Skip to main content
U.S. Department of Energy
Office of Scientific and Technical Information

Fabrication of Self-Cleaning, Reusable Titania Templates for Nanometer and Micrometer Scale Protein Patterning

Journal Article · · ACS Nano
 [1];  [2];  [2];  [3];  [4];  [3];  [4];  [4];  [2]
  1. Univ. of Sheffield (United Kingdom); Agency for Science, Technology and Research (A*STAR) (Republic of Singapore). Inst. of Materials Research and Engineering (IMRE)
  2. Univ. of Sheffield (United Kingdom)
  3. Univ. of Sheffield, Western Bank (United Kingdom)
  4. Agency for Science, Technology and Research (A*STAR) (Republic of Singapore). Inst. of Materials Research and Engineering (IMRE)
The photocatalytic self-cleaning characteristics of titania facilitate the fabrication of reuseable templates for protein nanopatterning. In this work, titania nanostructures were fabricated over square centimeter areas by interferometric lithography (IL) and nanoimprint lithography (NIL). With the use of a Lloyd’s mirror two-beam interferometer, self-assembled monolayers of alkylphosphonates adsorbed on the native oxide of a Ti film were patterned by photocatalytic nanolithography. In regions exposed to a maximum in the interferogram, the monolayer was removed by photocatalytic oxidation. In regions exposed to an intensity minimum, the monolayer remained intact. After exposure, the sample was etched in piranha solution to yield Ti nanostructures with widths as small as 30 nm. NIL was performed by using a silicon stamp to imprint a spin-cast film of titanium dioxide resin; after calcination and reactive ion etching, TiO2 nanopillars were formed. For both fabrication techniques, subsequent adsorption of an oligo(ethylene glycol) functionalized trichlorosilane yielded an entirely passive, protein-resistant surface. Near-UV exposure caused removal of this protein-resistant film from the titania regions by photocatalytic degradation, leaving the passivating silane film intact on the silicon dioxide regions. Proteins labeled with fluorescent dyes were adsorbed to the titanium dioxide regions, yielding nanopatterns with bright fluorescence. Subsequent near-UV irradiation of the samples removed the protein from the titanium dioxide nanostructures by photocatalytic degradation facilitating the adsorption of a different protein. The process was repeated multiple times. These simple methods appear to yield durable, reuseable samples that may be of value to laboratories that require nanostructured biological interfaces but do not have access to the infrastructure required for nanofabrication.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Photosynthetic Antenna Research Center (PARC)
Sponsoring Organization:
Biotechnology and Biological Sciences Research Council (BBSRC); Engineering and Physical Sciences Research Council (EPSRC); European Research Council (ERC); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
SC0001035
OSTI ID:
1385919
Journal Information:
ACS Nano, Journal Name: ACS Nano Journal Issue: 6 Vol. 9; ISSN 1936-0851
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (44)

