A versatile nanoarray electrode produced from block copolymer thin films for specific detection of proteins

Abstract This work describes how nanostructured thin films obtained from the self-assembly of block copolymers (BCPs) systems can be used as a nanoelectrode array (NEA) that can be programmed to specifically detect targeted molecules. Namely, poly(styrene-b-methacrylate) (PS-b-PMMA) thin films, after removal of PMMA phase, produced regular spaced 560 pores μm-2 with 16 nm of diameter. The nanopores were then chemically modified by the introduction of β-cyclodextrin (β-CD) molecules. By using the supramolecular interaction of β-CD and ferrocene (Fc), the pores could be programed by the introduction of molecules linked to Fc able to interact with target species. In the model system shown here, the linker had a biotin unit, aiming the detection of streptavidin. By changing the linker, other molecules can also be detected. This concept opens a window to many possibilities, including the development of devices for fast and versatile molecule detection.

[1]  Juan J de Pablo,et al.  Characterizing the Three-Dimensional Structure of Block Copolymers via Sequential Infiltration Synthesis and Scanning Transmission Electron Tomography. , 2015, ACS nano.

[2]  V. Rotello,et al.  Fabrication and characterization of nanoelectrode arrays formed via block copolymer self-assembly , 2001 .

[3]  P. Labbé,et al.  Redox strategy for reversible attachment of biomolecules using bifunctional linkers. , 2011, Chemical communications.

[4]  Luca Berdondini,et al.  Addressable nanoelectrode membrane arrays: fabrication and steady-state behavior. , 2007, Analytical chemistry.

[5]  Charles R. Martin,et al.  Nanomaterials: A Membrane-Based Synthetic Approach , 1994, Science.

[6]  C. Stafford,et al.  Nanoscopic Templates from Oriented Block Copolymer Films , 2000 .

[7]  Takashi Ito,et al.  Electrochemical impedance spectroscopy studies of organic-solvent-induced permeability changes in nanoporous films derived from a cylinder-forming diblock copolymer. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[8]  Bhanu Nandan,et al.  Hairy Core-Shell Polymer Nano-objects from Self-Assembled Block Copolymer Structures. , 2015, ACS applied materials & interfaces.

[9]  Jun Li,et al.  Novel Three-Dimensional Electrodes: Electrochemical Properties of Carbon Nanotube Ensembles , 2002 .

[10]  Sarah E. Mastroianni,et al.  Interfacial manipulations: controlling nanoscale assembly in bulk, thin film, and solution block copolymer systems. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[11]  C. Singh,et al.  Morphology, Crystal Structure and Charge Transport in Donor-Acceptor Block Copolymer Thin Films. , 2015, ACS applied materials & interfaces.

[12]  Christopher J. Ellison,et al.  Directed self-assembly of silicon-containing block copolymer thin films. , 2015, ACS applied materials & interfaces.

[13]  Heinrich M. Jaeger,et al.  Hierarchical self-assembly of metal nanostructures on diblock copolymer scaffolds , 2001, Nature.

[14]  Richard G. Compton,et al.  How Much Supporting Electrolyte Is Required to Make a Cyclic Voltammetry Experiment Quantitatively “Diffusional”? A Theoretical and Experimental Investigation , 2009 .

[15]  Yongxin Li,et al.  Surface chemical functionalization of cylindrical nanopores derived from a polystyrene-poly(methylmethacrylate) diblock copolymer via amidation. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[16]  Ting Xu,et al.  The influence of molecular weight on nanoporous polymer films , 2001 .

[17]  M. Hillmyer,et al.  Templating Nanoporous Polymers with Ordered Block Copolymers , 2008 .

[18]  Nanoscale adhesion, friction and wear of proteins on polystyrene. , 2013, Colloids and surfaces. B, Biointerfaces.

[19]  P. Ugo,et al.  Ionomer-coated electrodes and nanoelectrode ensembles as electrochemical environmental sensors: recent advances and prospects. , 2002, Chemphyschem : a European journal of chemical physics and physical chemistry.

[20]  P. Ugo,et al.  Gold nanoelectrode ensembles for direct trace electroanalysis of iodide. , 2006, Analytica chimica acta.

[21]  K. Hashimoto,et al.  Facile preparation of nanoelectrode ensembles using amphiphilic block copolymer film. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[22]  K. Guarini,et al.  Ultrahigh-density nanowire arrays grown in self-assembled diblock copolymer templates. , 2000, Science.

[23]  Lateef U. Syed,et al.  Electrochemical Protease Biosensor Based on Enhanced AC Voltammetry Using Carbon Nanofiber Nanoelectrode Arrays. , 2013, The journal of physical chemistry. C, Nanomaterials and interfaces.

[24]  K. W. Gotrik,et al.  Thin Film Morphologies of Bulk-Gyroid Polystyrene-block-polydimethylsiloxane under Solvent Vapor Annealing , 2014 .

[25]  M. Perego,et al.  High aspect ratio PS-b-PMMA block copolymer masks for lithographic applications. , 2014, ACS applied materials & interfaces.

[26]  Hao Yan,et al.  DNA-templated self-assembly of protein and nanoparticle linear arrays. , 2004, Journal of the American Chemical Society.

