Abstract
The authors describe a nanosized oxygen biosensor based on grafted starch particles with encapsulated hemoglobin (GS-Hb). Transmission electron microscopy showed the GS-Hb particles to have a typical diameter of 573 nm. UV–vis absorption spectra showed that the hemoglobin in GS-Hb retains its biological activity in terms of carrying and releasing oxygen. Cyclic voltammetric studies were performed with GS-Hb particles placed in a chitosan matrix on a glassy carbon electrode, revealing a pair of nearly reversible redox peaks. At a working potential of −0.40 V (vs. SCE), a linear response is found over the 0.97 μM to 0.35 mM oxygen concentration range, and the lower detection limit is 0.32 μM (~5 ppb; at an S/N ratio of 3). This range is wider than that produced when using red blood cells. In addition, the GS-Hb particles have a better oxygen-carrying ability, which may pave the way to the creation of oxygen carriers for use in transfusions.
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A glassy carbon electrode modified with hemoglobin in starch particles in a chitosan matrix shows excellent amperometric response to oxygen and also displays improved oxygen-carrying capability (compared to red blood cells).
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References
Liu H, Duan C, Yang C, Shen W, Wang F, Zhu Z (2015) A novel nitrite biosensor based on the direct electrochemistry of hemoglobin immobilized on MXene-Ti3C2. Sensors Actuators B Chem 218:60–66. doi:10.1016/j.snb.2015.04.090
Sun W, Hou F, Gong S, Han L, Wang W, Shi F, Xi J, Wang X, Li G (2015) Direct electrochemistry and electrocatalysis of hemoglobin on three-dimensional graphene modified carbon ionic liquid electrode. Sensors Actuators B Chem 219:331–337. doi:10.1016/j.snb.2015.05.015
Mao S, Long Y, Li W, Tu Y, Deng A (2013) Core-shell structured Ag@C for direct electrochemistry and hydrogen peroxide biosensor applications. Biosens Bioelectron 48:258–262. doi:10.1016/j.bios.2013.04.026
Chen X, Wang Q, Wang L, Gao F, Wang W, Hu Z (2015) Imidazoline derivative templated synthesis of broccoli-like Bi2S3 and its electrocatalysis towards the direct electrochemistry of hemoglobin. Biosens Bioelectron 66:216–223. doi:10.1016/j.bios.2014.11.020
Lin M, Pan D, Hu X, Han H, Li F (2015) Titanium carbide nanoparticles/ion-exchange polymer-based sensor for catalytic stripping determination of trace iron in coastal waters. Sensors Actuators B Chem 219:164–170. doi:10.1016/j.snb.2015.05.034
Zhao R, Liu X, Zhang J, Zhu J, Wong DKY (2015) Enhancing direct electron transfer of glucose oxidase using a gold nanoparticle |titanate nanotube nanocomposite on a biosensor. Electrochim Acta 163:64–70. doi:10.1016/j.electacta.2015.02.098
Yu YY, Guo CX, Yong YC, Li CM, Song H (2015) Nitrogen doped carbon nanoparticles enhanced extracellular electron transfer for high-performance microbial fuel cells anode. Chemosphere 140:26–33. doi:10.1016/j.chemosphere.2014.09.070
Xu Q, Shen Y, Tang J, Xue MH, Jiang L, Hu X (2015) Electrochemical method assisted immobilization and orientation of myoglobin into biomimetic brij 56 film and its direct electrochemistry study. ACS Appl Mater Interfaces 7(21):11286–11293. doi:10.1021/acsami.5b01492
Guitian Oliveira N, Sirgado T, Reis L, Pinto LFV, da Silva CL, Ferreira FC, Rodrigues A (2014) In vitro assessment of three dimensional dense chitosan-based structures to be used as bioabsorbable implants. J Mech Behav Biomed 40:413–425. doi:10.1016/j.jmbbm.2014.09.014
Yang JL, Huang YJ, Gao CM, Liu MZ, Zhang XJ (2014) Fabrication and evaluation of the novel reduction-sensitive starch nanoparticles for controlled drug release. Colloids Surf, B 115:368–376. doi:10.1016/j.colsurfb.2013.12.007
Zhang JJ, Ma XX, Fan DD, Zhu CH, Deng JJ, Hui JF, Ma P (2014) Synthesis and characterization of hyaluronic acid/human-like collagen hydrogels. Mat Sci Eng C-Mater 43:547–554. doi:10.1016/j.msec.2014.07.058
Gu F, Li B-Z, Xia H, Adhikari B, Gao Q (2015) Preparation of starch nanospheres through hydrophobic modification followed by initial water dialysis. Carbohyd Polym 115:605–612. doi:10.1016/j.carbpol.2014.08.102
Subramanian SB, Francis AP, Devasena T (2014) Chitosan-starch nanocomposite particles as a drug carrier for the delivery of bis-desmethoxy curcumin analog. Carbohyd Polym 114:170–178. doi:10.1016/j.carbpol.2014.07.053
Mauricio MR, da Costa PG, Haraguchi SK, Guilherme MR, Muniz EC, Rubira AF (2015) Synthesis of a microhydrogel composite from cellulose nanowhiskers and starch for drug delivery. Carbohyd Polym 115:715–722. doi:10.1016/j.carbpol.2014.07.063
