An inkjet-printable microemulsion system for colorimetric polydiacetylene supramolecules on paper substrates

Owing to their flexible, light-weight and disposable properties, paper-based electronic and sensor systems have gained much attention. Efficient immobilization and patterning of functional materials on paper substrates are critical to device performance. Herein, we report an inkjet printable and photopolymerizable diacetylene (DA) containing microemulsion system that can be readily transferred to paper substrates using a common office inkjet printer. UV-induced polymerization afforded clean formation of polydiacetylene (PDA) supramolecules on paper and the polymer displayed a typical thermochromism. The resolution of the printed PDA images was found to be equivalent to that of conventional black ink. The randomly oriented DA in the oil phase was found to be transformed to self-assembled layered structures upon printing. The printed PDA supramolecules derived from 5,7-dodecadiyne-1,12-diol bis[((butoxycarbonyl)methyl)urethane] (4BCMU) displayed a blue-to-red-to-yellow color transition upon heating. Thus, the blue colored 4BCMU-derived polymer was converted to a red colored PDA at 100 °C and further heating to 180 °C resulted in the generation of a yellow colored PDA. Upon cooling to room temperature, the yellow colored PDA became red and a complete colorimetric reversibility was observed between red (30 °C) and yellow (180 °C). The thermally promoted reversible PDA phase transition was successfully applied to a banknote to demonstrate an application to a potential counterfeit prevention method.

[1]  M. Sukwattanasinitt,et al.  Tuning of Thermochromic Properties of Polydiacetylene toward Universal Temperature Sensing Materials through Amido Hydrogen Bonding , 2010 .

[2]  Jong-Man Kim,et al.  Fluorogenic polydiacetylene supramolecules: immobilization, micropatterning, and application to label-free chemosensors. , 2008, Accounts of chemical research.

[3]  A. Matsumoto,et al.  Thermochromism of Polydiacetylenes in the Solid State and in Solution by the Self-Organization of Polymer Chains Containing No Polar Group , 2008 .

[4]  S. Sottini,et al.  UV polymerization of self-assembled monolayers of a novel diacetylene on silver: a spectroscopic analysis by surface plasmon resonance and surface enhanced Raman scattering. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[5]  Jaewon Yoon,et al.  Colorimetric sensors for volatile organic compounds (VOCs) based on conjugated polymer-embedded electrospun fibers. , 2007, Journal of the American Chemical Society.

[6]  F. W. Fowler,et al.  Preparation and structure of a tubular addition polymer: a true synthetic nanotube. , 2012, Journal of the American Chemical Society.

[7]  Xuli Chen,et al.  Electrochromatic carbon nanotube/polydiacetylene nanocomposite fibres. , 2009, Nature nanotechnology.

[8]  J. Lewis,et al.  Pen‐on‐Paper Flexible Electronics , 2011, Advanced materials.

[9]  Erica Sharpe,et al.  Paper bioassay based on ceria nanoparticles as colorimetric probes. , 2011, Analytical chemistry.

[10]  Erkang Wang,et al.  A nanoparticle autocatalytic sensor for Ag+ and Cu2+ ions in aqueous solution with high sensitivity and selectivity and its application in test paper. , 2011, Analytical chemistry.

[11]  Oktay Yarimaga,et al.  Network Polydiacetylene Films: Preparation, Patterning, and Sensor Applications , 2011 .

[12]  M. Sung,et al.  High-performance two-dimensional polydiacetylene with a hybrid inorganic-organic structure. , 2011, Angewandte Chemie.

[13]  B. A. Pindzola,et al.  Biosensing with polydiacetylene materials: structures, optical properties and applications. , 2007, Chemical communications.

[14]  Bora Yoon,et al.  Inkjet Printing of Conjugated Polymer Precursors on Paper Substrates for Colorimetric Sensing and Flexible Electrothermochromic Display , 2011, Advanced materials.

[15]  Raz Jelinek,et al.  A colorimetric assay for rapid screening of antimicrobial peptides , 2000, Nature Biotechnology.

[16]  Hong Xu,et al.  Magnetochromatic polydiacetylene by incorporation of Fe3O4 nanoparticles. , 2011, Angewandte Chemie.

[17]  P. Calvert.  Inkjet Printing for Materials and Devices , 2001 .

[18]  M. Schott.  The colors of polydiacetylenes: a commentary. , 2006, The journal of physical chemistry. B.

[19]  Jinsang Kim,et al.  Polydiacetylene liposome arrays for selective potassium detection. , 2008, Journal of the American Chemical Society.

[20]  M. Assali,et al.  Copper-catalyzed azide-alkyne cycloaddition in the synthesis of polydiacetylene: "click glycoliposome" as biosensors for the specific detection of lectins. , 2011, Chemistry.

[21]  J. Jang,et al.  Fabrication of Water‐Dispersible Polyaniline‐Poly(4‐styrenesulfonate) Nanoparticles For Inkjet‐Printed Chemical‐Sensor Applications , 2007 .

[22]  M. Bednarski,et al.  Direct colorimetric detection of a receptor-ligand interaction by a polymerized bilayer assembly. , 1993, Science.