[27]  M. Wark,et al.  Functionalized mesoporous silica films as a matrix for anchoring electrochemically active guests. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[28]  Yongxin Li,et al.  Electrochemical characterization of nanoporous films fabricated from a polystyrene-poly(methylmethacrylate) diblock copolymer: monitoring the removal of the PMMA domains and exploring the functional groups on the nanopore surface. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[29]  W A Lopes,et al.  Nonequilibrium self-assembly of metals on diblock copolymer templates. , 2002, Physical review. E, Statistical, nonlinear, and soft matter physics.

[30]  Schick,et al.  Stable and unstable phases of a diblock copolymer melt. , 1994, Physical review letters.

[31]  M. Perego,et al.  Fine tuning of lithographic masks through thin films of PS-b-PMMA with different molar mass by rapid thermal processing. , 2014, ACS applied materials & interfaces.

[32]  P. Ugo,et al.  Diffusion regimes at nanoelectrode ensembles in different ionic liquids , 2010 .

[33]  Takashi Ito,et al.  Linker-based control of electron propagation through ferrocene moieties covalently anchored onto insulator-based nanopores derived from a polystyrene-poly(methylmethacrylate) diblock copolymer. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[34]  M. Tuominen,et al.  A Route to Nanoscopic SiO2 Posts via Block Copolymer Templates , 2001 .

[35]  Alenka Vesel,et al.  Adsorption of protein streptavidin to the plasma treated surface of polystyrene , 2012 .

[36]  Takashi Ito,et al.  Complexation-induced control of electron propagation based on bounded diffusion through nanopore-tethered ferrocenes. , 2013, Journal of the American Chemical Society.

[37]  Charles R. Martin,et al.  Template Synthesis of Electronically Conductive Polymer Nanostructures , 1995 .

[38]  M. Morris,et al.  Swift nanopattern formation of PS-b-PMMA and PS-b-PDMS block copolymer films using a microwave assisted technique. , 2013, ACS nano.

[39]  Christopher K. Ober,et al.  Block copolymer patterns and templates , 2006 .

[40]  U. Steiner,et al.  Soft-etch mesoporous hole-conducting block copolymer templates. , 2010, ACS nano.

[41]  M. Perego,et al.  Ultrathin random copolymer-grafted layers for block copolymer self-assembly. , 2015, ACS applied materials & interfaces.

[42]  Bhanu Nandan,et al.  High-Resolution Metal Nanopatterning by Means of Switchable Block Copolymer Templates. , 2015, ACS applied materials & interfaces.

[43]  C. Laberty‐Robert,et al.  Design, Synthesis, and Properties of Inorganic and Hybrid Thin Films Having Periodically Organized Nanoporosity† , 2008 .

[44]  K. Yager,et al.  Self-assembled phases of block copolymer blend thin films. , 2014, ACS nano.

[45]  R. Riopelle,et al.  Efficient Perfacial Derivatization of Cyclodextrins at the Primary Face , 1996 .

[46]  D. Arrigan.  Nanoelectrodes, nanoelectrode arrays and their applications. , 2004, The Analyst.

[47]  Zhi‐Kang Xu,et al.  Systematic Investigation on the Formation of Honeycomb-Patterned Porous Films from Amphiphilic Block Copolymers , 2015 .

[48]  Jin Kon Kim,et al.  Precise Control of Nanopore Size in Thin Film Using Mixtures of Asymmetric Block Copolymer and Homopolymer , 2003 .

[49]  P. Labbé,et al.  Electrochemically controlled adsorption of Fc-functionalized polymers on beta-CD-modified self-assembled monolayers. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[50]  P. Labbé,et al.  Redox‐Driven Host–Guest Interactions Allow the Controlled Release of Captured Cells on RGD‐Functionalized Surfaces , 2014, Chembiochem : a European journal of chemical biology.

[51]  C. R. Martin,et al.  Template‐Fabricated Gold Nanowires and Nanotubes , 2003 .

[52]  C. Grant Willson,et al.  Block Copolymer Lithography , 2014 .

[53]  P. Ugo,et al.  Modification of nanoelectrode ensembles by thiols and disulfides to prevent non specific adsorption of proteins , 2011 .

[54]  M. Porter,et al.  Characterization and optimization of mixed thiol-derivatized beta-cyclodextrin/pentanethiol monolayers with high-density guest-accessible cavities. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[55]  Takashi Ito,et al.  Electrochemical characterization of recessed nanodisk-array electrodes prepared from track-etched membranes. , 2006, Analytical chemistry.

[56]  M. S. Onses.  Fabrication of nanopatterned poly(ethylene glycol) brushes by molecular transfer printing from poly(styrene-block-methyl methacrylate) films to generate arrays of Au nanoparticles. , 2015, Langmuir : the ACS journal of surfaces and colloids.

[57]  Yongxin Li,et al.  Effects of substrate roughness on the orientation of cylindrical domains in thin films of a polystyrene–poly(methylmethacrylate) diblock copolymer studied using atomic force microscopy and cyclic voltammetry , 2009 .

[58]  Thomas P. Russell,et al.  Temperature dependence of the interaction parameter of polystyrene and poly(methyl methacrylate) , 1990 .

[59]  W. Hinsberg,et al.  Block copolymer based nanostructures: materials, processes, and applications to electronics. , 2010, Chemical reviews.

[60]  Yu Xuan,et al.  Morphologies in solvent-annealed thin films of symmetric diblock copolymer. , 2006, The Journal of chemical physics.