Collins RE (1961) Transport of gases through hemoglobin solution. Science (New York, NY) 133(3464):1593–1594. doi:10.1126/science.133.3464.1593
Bossi D, Giardina B (1996) Chapter 1 Red cell physiology. Mol Aspects Med 17(2):117–128. doi:10.1016/0098-2997(96)88343-9
Sharan M, Popel AS (2002) A compartmental model for oxygen transport in brain microcirculation in the presence of blood substitutes. J Theor Biol 216(4):479–500. doi:10.1006/jtbi.2002.3001
Yang R, Gao G, Liu T, Liu S, Li G (2007) Enhanced ability of hemoglobin to carry oxygen by salidroside. Electrochem Commun 9(1):94–96. doi:10.1016/j.elecom.2006.08.042
Wang XD, Wolfbeis OS (2014) Optical methods for sensing and imaging oxygen: materials, spectroscopies and applications. Chem Soc Rev 43(10):3666–3761. doi:10.1039/c4cs00039k
Pan ZQ, Xie J, Liu XJ, Bao N, Gu HY (2014) Direct electron transfer from native human hemoglobin using a glassy carbon electrode modified with chitosan and a poly(N, N-diethylacrylamide) hydrogel containing red blood cells. Microchim Acta 181(11–12):1215–1221. doi:10.1007/s00604-014-1222-9
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(1–2):179–186. doi:10.1007/s00604-010-0392-3
Jia Y, Cui Y, Fei J, Du M, Dai L, Li J, Yang Y (2012) Construction and Evaluation of Hemoglobin-Based Capsules as Blood Substitutes. Adv Funct Mater 22(7):1446–1453. doi:10.1002/adfm.201102737
Ji N, Li XJ, Qiu C, Li GH, Sun QJ, Xiong L (2015) Effects of heat moisture treatment on the physicochemical properties of starch nanoparticles. Carbohydr Polym 117:605–609. doi:10.1016/j.carbpol.2014.10.005
Gao W, Sha B, Zou W, Liang X, Meng X, Xu H, Tang J, Wu D, Xu L, Zhang H (2011) Cationic amylose-encapsulated bovine hemoglobin as a nanosized oxygen carrier. Biomaterials 32(35):9425–9433. doi:10.1016/j.biomaterials.2011.08.046
Sun J, Huang Y, Shi Q, Chen X, Jing X (2009) Oxygen carrier based on hemoglobin/poly(L-lysine)-block-poly(L-phenylalanine) vesicles. Langmuir 25(24):13726–13729. doi:10.1021/la901194k
Dobrunz D, Toma AC, Tanner P, Pfohl T, Palivan CG (2012) Polymer nanoreactors with dual functionality: simultaneous detoxification of peroxynitrite and oxygen transport. Langmuir 28(45):15889–15899. doi:10.1021/la302724m
Laviron E (1979) General expression of the linear potential sweep voltammogram in the case of diffusionless electrochemical systems. J Electroanal Chem Interfacial Electrochem 101(1):19–28. doi:10.1016/S0022-0728(79)80075-3
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(1–2):119–126. doi:10.1016/S0022-0728(01)00669-6
Ren L, Dong J, Cheng X, Xu J, Hu P (2013) Hydrogen peroxide biosensor based on direct electrochemistry of hemoglobin immobilized on gold nanoparticles in a hierarchically porous zeolite. Microchim Acta 180(13–14):1333–1340. doi:10.1007/s00604-013-1064-x
Baghayeri M, Zare EN, Lakouraj MM (2014) Monitoring of hydrogen peroxide using a glassy carbon electrode modified with hemoglobin and a polypyrrole-based nanocomposite. Microchim Acta 182(3–4):771–779. doi:10.1007/s00604-014-1387-2
Pita M, Gutierrez-Sanchez C, Toscano MD, Shleev S, De Lacey AL (2013) Oxygen biosensor based on bilirubin oxidase immobilized on a nanostructured gold electrode. Bioelectrochemistry 94:69–74. doi:10.1016/j.bioelechem.2013.07.001
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(1–2):90–97. doi:10.1016/j.aca.2011.04.032
Zheng R-J, Fang Y-M, Qin S-F, Song J, Wu A-H, Sun J-J (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(2):488–493. doi:10.1016/j.snb.2011.05.005
Lin Z, Liu Y, Chen G (2008) TiO2/Nafion film based electrochemiluminescence for detection of dissolved oxygen. Electrochem Commun 10(10):1629–1632. doi:10.1016/j.elecom.2008.08.015
Luo W, Abbas ME, Zhu L, Zhou W, Li K, Tang H, Liu S, Li W (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(1–2):63–67. doi:10.1016/j.aca.2009.03.024
Acknowledgments
This work was financially supported by the National Natural Science Foundation of China (Grant numbers: 21475070; 21175075), the Natural Science Foundation of Jiangsu Province (Grant number: BK2011047, BK2012651), the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD), and the 226 Scientific Research Project of Nantong City.
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Xiaojun Liu and Zhongqin Pan contributed equally to this work.
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Liu, X., Pan, Z., Dong, Z. et al. Amperometric oxygen biosensor based on hemoglobin encapsulated in nanosized grafted starch particles. Microchim Acta 183, 353–359 (2016). https://doi.org/10.1007/s00604-015-1655-9
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DOI: https://doi.org/10.1007/s00604-015-1655-9