniguchi VT, Sailasuta-Scott N, Anson FC, Gray HB (1980) Thermodynamics of metallo protein electron transfer reactions. Pure Appl Chem 52:2275–2281
Gu HY, Yu AM, Chen HY (2001) Direct electron transfer and characterization of hemoglobin immobilized on a Au colloid-cysteamine-modified gold electrode. J Electroanal Chem 516:119–126
Haghighi B, Bozorgzadeh S (2011) Enhanced electrochemiluminescence from luminol at multi-walled carbon nanotubes decorated with palladium nanoparticles: A novel route for the fabrication of an oxygen sensor and a glucose biosensor. Anal Chim Acta 697:90–97
Wang XD, Wolfbeis OS (2014) Optical methods for sensing and imaging oxygen: materials, spectroscopies and applications. Chem Soc Rev 43:3666–3761
Lin ZY, Liu Y, Chen GN (2008) TiO2/Nafion film based electrochemiluminescence for detection of dissolved oxygen. Electrochem Commun 10:1629–1632
Zheng RJ, Fang YM, Qin SF, Song J, Wu AH, Sun JJ (2011) A dissolved oxygen sensor based on hot electron induced cathodic electrochemiluminescence at a disposable CdS modified screen-printed carbon electrode. Sensors Actuators B Chem 157:488–493
Luo W, Abbas ME, Zhu LH, Zhou WY, Li KJ, Tang HQ, Liu SS, Li WY (2009) A simple fluorescent probe for the determination of dissolved oxygen based on the catalytic activation of oxygen by iron(II) chelates. Anal Chim Acta 640:63–67
Acknowledgments
The authors would like to thank the National Natural Science Foundation of China (NSFC, Nos. 21075087, 21175097, 81202249 and 21375066) and a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions for financial support of this research.
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
The author(s) declare that they have no competing interests.
Electronic Supplementary Material
ESM 1
(DOCX 293 kb)
Rights and permissions
About this article
Cite this article
Liu, Y., Wang, Q., She, P. et al. Chitosan-coated hemoglobin microcapsules for use in an electrochemical sensor and as a carrier for oxygen. Microchim Acta 183, 2847–2854 (2016). https://doi.org/10.1007/s00604-016-1908-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00604-016-1908-2