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Enhanced and tunable oxygen carrier and amperometric sensor based on a glassy carbon electrode assembly of a hemoglobin-chitosan-Fe3O4 composite

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Abstract

The authors have prepared organized assemblies of a hemoglobin-chitosan(CS)@Fe3O4 composite on glassy carbon electrodes (GCEs) via three strategies with the aim of preparing tunable Hb-coated GCEs with good stability and long-term oxygen storage capability. The formation and morphology of the Hb-CS@Fe3O4 composite was characterized by scanning electrochemical microscopy, XRD and UV–vis spectroscopy. It is shown that Hb is fully integrated into the CS@Fe3O4 and can be manipulated by a magnetic field whilst maintaining its biological activity. In the absence of oxygen, a surface-controlled electrode process occurs with an interfacial electron transfer rate (k s) of 2.14 s−1. The modified GCE also has a favorable oxygen storage lifetime (almost 6 h). One Hb-CS@Fe3O4 film on the electrode displays particularly good electrocatalytic reduction activity towards oxygen. The linear range for detection of O2 is 1.2 × 10−7 ~ 2.0 × 10−4 mol L−1 with a detection limit of 4.0 × 10−8 mol L−1. In our opinion, this method has great potential in terms of enhanced oxygen storage capability of Hb, which can be applied in special situations such as space operations, down hole mining, mountaineering and diving.

Hb-CS@Fe3O4 composites were prepared by three strategies, and oxygen carrying capability was studied. The corresponding modified electrode constructed on the basis of the magnetic field environment was superior in terms of stability, sensitivity and O2 storage time, showing wider linear range and lower detection limit.

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References

  1. Winslow RM (2007) The role of hemoglobin oxygen affinity in oxygen transport at high altitude. Respir Physiol Neurobiol 158:121–127

    Article  CAS  Google Scholar 

  2. Yonetani T, Laberge M (2008) Protein dynamics explain the allosteric behaviors of hemoglobin. Biochim Biophys Acta, Proteins Proteomics 1784:1146–1158

    Article  CAS  Google Scholar 

  3. Ang SH, Rambeli M, Thevarajah TM, Alias YB, Khor SM (2016) Quantitative, single-step dual measurement of hemoglobin A1c and total hemoglobin in human whole blood using a gold sandwich immunochromatographic assay for personalized medicine. Biosens Bioelectron 78:187–193

    Article  CAS  Google Scholar 

  4. Elwell CE, Leung TS, Harrison DK (2016) Oxygen transport to tissue XXXVII, part 1, chapter 2

  5. Porte L, Abel M, Amsalem P, Bocquet F, Bocquet FC, Chevallier V, Clair S, Delafosse G, Desbief S, Gadenne V, Giovanelli L, Koudia M, Ksari Y, Loppacher C, Merlen A, Nony L, Ourdjini O (2012) Self-organised growth of molecular arrays at surfaces. Int J Nanotechnol 9:325–354

    Article  CAS  Google Scholar 

  6. Yu CM, Wang YD, Wang L, Zhu ZK, Bao N, Gu HY (2013) Nanostructured biosensors built with layer-by-layer electrostatic assembly of hemoglobin and Fe3O4@Pt nanoparticles. Colloids Surf B: Biointerfaces 103:231–237

    Article  CAS  Google Scholar 

  7. Bunn HF (1987) Subunit assembly of hemoglobin: an important determinant of hematologic phenotype. Blood 69:1–6

    CAS  Google Scholar 

  8. Wang CH, Yang C, Song YY, Gao W, Xia XH (2005) Adsorption and direct electron transfer from hemoglobin into a three-dimensionally ordered. macroporous gold film. Adv Funct Mater 15:1267–1275

    Article  CAS  Google Scholar 

  9. Higashi T, Yamagishi A, Takeuchi T, Kawaguchi N, Sagawa S, Onishi S, Date M (1993) Orientation of erythrocytes in a strong static magnetic field. Blood 82:1328–1334

    CAS  Google Scholar 

  10. Kuchel PW, Durrant CJ, Chapman BE, Jarrett PS, Regan DG (2000) Evidence of red cell alignment in the magnetic field of an NMR spectrometer based on the diffusion tensor of water. J Magn Reson 145:291–301

    Article  CAS  Google Scholar 

  11. Wang YH, Yu CM, Pan ZQ, Wang YF, Guo JW, Gu HY (2013) A gold electrode modified with hemoglobin and the chitosan@Fe3O4 nanocomposite particles for direct electrochemistry of hydrogen peroxide. Microchim Acta 180:659–667

    Article  CAS  Google Scholar 

  12. Luo XL, Xu JJ, Zhang Q, Yang GJ, Chen HY (2005) Electrochemically deposited chitosan hydrogel for horseradish peroxidase immobilization through gold nanoparticles self-assembly. Biosens Bioelectron 21:190–196

    Article  CAS  Google Scholar 

  13. 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

    Article  CAS  Google Scholar 

  14. Yu CM, Gou LL, Zhou XH, Bao N, Gu HY (2011) Chitosan-Fe3O4 nanocomposite based electrochemical sensors for the determination of bisphenol A. Electrochim Acta 56:9056–9063

    Article  CAS  Google Scholar 

  15. Zheng J, Zhao JC, Gong C, Liu P, Chen Y, Huang H, He PG, Fang YZ (2012) Preparation of the ordered mesoporous carbon/Fe3O4 and its application for the direct electrochemistry of hemoglobin. Acta Chim Sin 70:617–623

