Solution growth of 3D MnO2 mesh comprising 1D nanofibres as a novel sensor for selective and sensitive detection of biomolecules.

This work is the first report describing the solution grown 3D manganese oxide nanofibrous (MnO2 NFs) mesh and its potential for the simultaneous detection of biomolecules such as ascorbic acid and uric acid. The mesh is synthesized by a facile, one-pot, and cost-effective hydrothermal approach without using any template or structure directing compound. The morphology consists of randomly placed nanofibres possessing a diameter in the range of 10-25 nm, and length of several micron; constituting a highly porous and flexible material. The electrochemical potential was examined by recording cyclic voltammetry signals towards ascorbic acid and uric acid. The special mesh morphology offers a large surface area to promote enhanced electrochemical activity, and also provided a macroporous network that supported efficient mass transport. Additionally, the strong electronic cloud and roughness of MnO2 NFs mesh facilitated the fast oxidation of species at very low potential. The lower detection limit was found to be 1.33 µM (S/N = 3) and 1.03 µM (S/N = 3) for ascorbic acid and uric acid, respectively. The MnO2 NFs mesh modified electrodes can robustly differentiate both of them by giving well separate signals (Δ = 500 mV) indicating capability of the material towards selective detection. The sensor has been successfully applied to human blood and urine samples and the recoveries were found statistically significant. These results demonstrate the practical feasibility of 3D mesh to develop sensors for the accurate diagnosis of clinically important molecules.

[1]  Ulrich Schlecht,et al.  V2O5 nanofibres: novel gas sensors with extremely high sensitivity and selectivity to amines , 2005 .

[2]  Na Li,et al.  MnO2-modified persistent luminescence nanoparticles for detection and imaging of glutathione in living cells and in vivo. , 2014, Chemistry.

[3]  Jimin Liang,et al.  Radiolabeled, Antibody-Conjugated Manganese Oxide Nanoparticles for Tumor Vasculature Targeted Positron Emission Tomography and Magnetic Resonance Imaging. , 2017, ACS applied materials & interfaces.

[4]  P. Gai,et al.  Synthesis of a three-layered SiO2@Au nanoparticle@polyaniline nanocomposite and its application in simultaneous electrochemical detection of uric acid and ascorbic acid. , 2016, Journal of materials chemistry. B.

[5]  Q. Wei,et al.  Facile synthesis of cuprous oxide nanowires decorated graphene oxide nanosheets nanocomposites and its application in label-free electrochemical immunosensor. , 2017, Biosensors & bioelectronics.

[6]  Seon-Jin Choi,et al.  Heterogeneous Sensitization of Metal-Organic Framework Driven Metal@Metal Oxide Complex Catalysts on an Oxide Nanofiber Scaffold Toward Superior Gas Sensors. , 2016, Journal of the American Chemical Society.

[7]  Jin Hyeok Kim,et al.  Electrospinning: A versatile technique for making of 1D growth of nanostructured nanofibers and its applications: an experimental approach , 2017 .

[8]  Dianyun Zhao,et al.  A highly sensitive and stable electrochemical sensor for simultaneous detection towards ascorbic acid, dopamine, and uric acid based on the hierarchical nanoporous PtTi alloy. , 2016, Biosensors & bioelectronics.

[9]  Xuan Zhang,et al.  One-pot facile fabrication of graphene-zinc oxide composite and its enhanced sensitivity for simultaneous electrochemical detection of ascorbic acid, dopamine and uric acid , 2016 .

[10]  Hee‐Tak Kim,et al.  Dimensional effects of nanostructured Mg/MgH2 for hydrogen storage applications: A review , 2017 .

[11]  P. Yao,et al.  Metal nanodroplets catalyzed growth of ZnS nanowires with a high aspect ratio via long-pulse-width laser ablation in the liquid phase , 2017 .

[12]  J. Heremans,et al.  Continuous-feed nanocasting process for the synthesis of bismuth nanowire composites. , 2017, Chemical communications.

[13]  J. Rusling,et al.  Robust Mesoporous Manganese Oxide Catalysts for Water Oxidation , 2015 .

[14]  Wei Wei,et al.  Fabrication of lithium manganese oxide nanoribbons by electrospinning: A general strategy and formation mechanism , 2016 .

[15]  G. M. Rao,et al.  Synthesis and electrocatalytic properties of manganese dioxide for non-enzymatic hydrogen peroxide sensing , 2015 .

[16]  G. Yushin,et al.  Transformation of bulk alloys to oxide nanowires , 2017, Science.

[17]  Dianping Tang,et al.  Novel photoelectrochemical immunosensor for disease-related protein assisted by hemin/G-quadruplex-based DNAzyme on gold nanoparticles to enhance cathodic photocurrent on p-CuBi2O4 semiconductor. , 2017, Biosensors & bioelectronics.

