Optically Transparent Antibacterial Films Capable of Healing Multiple Scratches

Optically transparent antibacterial films capable of healing scratches and restoring transparency are fabricated by exponential layer-by-layer assembly of branched polyethylenimine (bPEI)/poly(acrylic acid) (PAA) films and post-diffusion of cetyltrimethylammonium bromide micelles encapsulated with antibacterial agent triclosan. The triclosan-loaded bPEI/PAA transparent films can effectively inhibit the growth of gram-positive and gram-negative bacteria by the sustained release of triclosan molecules. Healing of multiple scratches on the triclosan-loaded bPEI/PAA films can be conveniently achieved by immersing the films in water or spraying water on the damaged films, which also fully restores their transparency. The self-healing ability of these transparent antibacterial films originates from the ability of bPEI and PAA to flow and recombine in the presence of water. The triclosan-loaded bPEI/PAA films have satisfactory mechanical stability under ambient conditions, and thus show potential for application as transparent protective films with antibacterial properties.

[1]  Justin R. Kumpfer,et al.  Optically healable supramolecular polymers , 2011, Nature.

[2]  Junqi Sun,et al.  Water-enabled self-healing of polyelectrolyte multilayer coatings. , 2011, Angewandte Chemie.

[3]  Xiaolong Wang,et al.  Self-healing superamphiphobicity. , 2011, Chemical communications.

[4]  Antoni R. Slabas,et al.  Molecular basis of triclosan activity , 1999, Nature.

[5]  S. Nutt,et al.  A Thermally Re-mendable Cross-Linked Polymeric Material , 2002, Science.

[6]  P. Cordier,et al.  Self-healing and thermoreversible rubber from supramolecular assembly , 2008, Nature.

[7]  L. Lyon,et al.  Autonomic self-healing of hydrogel thin films. , 2010, Angewandte Chemie.

[8]  F. Caruso,et al.  Facile tailoring of film morphology and release properties using layer-by-layer assembly of thermoresponsive materials. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[9]  Dongpeng Yan,et al.  Heterogeneous Transparent Ultrathin Films with Tunable‐Color Luminescence Based on the Assembly of Photoactive Organic Molecules and Layered Double Hydroxides , 2011 .

[10]  Kishor L Handore,et al.  Soft optical devices from self-healing gels formed by oil and sugar-based organogelators. , 2011, Angewandte Chemie.

[11]  Michael F. Rubner,et al.  Methods of Loading and Releasing Low Molecular Weight Cationic Molecules in Weak Polyelectrolyte Multilayer Films , 2002 .

[12]  S. White,et al.  Self‐Healing Polymer Coatings , 2009 .

[13]  Byeong-Su Kim,et al.  Hydrogen-bonding layer-by-layer-assembled biodegradable polymeric micelles as drug delivery vehicles from surfaces. , 2008, ACS nano.

[14]  Joong Tark Han,et al.  Highly tunable charge transport in layer-by-layer assembled graphene transistors. , 2012, ACS nano.

[15]  Aaron C. Jackson,et al.  Transparent Self‐Healing Polymers Based on Encapsulated Plasticizers in a Thermoplastic Matrix , 2011 .

[16]  J. Lewis,et al.  Self‐Healing Materials with Interpenetrating Microvascular Networks , 2009 .

[17]  Christopher J. Barrett,et al.  pH-Dependent Loading and Release Behavior of Small Hydrophilic Molecules in Weak Polyelectrolyte Multilayer Films , 2004 .

[18]  Wi Hyoung Lee,et al.  Nanostructured hybrid transparent conductive films with antibacterial properties. , 2012, ACS nano.

[19]  Catherine Picart,et al.  Buildup Mechanism for Poly(l-lysine)/Hyaluronic Acid Films onto a Solid Surface , 2001 .

[20]  Krzysztof Matyjaszewski,et al.  Repeatable photoinduced self-healing of covalently cross-linked polymers through reshuffling of trithiocarbonate units. , 2011, Angewandte Chemie.

[21]  Zhenan Bao,et al.  Highly Conductive and Transparent PEDOT:PSS Films with a Fluorosurfactant for Stretchable and Flexible Transparent Electrodes , 2012 .

