Surface functionalized halloysite nanotubes decorated with silver nanoparticles for enzyme immobilization and biosensing.

Improving enzyme immobilization with high loading capacity and achieving direct electron transfer (DET) between the enzyme and the electrode surface is key to designing highly sensitive enzymatic electrochemical biosensors. Herein, we report a novel approach based on the selective modification of the outer surface of halloysite nanotubes (HNTs) that supports silver nanoparticles (AgNPs) to obtain a hybrid nanocomposite. AgNPs of about 10 nm average size could be uniformly supported on silane-modified HNTs through in situ reduction of Ag+ ions. The resultant nanocomposite shows an excellent support capability for the effective immobilization and electrical wiring of redox enzyme glucose oxidase (GOx). The GOx immobilized HNT/AgNPs were deposited on the glassy carbon electrode (GCE) and utilized for the bioelectrocatalyzed electrochemical detection of glucose. The GOx modified composite electrodes show glucose sensitivity as high as 5.1 μA mM-1 cm-2, which is higher than for the electrodes prepared without surface functionalization.

[1]  Dongil Lee,et al.  Ionic liquid of a gold nanocluster: a versatile matrix for electrochemical biosensors. , 2014, ACS nano.

[2]  Yuehe Lin,et al.  Glucose Biosensors Based on Carbon Nanotube Nanoelectrode Ensembles , 2004 .

[3]  Jing Ouyang,et al.  Palladium nanoparticles deposited on silanized halloysite nanotubes: synthesis, characterization and enhanced catalytic property , 2013, Scientific Reports.

[4]  Hui Liu,et al.  Graphene oxide as a matrix for enzyme immobilization. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[5]  R. Zbořil,et al.  A glucose biosensor based on surface active maghemite nanoparticles. , 2013, Biosensors & bioelectronics.

[6]  M. Housaindokht,et al.  Construction of an Amperometric Glucose Biosensor by Immobilization of Glucose Oxidase on Nanocomposite at the Surface of FTO Electrode , 2014 .

[7]  Michael Woerner,et al.  Enzyme-capped relay-functionalized mesoporous carbon nanoparticles: effective bioelectrocatalytic matrices for sensing and biofuel cell applications. , 2013, ACS nano.

[8]  Lijia Pan,et al.  Rational design and applications of conducting polymer hydrogels as electrochemical biosensors. , 2015, Journal of materials chemistry. B.

[9]  M. Meyyappan,et al.  Chitosan supported silver nanowires as a platform for direct electrochemistry and highly sensitive electrochemical glucose biosensing , 2016 .

[10]  Philippe Cinquin,et al.  Mediatorless high-power glucose biofuel cells based on compressed carbon nanotube-enzyme electrodes , 2011, Nature communications.

[11]  Mingliang Du,et al.  Green synthesis of halloysite nanotubes supported Ag nanoparticles for photocatalytic decomposition of methylene blue , 2012 .

[12]  Sanat K. Kumar,et al.  Surface-mediated protein disaggregation. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[13]  Charles R. Martin,et al.  Synthesis of polymeric microcapsule arrays and their use for enzyme immobilization , 1994, Nature.

[14]  Igor L. Medintz,et al.  Functionalizing nanoparticles with biological molecules: developing chemistries that facilitate nanotechnology. , 2013, Chemical reviews.

[15]  Longwei Yin,et al.  Platinum nanoparticle modified polyaniline-functionalized boron nitride nanotubes for amperometric glucose enzyme biosensor. , 2011, ACS applied materials & interfaces.

[16]  Hongyu Zhou,et al.  Functionalized carbon nanotubes specifically bind to alpha-chymotrypsin's catalytic site and regulate its enzymatic function. , 2009, Nano letters.

[17]  I. Sanchez,et al.  Chitosan/silver nanocomposites: Synergistic antibacterial action of silver nanoparticles and silver ions , 2015 .

[18]  Shuhui Zhong,et al.  TiO2/Halloysite Composites Codoped with Carbon and Nitrogen from Melamine and Their Enhanced Solar-Light-Driven Photocatalytic Performance , 2015 .

[19]  O. A. Fuentes,et al.  Temperature-induced Au nanostructure synthesis in a nonaqueous deep-eutectic solvent for high performance electrocatalysis , 2015 .

[20]  X. Lou,et al.  Hierarchically structured one-dimensional TiO2 for protein immobilization, direct electrochemistry, and mediator-free glucose sensing. , 2011, ACS nano.

[21]  Di Li,et al.  A silicon nanowire-based electrochemical glucose biosensor with high electrocatalytic activity and sensitivity. , 2010, Nanoscale.

[22]  Chengdong Zhang,et al.  Activity of catalase adsorbed to carbon nanotubes: effects of carbon nanotube surface properties. , 2013, Talanta.

[23]  C. Sicard,et al.  Design of metal organic framework-enzyme based bioelectrodes as a novel and highly sensitive biosensing platform. , 2015, Journal of materials chemistry. B.

[24]  Ping Wang,et al.  Challenges in biocatalysis for enzyme-based biofuel cells. , 2006, Biotechnology advances.

[25]  D. Porath,et al.  Wiring of redox enzymes on three dimensional self-assembled molecular scaffold. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[26]  K. Stevenson,et al.  Influence of surface adsorption on the interfacial electron transfer of flavin adenine dinucleotide and glucose oxidase at carbon nanotube and nitrogen-doped carbon nanotube electrodes. , 2013, Analytical chemistry.