A Universal Scheme for Patterning of Oxides via Thermal Nanoimprint Lithography journal November 2012
Direct-Write Dip-Pen Nanolithography of Proteins on Modified Silicon Oxide Surfaces journal May 2003
Facile Preparation of Complex Protein Architectures with Sub-100-nm Resolution on Surfaces journal September 2007
Making Protein Patterns by Writing in a Protein-Repelling Matrix journal July 2009
“Dark” Photocatalysis: The Degradation of Organic Molecules Anchored to Dark Microdomains of Titanium Dioxide journal June 2003
Micrometer and Nanometer Scale Photopatterning of Proteins on Glass Surfaces by Photo-degradation of Films Formed from Oligo(Ethylene Glycol) Terminated Silanes journal December 2012
Adsorption of phosphorus acids on alumina journal September 1988
Passivated Aluminum Nanohole Arrays for Label-Free Biosensing Applications journal December 2013
Layered metal phosphates and phosphonates: from crystals to monolayers journal September 1992
Cyan and Yellow Super Fluorescent Proteins with Improved Brightness, Protein Folding, and FRET Förster Radius , journal May 2006
Convenient methods for patterning the adhesion of mammalian cells to surfaces using self-assembled monolayers of alkanethiolates on gold journal June 1993
Directed Formation of Micro- and Nanoscale Patterns of Functional Light-Harvesting LH2 Complexes journal November 2007
Photocatalytic Patterning and Modification of Graphene journal March 2011
Protein Micro- and Nanopatterning Using Aminosilanes with Protein-Resistant Photolabile Protecting Groups journal March 2011
Zwitterionic Poly(amino acid methacrylate) Brushes journal June 2014
Site-Specific Immobilization and Micrometer and Nanometer Scale Photopatterning of Yellow Fluorescent Protein on Glass Surfaces journal January 2009
Remote Photocatalytic Activity as Probed by Measuring the Degradation of Self-Assembled Monolayers Anchored near Microdomains of Titanium Dioxide journal April 2001
Photocatalytic Decomposition of Alkylsiloxane Self-Assembled Monolayers on Titanium Oxide Surfaces journal August 2003
Self-Assembled Monolayers of Dodecyl and Hydroxy-dodecyl Phosphates on Both Smooth and Rough Titanium and Titanium Oxide Surfaces journal April 2002
Orientation in Methyl- and Hydroxyl-Terminated Self-Assembled Alkanephosphate Monolayers on Titanium Oxide Surfaces Investigated with Soft X-ray Absorption journal May 2002
AFM Study on Protein Immobilization on Charged Surfaces at the Nanoscale:  Toward the Fabrication of Three-Dimensional Protein Nanostructures journal November 2003
Fabrication of Multiscale Surface-Chemical Gradients by Means of Photocatalytic Lithography journal February 2007
Fabrication of Biomolecular Nanostructures by Scanning Near-Field Photolithography of Oligo(ethylene glycol)-Terminated Self-Assembled Monolayers journal June 2007
Rewritable Superhydrophilic−Superhydrophobic Patterns on a Sintered Titanium Dioxide Substrate journal June 2010
Influence of Alkyl Chain Length on Phosphate Self-Assembled Monolayers journal June 2007
TiO 2 −Catalyzed Photodegradation of Porphyrins: Mechanistic Studies and Application in Monolayer Photolithography journal May 2009
Photopatterning, Etching, and Derivatization of Self-Assembled Monolayers of Phosphonic Acids on the Native Oxide of Titanium journal July 2009
Self-Assembled Monolayers of Alkylphosphonic Acids on Metal Oxides journal January 1996
Structural Chemistry of Self-Assembled Monolayers of Octadecylphosphoric Acid on Tantalum Oxide Surfaces journal April 2000
Long-Range Energy Propagation in Nanometer Arrays of Light Harvesting Antenna Complexes journal April 2010
Plasmonic Nanosensors for Simultaneous Quantification of Multiple Protein–Protein Binding Affinities journal September 2014
Highly Sensitive Biosensing Using Arrays of Plasmonic Au Nanodisks Realized by Nanoimprint Lithography journal January 2011
Photocatalytic Nanolithography of Self-Assembled Monolayers and Proteins journal August 2013
Light-induced amphiphilic surfaces journal July 1997
Adjustment of the bioresistivity by electron irradiation: self-assembled monolayers of oligo(ethyleneglycol)-terminated alkanethiols with embedded cleavable group journal January 2010
Biosensors: sense and sensibility journal January 2013
Optical and Interferometric Lithography - Nanotechnology Enablers journal October 2005
Protein Nanoarrays Generated By Dip-Pen Nanolithography journal February 2002
Geometric Control of Cell Life and Death journal May 1997
"Dip-Pen" Nanolithography journal January 1999
Engineering cell shape and function journal April 1994
Nanolithography Based on Photocatalysis of TiO 2 Using an Atomic Force Microscope journal July 2005
Cell Spreading and Focal Adhesion Dynamics Are Regulated by Spacing of Integrin Ligands journal April 2007
Self-assembled monolayers and titanium dioxide: From surface patterning to potential applications journal January 2011

Cited By (4)

A novel design strategy for nanoparticles on nanopatterns: interferometric lithographic patterning of Mms6 biotemplated magnetic nanoparticles journal January 2016
Superhydrophilic Coating Induced Temporary Conductivity for Low-Cost Coating and Patterning of Insulating Surfaces journal October 2016
Scanning Nanowelding Lithography for Rewritable One‐Step Patterning of Sub‐50 nm High‐Aspect‐Ratio Metal Nanostructures journal July 2018
Template mediated protein self-assembly as a valuable tool in regenerative therapy journal April 2018