    Article  CAS  Google Scholar 

  16. Elanchezhiyan SS, Sivasurian N, Meenakshi S (2016) Enhancement of oil recovery using zirconium-chitosan hybrid composite by adsorptive method. Carbohydr Polym 145:103–113

    Article  CAS  Google Scholar 

  17. Gandhi MR, Meenakshi S (2012) Preparation and characterization of silica gel/chitosan composite for the removal of Cu(II) and Pb(II). Int J Biol Macromol 50:650–657

    Article  Google Scholar 

  18. Yu CM, Guo JW, Gu HY (2009) Direct electrochemical behavior of hemoglobin at surface of Au@Fe3O4 magnetic nanoparticles. Microchim Acta 166:215–220

    Article  CAS  Google Scholar 

  19. Jolly P, Tamboli V, Harniman RL, Estrela P, Allender CJ, Bowen JL (2016) Aptamer-MIP hybrid receptor for highly sensitive electrochemical detection of prostate specific antigen. Biosens Bioelectron 75:188–195

    Article  CAS  Google Scholar 

  20. Cai W, Peck JR, van der Weide DW, Hamers RJ (2004) Direct electrical detection of hybridization at DNA-modified silicon surfaces. Biosens Bioelectron 19:1013–1019

    Article  CAS  Google Scholar 

  21. Miao P, Wang BB, Han K, Tang YG (2014) Electrochemical impedance spectroscopy study of proteolysis using unmodified gold nanoparticles. Electrochem Commun 47:21–24

    Article  CAS  Google Scholar 

  22. Chen GY, Sun H, Hou SF (2016) Electrochemistry and electrocatalysis of myoglobin immobilized in sulfonated graphene oxide and Nafion films. Anal Biochem 502:43–49

    Article  CAS  Google Scholar 

  23. Zhao G, Xu JJ, Chen HY (2006) Fabrication, characterization of Fe3O4 multilayer film and its application in promoting direct electron transfer of hemoglobin. Electrochem Commun 8:148–154

    Article  CAS  Google Scholar 

  24. 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 56:3238–3247

    Article  CAS  Google Scholar 

  25. Bond AM (1980) Modern polarographic methods in analytical chemistry.

  26. 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

    Article  CAS  Google Scholar 

  27. Liu Y, Gong J, Wu WP, Fang YT, Wang Q, Gu HY (2016) A novel bio-nanocomposite based on hemoglobin and carboxyl graphene for enhancing the ability of carrying oxygen. Sensors Actuators B Chem 222:588–597

    Article  CAS  Google Scholar 

  28. Liu XJ, Pan ZQ, Dong ZL, Lu YN, Sun QL, Wu TT, Bao N, He H, Gu HY (2016) Amperometric oxygen biosensor based on hemoglobin encapsulated in nanosized grafted starch particles. Microchim Acta 183:353–359

    Article  CAS  Google Scholar 

  29. Lin ZY, Liu Y, Chen GN (2008) TiO2/Nafion film based electrochemiluminescence for detection of dissolved oxygen. Electrochem Commun 10:1629–1632

    Article  CAS  Google Scholar 

  30. 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

    Article  CAS  Google Scholar 

  31. Sun LJ, Liu XJ, Sun QL, Cai M, Zhou JJ, Dong ZL, Bao N, Gu HY, He H (2016) Layer-by-layer assembly of hemoglobin and gold nanoparticles for enhancing the ability of oxygen carrying. Appl Surf Sci 363:566–571

    Article  CAS  Google Scholar 

  32. Lu YN, Hu TT, Wu TT, Liu XJ, Bao N, Yu CM, He H, Gu HY (2016) Construction of electrochemical avenue for evaluating oxygen-carrying performance of a microsphere-based oxygen carrier with bovine serum albumin protection layer. J Electroanal Chem 781:327–331

    Article  CAS  Google Scholar 

  33. Liu Y, Wang Q, She P, Gong J, Wu WP, Xu SM, Li JG, Zhao K, Deng AP (2016) Chitosan-coated hemoglobin microcapsules for use in an electrochemical sensor and as a carrier for oxygen. Microchim Acta 183:2847–2854

    Article  CAS  Google Scholar 

Download references

Acknowledgments

This work was funded by the National Natural Science Foundation of China (21475070, 31400847), the Jiangsu Province Natural Science Foundation (BK20151267) and Foundation of Nantong Natural Science Projects (MS12015030, MS12015028, MS12015046). A project funded by the priority academic program development of Jiangsu Higher Education Institutions (PAAD).

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    Authors and Affiliations

    1. School of Public Health, Center of Analysis and Testing, Institute of Analytical Chemistry for Life Science, Nantong University, Nantong, 226019, People’s Republic of China

      Yuanhong Wang, Fang Zhang, Chunmei Yu & Haiying Gu

    2. Institute of Analytical Chemistry, Soochow University, Suzhou, 215123, People’s Republic of China

      Yuanhong Wang & Yifeng Tu

    3. Suzhou Institute of Biomedical Engineering and Technology, Chinese Academy of Sciences, Suzhou, 215163, People’s Republic of China

      Peng Miao

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    1. Yuanhong Wang
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    2. Fang Zhang
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    Correspondence to Peng Miao or Haiying Gu.

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    Yuanhong Wang and Fang Zhang contributed equally to this work.

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    Wang, Y., Zhang, F., Yu, C. et al. Enhanced and tunable oxygen carrier and amperometric sensor based on a glassy carbon electrode assembly of a hemoglobin-chitosan-Fe3O4 composite. Microchim Acta 184, 1437–1444 (2017). https://doi.org/10.1007/s00604-017-2137-z

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