[22]  Hongyu Zhang,et al.  Layer-by-layer assembly: from conventional to unconventional methods. , 2007, Chemical communications.

[23]  Benjamin C. K. Tee,et al.  An electrically and mechanically self-healing composite with pressure- and flexion-sensitive properties for electronic skin applications. , 2012, Nature nanotechnology.

[24]  Yoshifumi Amamoto,et al.  Self-healing of chemical gels cross-linked by diarylbibenzofuranone-based trigger-free dynamic covalent bonds at room temperature. , 2012, Angewandte Chemie.

[25]  K. V. Van Vliet,et al.  Electrochemically Controlled Swelling and Mechanical Properties of a Polymer Nanocomposite Keywords: Polymer Nanocomposite · Electrochemistry · Prussian Blue · Responsive Materials · Layer-by-layer Thin Film · Swelling · Nanoindentation , 2009 .

[26]  Tong Lin,et al.  Durable, self-healing superhydrophobic and superoleophobic surfaces from fluorinated-decyl polyhedral oligomeric silsesquioxane and hydrolyzed fluorinated alkyl silane. , 2011, Angewandte Chemie.

[27]  B. Blaiszik,et al.  A Self‐healing Conductive Ink , 2012, Advanced materials.

[28]  Hang Sun,et al.  Functional Free‐Standing Graphene Honeycomb Films , 2013 .

[29]  Yang Li,et al.  Mechanically stable antireflection and antifogging coatings fabricated by the layer-by-layer deposition process and postcalcination. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[30]  Mary M. Caruso,et al.  Mechanically-induced chemical changes in polymeric materials. , 2009, Chemical reviews.

[31]  Zhihua Liu,et al.  Surface molecular imprinted layer-by-layer film attached to a porous membrane for selective filtration. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[32]  M. Urban,et al.  Self-Repairing Oxetane-Substituted Chitosan Polyurethane Networks , 2009, Science.

[33]  S. Rowan,et al.  Using the dynamic bond to access macroscopically responsive structurally dynamic polymers. , 2011, Nature materials.

[34]  Helmuth Möhwald,et al.  Self‐Healing Anticorrosion Coatings Based on pH‐Sensitive Polyelectrolyte/Inhibitor Sandwichlike Nanostructures , 2008, Advanced materials.

[35]  G. Pharr,et al.  An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments , 1992 .

[36]  T. J. McCarthy,et al.  A surprise from 1954: siloxane equilibration is a simple, robust, and obvious polymer self-healing mechanism. , 2012, Journal of the American Chemical Society.

[37]  Nancy R. Sottos,et al.  Full Recovery of Fracture Toughness Using a Nontoxic Solvent‐Based Self‐Healing System , 2008 .

[38]  N. Sottos,et al.  Autonomic healing of polymer composites , 2001, Nature.

[39]  Kyle A. Williams,et al.  Towards electrically conductive, self-healing materials , 2007, Journal of The Royal Society Interface.

[40]  Gero Decher,et al.  Fuzzy Nanoassemblies: Toward Layered Polymeric Multicomposites , 1997 .

[41]  M. Rubner,et al.  Reversibly erasable nanoporous anti-reflection coatings from polyelectrolyte multilayers , 2002, Nature materials.

[42]  T. J. McCarthy,et al.  Poly(4-methyl-1-pentene)-Supported Polyelectrolyte Multilayer Films: Preparation and Gas Permeability1 , 1997 .

[43]  Nancy R. Sottos,et al.  Restoration of Conductivity with TTF‐TCNQ Charge‐Transfer Salts , 2010 .

[44]  J. Lewis,et al.  Self-healing materials with microvascular networks. , 2007, Nature materials.

[45]  Junqi Sun,et al.  Exponential growth of layer-by-layer assembled coatings with well-dispersed ultrafine nanofillers: a facile route to scratch-resistant and transparent hybrid coatings , 2010 .

[46]  R. Advíncula,et al.  pH-sensitive bipolar ion-permselective ultrathin films. , 2004, Journal of the American Chemical Society.

[47]  Yang Li,et al.  Layer-by-layer assembly for rapid fabrication of thick polymeric films. , 2012, Chemical Society reviews.

[48]  Ming Qiu Zhang,et al.  Self-Healing Polymeric Materials Using Epoxy/Mercaptan as the Healant , 2008 .

