A novel nitrite biosensor based on the direct electrochemistry of horseradish peroxidase immobilized on porous Co 3 O 4 nanosheets and reduced graphene oxide composite modified electrode

Abstract Porous Co3O4 hexagonal nanosheets (PCHNSs) with a well-defined morphology have been synthesized successfully via a hydrothermal process and followed by calcinations. Co3O4 nanosheets immobilizing horseradish peroxidase (HRP), together with reduced graphene oxide, have been used to modify glassy carbon electrode to fabricate a mediator-free biosensor. The morphology and structure of PCHNSs are studied by XRD, FESEM, and HRTEM techniques. Spectroscopic and electrochemical results reveal that Co3O4/rGO composite film is an excellent immobilization matrix with biocompatibility for enzymes, affording good enzymes’ bioactivity and stability. Meanwhile, due to the unique structure of the modified electrode, the direct electron transfer of HRP is facilitated and the prepared nitrite biosensors display good performance—a wide linear range of 1–5400 μM, an extremely low limit of detection (LOD) as 0.21 μM and a limit of quantification as (LOQ) as 0.58 μM. This work suggests that Co3O4/rGO composite film is a potential matrix for enzymes’ immobilization and biosensors’ preparation.

[1]  Tinglin Huang,et al.  Direct electrochemistry and electrocatalysis of hemoglobin in composite film based on ionic liquid and NiO microspheres with different morphologies. , 2011, Biosensors & bioelectronics.

[2]  Akhilesh Kumar Mishra,et al.  Graphene and Beyond Graphene MoS2: A New Window in Surface-Plasmon-Resonance-Based Fiber Optic Sensing , 2016 .

[3]  Xiaoling Xiao,et al.  Single-crystal CeO2 nanocubes used for the direct electron transfer and electrocatalysis of horseradish peroxidase. , 2009, Biosensors & bioelectronics.

[4]  Hui Chen,et al.  Peroxynitrous-acid-induced chemiluminescence of fluorescent carbon dots for nitrite sensing. , 2011, Analytical chemistry.

[5]  S. Dou,et al.  Single Crystalline Co3O4 Nanocrystals Exposed with Different Crystal Planes for Li-O2 Batteries , 2014, Scientific Reports.

[6]  Jianbin Zheng,et al.  Direct electrochemistry and electrocatalysis of heme-proteins immobilized in porous carbon nanofiber/room-temperature ionic liquid composite film , 2010 .

[7]  Lixian Sun,et al.  Direct electrochemistry and enhanced electrocatalysis of horseradish peroxidase based on flowerlike ZnO–gold nanoparticle–Nafion nanocomposite , 2009 .

[8]  R. Mallavia,et al.  Immobilization and Characterization of 2,3-diaminonaphthalene/cyclodextrin Complexes in a Sol–Gel Matrix: A New Fluorimetric Sensor for Nitrite , 2008, Journal of Fluorescence.

[9]  Qin Xu,et al.  Direct electrochemistry of horseradish peroxidase based on biocompatible carboxymethyl chitosan-gold nanoparticle nanocomposite. , 2006, Biosensors & bioelectronics.

[10]  Lo Gorton,et al.  Comment on "Direct electrochemistry and electrocatalysis of heme proteins entrapped in agarose hydrogel films in room-temperature ionic liquids". , 2005, Langmuir : the ACS journal of surfaces and colloids.

[11]  Lan Yang,et al.  Direct electrochemistry and electrocatalysis of horseradish peroxidase in alpha-zirconium phosphate nanosheet film. , 2008, Bioelectrochemistry.

[12]  Miller,et al.  A multicomponent mobile phase for ion chromatography applied to the separation of anions from the residue of low explosives , 2000, Analytical chemistry.

[13]  Wensheng Yang,et al.  Direct electrochemistry and electrocatalysis based on a film of horseradish peroxidase intercalated into Ni-Al layered double hydroxide nanosheets. , 2008, Biosensors & bioelectronics.

[14]  L. Backer,et al.  A Review of Nitrates in Drinking Water: Maternal Exposure and Adverse Reproductive and Developmental Outcomes , 2005, Environmental health perspectives.

[15]  Fen Xu,et al.  Glucose biosensor based on electrodeposition of platinum nanoparticles onto carbon nanotubes and immobilizing enzyme with chitosan-SiO(2) sol-gel. , 2008, Biosensors & bioelectronics.

[16]  A. McNeil,et al.  Modifying a known gelator scaffold for nitrite detection. , 2014, Chemical communications.

[17]  Jin Huang,et al.  An excellent enzyme biosensor based on Sb-doped SnO2 nanowires. , 2010, Biosensors & bioelectronics.

[18]  J. Greaves,et al.  Nitrite Reduction by Myoglobin in Surfactant Films , 1997 .

[19]  Jinghong Li,et al.  Hemoglobin entrapped within a layered spongy Co3O4 based nanocomposite featuring direct electron transfer and peroxidase activity , 2007 .

