Reversible Light-Switching of Enzymatic Activity on Orthogonally Functionalized Polymer Brushes.

Copolymer brushes, composed of glycidyl methacrylate and a furan-protected maleimide-containing monomer, were grafted from radical initiators at the surface of irradiation-activated fluoropolymer foils. After postpolymerization modification with enzymatically active microperoxidase-11 and photochromic spiropyran moieties, the polymer brushes catalyzed the oxidation of 3,3'5,5'-tetramethylbenzidine. Exposure to either UV or visible-light allowed switching the turnover by more than 1 order of magnitude, as consequence of the reversible, light-induced spiropyran-merocyanine transition. The modified samples were integrated into an optofluidic device that allowed the reversible switching of enzymatic activity for several cycles under flow, validating the potential for application in smart lab-on-a-chip systems.

[1]  N. Spencer,et al.  From pH- to Light-Response: Postpolymerization Modification of Polymer Brushes Grafted onto Microporous Polymeric Membranes , 2017, ACS omega.

[2]  N. Spencer,et al.  Understanding the effect of hydrophobic protecting blocks on the stability and biopassivity of polymer brushes in aqueous environments: A Tiramisù for cell-culture applications , 2016 .

[3]  Victor J. Cadarso,et al.  Integrated hollow microneedle-optofluidic biosensor for therapeutic drug monitoring in sub-nanoliter volumes , 2016, Scientific Reports.

[4]  N. Spencer,et al.  The influence of surface grafting on the growth rate of polymer chains , 2016 .

[5]  N. Spencer,et al.  Fabrication of Thiol-Ene "Clickable" Copolymer-Brush Nanostructures on Polymeric Substrates via Extreme Ultraviolet Interference Lithography. , 2015, ACS applied materials & interfaces.

[6]  N. Spencer,et al.  Light-responsive polymer surfaces via postpolymerization modification of grafted polymer-brush structures. , 2014, Langmuir : the ACS journal of surfaces and colloids.

[7]  T. N. Gevrek,et al.  Maleimide-Functionalized Thiol Reactive Copolymer Brushes: Fabrication and Post-Polymerization Modification , 2014 .

[8]  B. Feringa,et al.  Photo-controlled deactivation of immobilised lipase. , 2014, Chemical communications.

[9]  L. Ionov,et al.  Programmable patterning of protein bioactivity by visible light. , 2014, Nano letters.

[10]  Qian Yu,et al.  Nanopatterned antimicrobial enzymatic surfaces combining biocidal and fouling release properties. , 2014, Nanoscale.

[11]  P. Théato,et al.  Efficient Multicomponent Postpolymerization Modification Based on Kabachnik-Fields Reaction. , 2014, ACS macro letters.

[12]  F. D. Du Prez,et al.  One-Pot Double Modification of p(NIPAAm): A Tool for Designing Tailor-Made Multiresponsive Polymers. , 2013, ACS macro letters.

[13]  P. Théato,et al.  Three-Component Reactions for Post-Polymerization Modifications. , 2013, ACS macro letters.

[14]  Omar Azzaroni,et al.  Polymer brushes here, there, and everywhere: Recent advances in their practical applications and emerging opportunities in multiple research fields , 2012 .

[15]  A. Pingoud,et al.  Restriction endonuclease SsoII with photoregulated activity--a "molecular gate" approach. , 2011, Bioconjugate chemistry.

[16]  G. London,et al.  Light-induced control of protein translocation by the SecYEG complex. , 2010, Angewandte Chemie.

[17]  Jean-François Gohy,et al.  Light-responsive block copolymers. , 2010, Macromolecular rapid communications.

[18]  H. Solak,et al.  Functionalization of fluoropolymer surfaces with nanopatterned polyelectrolyte brushes , 2010 .

[19]  N. Ayres.  Polymer brushes: Applications in biomaterials and nanotechnology , 2010 .

[20]  H. Klok,et al.  Polymer Brushes via Surface‐Initiated Controlled Radical Polymerization: Synthesis, Characterization, Properties, and Applications , 2010 .

[21]  M. C. Stuart,et al.  Emerging applications of stimuli-responsive polymer materials. , 2010, Nature materials.

[22]  B. Spengler,et al.  Controlling the enzymatic activity of a restriction enzyme by light , 2009, Proceedings of the National Academy of Sciences.

[23]  Jun‐Jie Zhu,et al.  Thermosensitive Behavior of Poly(N-isopropylacrylamide) and Release of Incorporated Hemoglobin , 2009 .

[24]  César Fernández-Sánchez,et al.  Optical biosensor based on hollow integrated waveguides. , 2008, Analytical chemistry.

[25]  R. Sanyal,et al.  A Diels‐Alder/retro Diels‐Alder strategy to synthesize polymers bearing maleimide side chains , 2007 .

[26]  Mark Hayes,et al.  Photo-, thermally, and pH-responsive microgels. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[27]  K. Neoh,et al.  Thermoresponsive comb-shaped copolymer-Si(100) hybrids for accelerated temperature-dependent cell detachment. , 2006, Biomaterials.

[28]  T. Okano,et al.  Influence of insulin immobilization to thermoresponsive culture surfaces on cell proliferation and thermally induced cell detachment. , 2005, Biomaterials.

[29]  William J. Brittain,et al.  Polymer brushes : synthesis, characterization, applications , 2004 .

[30]  H. Solak,et al.  Preparation of micro- and nanopatterns of polymer chains grafted onto flexible polymer substrates. , 2004, Journal of the American Chemical Society.

[31]  E. Wang,et al.  Hydrogen peroxide biosensor based on microperoxidase-11 entrapped in lipid membrane. , 2003, Biosensors & bioelectronics.

[32]  Itamar Willner,et al.  Photoswitchable Biomaterials: En Route to Optobioelectronic Systems , 1997 .

[33]  I. Willner,et al.  Light-controlled electron transfer reactions at photoisomerizable monolayer electrodes by means of electrostatic interactions: active interfaces for the amperometric transduction of recorded optical signals , 1997 .

[34]  Shai Rubin,et al.  Control of the Structure and Functions of Biomaterials by Light , 1996 .