[27]  K. Jiao,et al.  Unadulterated Glucose Biosensor Based on Direct Electron Transfer of Glucose Oxidase Encapsulated Chitosan Modified Glassy Carbon Electrode , 2008 .

[28]  J. Narang,et al.  Construction of a triglyceride amperometric biosensor based on chitosan-ZnO nanocomposite film. , 2011, International journal of biological macromolecules.

[29]  Daniel N. Tran,et al.  Perspective of Recent Progress in Immobilization of Enzymes , 2011 .

[30]  Xiaocheng Jiang,et al.  Nanoparticle facilitated extracellular electron transfer in microbial fuel cells. , 2014, Nano letters.

[31]  P. Das,et al.  Covalently functionalized single-walled carbon nanotubes at reverse micellar interface: a strategy to improve lipase activity. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[32]  M. Lyons,et al.  Immobilized enzyme-single-wall carbon nanotube composites for amperometric glucose detection at a very low applied potential. , 2008, Chemical communications.

[33]  J. Ge,et al.  Facile synthesis of multiple enzyme-containing metal-organic frameworks in a biomolecule-friendly environment. , 2015, Chemical communications.

[34]  Plamen Atanassov,et al.  Engineering of glucose oxidase for direct electron transfer via site-specific gold nanoparticle conjugation. , 2011, Journal of the American Chemical Society.

[35]  Itamar Willner,et al.  Long-range electrical contacting of redox enzymes by SWCNT connectors. , 2004, Angewandte Chemie.

[36]  Zongwen Liu,et al.  Organosilane functionalization of halloysite nanotubes for enhanced loading and controlled release , 2012, Nanotechnology.

[37]  Rıfat Emrah Özel,et al.  Single Cell "Glucose Nanosensor" Verifies Elevated Glucose Levels in Individual Cancer Cells. , 2016, Nano letters.

[38]  Ravi S Kane,et al.  Structure, function, and stability of enzymes covalently attached to single-walled carbon nanotubes. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[39]  Itamar Willner,et al.  Nano-engineered flavin-dependent glucose dehydrogenase/gold nanoparticle-modified electrodes for glucose sensing and biofuel cell applications. , 2011, ACS nano.

[40]  M. Stutzmann,et al.  Functional Polymer Brushes on Diamond as a Platform for Immobilization and Electrical Wiring of Biomolecules , 2013 .

[41]  P. Khiew,et al.  A bio-electrochemical sensing platform for glucose based on irreversible, non-covalent pi–pi functionalization of graphene produced via a novel, green synthesis method , 2015 .

[42]  Y. Lvov,et al.  Clay nanotube encapsulation for functional biocomposites. , 2014, Advances in colloid and interface science.

[43]  Enhanced Charge Transport in Enzyme-Wired Organometallic Block Copolymers for Bioenergy and Biosensors , 2012 .

[44]  Bing Zhang,et al.  Surface modification of halloysite nanotubes with dopamine for enzyme immobilization. , 2013, ACS applied materials & interfaces.

[45]  Yi Shi,et al.  A nanostructured conductive hydrogels-based biosensor platform for human metabolite detection. , 2015, Nano letters.

[46]  Rajesh R Naik,et al.  Enzyme immobilization in a biomimetic silica support , 2004, Nature Biotechnology.

[47]  Luis M Liz-Marzán,et al.  Plasmonic nanosensors with inverse sensitivity by means of enzyme-guided crystal growth. , 2018, Nature materials.

[48]  A. Tang,et al.  Applications and interfaces of halloysite nanocomposites , 2016 .

[49]  S. Das,et al.  A facile approach to fabricate halloysite/metal nanocomposites with preformed and in situ synthesized metal nanoparticles: a comparative study of their enhanced catalytic activity. , 2015, Dalton transactions.

[50]  K. Hwa,et al.  Synthesis of zinc oxide nanoparticles on graphene-carbon nanotube hybrid for glucose biosensor applications. , 2014, Biosensors & bioelectronics.

[51]  G. Luna‐Bárcenas,et al.  Structure and Properties of Chitosan-silver Nanoparticles Nanocomposites , 2015 .

[52]  Ruoxia Zhao,et al.  ENHANCING DIRECT ELECTRON TRANSFER OF GLUCOSE OXIDASE USING A GOLD NANOPARTICLE |TITANATE NANOTUBE NANOCOMPOSITE ON A BIOSENSOR , 2015 .

[53]  Viviana Scognamiglio,et al.  Nanotechnology in glucose monitoring: advances and challenges in the last 10 years. , 2013, Biosensors & bioelectronics.

[54]  David M J S Bowman,et al.  Flammable biomes dominated by eucalypts originated at the Cretaceous-Palaeogene boundary. , 2011, Nature communications.

[55]  J. Dupont,et al.  Biosensor based on platinum nanoparticles dispersed in ionic liquid and laccase for determination of adrenaline , 2009 .

[56]  G. Nöll,et al.  Strategies for "wiring" redox-active proteins to electrodes and applications in biosensors, biofuel cells, and nanotechnology. , 2011, Chemical Society reviews.

[57]  Itamar Willner,et al.  "Plugging into Enzymes": Nanowiring of Redox Enzymes by a Gold Nanoparticle , 2003, Science.