[18]  Raghava Reddy Kakarla,et al.  Advanced electrochemical energy storage supercapacitors based on the flexible carbon fiber fabric-coated with uniform coral-like MnO2 structured electrodes , 2017 .

[19]  Youyu Zhang,et al.  Gold nanoclusters as switch-off fluorescent probe for detection of uric acid based on the inner filter effect of hydrogen peroxide-mediated enlargement of gold nanoparticles. , 2017, Biosensors & bioelectronics.

[20]  Yadong Li,et al.  Synthesis and formation mechanism of manganese dioxide nanowires/nanorods. , 2003, Chemistry.

[21]  Zhiyong Zhang,et al.  Uniform ZnO nanowire arrays: Hydrothermal synthesis, formation mechanism and field emission performance , 2015 .

[22]  G. Cuniberti,et al.  Electron-beam induced synthesis of nanostructures: a review. , 2016, Nanoscale.

[23]  Z. Ghazi,et al.  The influence of the substituent on the phenol oxidation rate and reactive species in cubic MnO2 catalytic ozonation , 2016 .

[24]  X. Hou,et al.  Simultaneously electrochemical detection of uric acid and ascorbic acid using glassy carbon electrode modified with chrysanthemum-like titanium nitride , 2017 .

[25]  J. Strunk,et al.  Manganese Oxides in Heterogeneous (Photo)Catalysis: Possibilities and Challenges , 2015 .

[26]  Mingji Li,et al.  Electrochemical biosensor based on one-dimensional MgO nanostructures for the simultaneous determination of ascorbic acid, dopamine, and uric acid , 2014 .

[27]  O. Akpolat,et al.  Ascorbic Acid Detection with MnO2-Modified GCPE , 2016, Food Analytical Methods.

[28]  Hongying Liu,et al.  Synthesis of ZnO nanorods-Au nanoparticles hybrids via in-situ plasma sputtering-assisted method for simultaneous electrochemical sensing of ascorbic acid and uric acid , 2016 .

[29]  T. Dang,et al.  Fast degradation of dyes in water using manganese-oxide-coated diatomite for environmental remediation , 2016 .

[30]  J. Arbiol,et al.  Unveiling the Nucleation and Coarsening Mechanisms of Solution-Derived Self-Assembled Epitaxial Ce0.9Gd0.1O2–y Nanostructures , 2017 .

[31]  M. K. Naskar,et al.  Bi-template assisted synthesis of mesoporous manganese oxide nanostructures: Tuning properties for efficient CO oxidation. , 2016, Physical chemistry chemical physics : PCCP.

[32]  M. F. Cerqueira,et al.  Tunable Performance of Manganese Oxide Nanostructures as MRI Contrast Agents. , 2017, Chemistry.

[33]  H. Bagheri,et al.  A novel electrochemical platform for sensitive and simultaneous determination of dopamine, uric acid and ascorbic acid based on Fe3O4SnO2Gr ternary nanocomposite , 2017 .

[34]  Xiujian Zhao,et al.  Tremendous effect of the morphology of birnessite-type manganese oxide nanostructures on catalytic activity. , 2014, ACS applied materials & interfaces.

[35]  R. Karthikeyan,et al.  Fabrication of nitrogen-doped carbon dots for screening the purine metabolic disorder in human fluids. , 2017, Biosensors & bioelectronics.

[36]  R. Ma,et al.  Layered MnO2 Nanobelts: Hydrothermal Synthesis and Electrochemical Measurements , 2004 .

[37]  Qiyuan He,et al.  Recent Advances in Cantilever-Free Scanning Probe Lithography: High-Throughput, Space-Confined Synthesis of Nanostructures and Beyond. , 2017, ACS nano.

[38]  G. Campet,et al.  Hydrothermal Synthesis and Pseudocapacitance Properties of α-MnO2 Hollow Spheres and Hollow Urchins , 2007 .

[39]  Hui Huang,et al.  Structure-property relationship of bifunctional MnO2 nanostructures: highly efficient, ultra-stable electrochemical water oxidation and oxygen reduction reaction catalysts identified in alkaline media. , 2014, Journal of the American Chemical Society.

[40]  Guangxia Yu,et al.  A facile and practical biosensor for choline based on manganese dioxide nanoparticles synthesized in-situ at the surface of electrode by one-step electrodeposition. , 2016, Talanta.

[41]  N. Yao,et al.  Stable synthesis of few-layered boron nitride nanotubes by anodic arc discharge , 2017, Scientific Reports.

[42]  Weifeng Wei,et al.  Manganese oxide-based materials as electrochemical supercapacitor electrodes. , 2011, Chemical Society reviews.

[43]  S. Prasad,et al.  Surface modification of ZnO nanostructured electrodes with thiol and phosphonic acid moieties for biosensing applications , 2017 .

[44]  Hong-Yuan Chen,et al.  Ascorbic acid sensor based on ion-sensitive field-effect transistor modified with MnO2 nanoparticles , 2004 .