[20]  P. I. Reed,et al.  GASTRIC JUICE N-NITROSAMINES IN HEALTH AND GASTRODUODENAL DISEASE , 1981, The Lancet.

[21]  L. Nie,et al.  Amperometric glucose biosensor based on adsorption of glucose oxidase at platinum nanoparticle-modified carbon nanotube electrode. , 2004, Analytical biochemistry.

[22]  Y. Long,et al.  Core-shell structured Ag@C for direct electrochemistry and hydrogen peroxide biosensor applications. , 2013, Biosensors & bioelectronics.

[23]  J. Xu,et al.  Direct electrochemistry of horseradish peroxidase on TiO(2) nanotube arrays via seeded-growth synthesis. , 2008, Biosensors & bioelectronics.

[24]  S. Luis,et al.  Cross-linked poly(2-hydroxyethylmethacrylate) films doped with 1,2-diaminoanthraquinone (DAQ) as efficient materials for the colorimetric sensing of nitric oxide and nitrite anion , 2006 .

[25]  Xiurong Yang,et al.  Use of fluorescent gold nanoclusters for the construction of a NAND logic gate for nitrite. , 2013, Chemical communications.

[26]  Chenhui Yang,et al.  A novel nitrite biosensor based on the direct electrochemistry of hemoglobin immobilized on MXene-Ti3C2 , 2015 .

[27]  J. Fei,et al.  Biocompatible hybrid film of β-cyclodextrin and ionic liquids: A novel platform for electrochemical biosensing , 2011 .

[28]  Wensheng Yang,et al.  Nanosheet-based titania microspheres with hollow core-shell structure encapsulating horseradish peroxidase for a mediator-free biosensor. , 2011, Biomaterials.

[29]  Ling Huang,et al.  Room-temperature synthesis of Co(OH)2 hexagonal sheets and their topotactic transformation into Co3O4 (111) porous structure with enhanced lithium-storage properties , 2013 .

[30]  Qingshan Lu,et al.  Immobilization and catalytic activity of horseradish peroxidase on molybdenum disulfide nanosheets modified electrode , 2013 .

[31]  P. J. Ollivier,et al.  Layer-by-Layer Assembly of Ultrathin Composite Films from Micron-Sized Graphite Oxide Sheets and Polycations , 1999 .

[32]  L. Qu,et al.  Direct electrochemistry and electrocatalysis of horseradish peroxidase immobilized in graphene oxide–Nafion nanocomposite film , 2012 .

[33]  I. Naranjo-Rodríguez,et al.  Graphite grains studded with silver nanoparticles: description and application in promoting direct biocatalysis between heme protein and the resulting carbon paste electrode. , 2012, Colloids and surfaces. B, Biointerfaces.

[34]  Banshi D. Gupta,et al.  SPR based fiber optic sensor for refractive index sensing with enhanced detection accuracy and figure of merit in visible region , 2015 .

[35]  Nengqin Jia,et al.  Direct electrochemistry and electrocatalysis of horseradish peroxidase based on halloysite nanotubes/chitosan nanocomposite film , 2010 .

[36]  F. Gao,et al.  Direct electrochemistry of horseradish peroxidase on graphene-modified electrode for electrocatalytic reduction towards H2O2 , 2011 .

[37]  Qing Zhang,et al.  Porous nanosheet-based ZnO microspheres for the construction of direct electrochemical biosensors. , 2008, Biosensors & bioelectronics.

[38]  Banshi D. Gupta,et al.  Fabrication and characterization of a surface plasmon resonance based fiber optic sensor using gel entrapment technique for the detection of low glucose concentration , 2013 .

[39]  Hui Liu,et al.  A novel nitrite biosensor based on the direct electron transfer hemoglobin immobilized in the WO3 nanowires with high length-diameter ratio. , 2015, Materials science & engineering. C, Materials for biological applications.

[40]  W. Cho,et al.  Electrochemical Reduction of NO by Myoglobin in Surfactant Film: Characterization and Reactivity of The Nitroxyl (NO-) Adduct , 1998 .

[41]  Hian Kee Lee,et al.  Direct electrochemistry and electrocatalysis of hemoglobin in nafion/carbon nanochip film on glassy carbon electrode. , 2009, The journal of physical chemistry. B.

[42]  Wei Sun,et al.  Urchinlike MnO2 nanoparticles for the direct electrochemistry of hemoglobin with carbon ionic liquid electrode. , 2011, Biosensors & bioelectronics.

[43]  F. Gao,et al.  Imidazoline derivative templated synthesis of broccoli-like Bi2S3 and its electrocatalysis towards the direct electrochemistry of hemoglobin. , 2015, Biosensors & bioelectronics.

[44]  J. Gabbay,et al.  Rapid spectrophotometric micro-determination of nitrites in water. , 1977, The Analyst.

[45]  P. Hegde,et al.  Determination of nitrite by simple diazotization method , 2003 .