[49]  Stuart J Rowan,et al.  High-strength, healable, supramolecular polymer nanocomposites. , 2012, Journal of the American Chemical Society.

[50]  P. Hammond,et al.  High-Contrast Electrochromic Thin Films via Layer-by-Layer Assembly of Starlike and Sulfonated Polyaniline , 2010 .

[51]  Yang Li,et al.  Polyelectrolyte Multilayers Impart Healability to Highly Electrically Conductive Films , 2012, Advanced materials.

[52]  George M. Pharr,et al.  Nanoindentation and the dynamic characterization of viscoelastic solids , 2008 .

[53]  Hesheng Xia,et al.  Poly(vinyl alcohol) Hydrogel Can Autonomously Self-Heal. , 2012, ACS macro letters.

[54]  Aaron M Kushner,et al.  Multiphase design of autonomic self-healing thermoplastic elastomers. , 2012, Nature chemistry.

[55]  Mikhail L. Zheludkevich,et al.  Anticorrosion Coatings with Self-Healing Effect Based on Nanocontainers Impregnated with Corrosion Inhibitor , 2007 .

[56]  Maurizio Prato,et al.  Single-wall carbon nanotubes as integrative building blocks for solar-energy conversion. , 2005, Angewandte Chemie.

[57]  R. Wool.  Self-healing materials: a review. , 2008, Soft matter.

[58]  Eric Verploegen,et al.  Extended Release Antibacterial Layer-by-Layer Films Incorporating Linear-Dendritic Block Copolymer Micelles , 2007 .

[59]  Jia-cong Shen,et al.  Layer-by-layer assembled polyampholyte microgel films for simultaneous release of anionic and cationic molecules. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[60]  Scott R White,et al.  Programmable microcapsules from self-immolative polymers. , 2010, Journal of the American Chemical Society.

[61]  M. Meneghetti,et al.  Advances in self-healing optical materials , 2012 .

[62]  A. Bauer,et al.  Antibiotic susceptibility testing by a standardized single disk method. , 1966, American journal of clinical pathology.

[63]  Dongpeng Yan,et al.  CdTe Quantum Dots/Layered Double Hydroxide Ultrathin Films with Multicolor Light Emission via Layer‐by‐Layer Assembly , 2012 .

[64]  Scott R. White,et al.  Room-Temperature Polydimethylsiloxane-Based Self-Healing Polymers , 2012 .

[65]  Martha E. Grady,et al.  Autonomic Restoration of Electrical Conductivity , 2012, Advanced materials.

[66]  Gero Decher,et al.  Toward Layered Polymeric Multicomposites , 1997 .

[67]  Jia-cong Shen,et al.  A facile room temperature layer-by-layer deposition process for the fabrication of ultrathin films with noncentrosymmetrically oriented azobenzene chromophores. , 2006, Chemical communications.

[68]  Jeffrey S. Moore,et al.  Self-Healing Polymers and Composites , 2010 .

[69]  G. Prestwich,et al.  Molecular basis for the explanation of the exponential growth of polyelectrolyte multilayers , 2002, Proceedings of the National Academy of Sciences of the United States of America.

[70]  Caruso,et al.  Nanoengineering of inorganic and hybrid hollow spheres by colloidal templating , 1998, Science.

[71]  Yang Li,et al.  Bioinspired self-healing superhydrophobic coatings. , 2010, Angewandte Chemie.

[72]  Frank G. Shi,et al.  Thickness dependence of elastic modulus and hardness of on-wafer low-k ultrathin polytetrafluoroethylene films , 2000 .

[73]  Paula T Hammond,et al.  Exponential growth of LBL films with incorporated inorganic sheets. , 2008, Nano letters.

[74]  M. Prato,et al.  Nanosized inorganic/organic composites for solar energy conversion , 2005 .

[75]  J. Leckie,et al.  Virus transfer between fingerpads and fomites , 2010, Journal of applied microbiology.

[76]  S. Sukhishvili,et al.  Multiresponsive clay-containing layer-by-layer films. , 2011, ACS nano.

[77]  Sindy K. Y. Tang,et al.  Bioinspired self-repairing slippery surfaces with pressure-stable omniphobicity , 2011, Nature.