[23]  Jianguo Huang,et al.  Immobilization of oligonucleotides onto zirconia-modified filter paper and specific molecular recognition. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[24]  Shlomo Magdassi and,et al.  Patterning of Organic Nanoparticles by Ink-jet Printing of Microemulsions , 2003 .

[25]  Simon Song,et al.  A thermoresponsive fluorogenic conjugated polymer for a temperature sensor in microfluidic devices. , 2009, Journal of the American Chemical Society.

[26]  T. Hasegawa,et al.  Chemical wiring and soldering toward all-molecule electronic circuitry. , 2011, Journal of the American Chemical Society.

[27]  Signal amplification by magnetic force on polydiacetylene supramolecules for detection of prostate cancer. , 2012, Small.

[28]  M. Im,et al.  Thermofluorescent Conjugated Polymer Sensors for Nano- and Microscale Temperature Monitoring , 2011 .

[29]  F. W. Fowler,et al.  Single-crystal-to-single-crystal topochemical polymerizations by design. , 2008, Accounts of chemical research.

[30]  Dong June Ahn,et al.  Immobilized Polydiacetylene Vesicles on Solid Substrates for Use as Chemosensors , 2003 .

[31]  Huisheng Peng,et al.  Chromatic polydiacetylene with novel sensitivity. , 2010, Chemical Society reviews.

[32]  A. Steckl,et al.  Electrowetting on paper for electronic paper display. , 2010, ACS applied materials & interfaces.

[33]  Jean‐François Morin,et al.  Topochemical polymerization of a diarylbutadiyne derivative in the gel and solid states. , 2011, Organic letters.

[34]  Tao Yi,et al.  Peptide functionalized polydiacetylene liposomes act as a fluorescent turn-on sensor for bacterial lipopolysaccharide. , 2011, Journal of the American Chemical Society.

[35]  Y. Mély,et al.  Core functionalization of polydiacetylene micelles by a “click” reaction , 2011 .

[36]  Justyn Jaworski,et al.  Polydiacetylene incorporated with peptide receptors for the detection of trinitrotoluene explosives. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[37]  Jinsang Kim,et al.  Effect of the Molecular Size of Analytes on Polydiacetylene Chromism , 2010 .

[38]  Qi-jin Zhang,et al.  Stable Hydrogen-Bonding Complexes of Poly(4-vinylpyridine) and Polydiacetylenes for Photolithography and Sensing , 2009 .

[39]  J. V. van Hest,et al.  Effect of the diacetylene position on the chromatic properties of polydiacetylenes from self-assembled peptide amphiphiles. , 2010, Biomacromolecules.

[40]  Gerhard Wegner,et al.  Topochemische Reaktionen von Monomeren mit konjugierten Dreifachbindungen / Tochemical Reactions of Monomers with conjugated triple Bonds , 1969 .

[41]  Simon Song,et al.  Probing Temperature on a Microfluidic Chip with Thermosensitive Conjugated Polymer Supramolecules , 2010 .

[42]  P. Kohli,et al.  Investigating Molecular Interactions in Biosensors Based on Fluorescence Resonance Energy Transfer , 2010 .

[43]  Justyn Jaworski,et al.  Selective and sensitive TNT sensors using biomimetic polydiacetylene-coated CNT-FETs. , 2011, ACS nano.

[44]  Ling Zang,et al.  Paper-based vapor detection of hydrogen peroxide: colorimetric sensing with tunable interface. , 2011, ACS applied materials & interfaces.

[45]  Emanuel Carrilho,et al.  Paper-based ELISA. , 2010, Angewandte Chemie.

[46]  Juyoung Yoon,et al.  Visual detection of copper ions based on azide- and alkyne-functionalized polydiacetylene vesicles , 2011 .

[47]  Jinsang Kim,et al.  Selective and sensitive detection of melamine by intra/inter liposomal interaction of polydiacetylene liposomes. , 2011, Chemical communications.

[48]  F. Serein-Spirau,et al.  Self-organized ureido substituted diacetylenic organogel. Photopolymerization of one-dimensional supramolecular assemblies to give conjugated nanofibers. , 2006, Journal of the American Chemical Society.

[49]  Takao Someya,et al.  Organic Electronics on Banknotes , 2011, Advanced materials.

[50]  Wei Shen,et al.  Biosurface engineering through ink jet printing. , 2010, Colloids and surfaces. B, Biointerfaces.

[51]  B. Boury,et al.  Tuning Topochemical Polymerization of Diacetylenes: A Joint Synthetic, Structural, Photophysical, and Theoretical Study of a Series of Analogues of a Known Reactive Monomer, 1,6-Bis(diphenylamino)-2,4-hexadiyne (THD) , 2010 .

[52]  R. Koepsel,et al.  Surface dispersion and hardening of self-assembled diacetylene nanotubes. , 2005, Nano letters.

[53]  T. Chung,et al.  Rod to coil transition and aggregation in soluble polydiacetylenes: Semidilute regime , 1986 .

[54]  Juyoung Yoon,et al.  Thin-film formation of imidazolium-based conjugated polydiacetylenes and their application for sensing anionic surfactants. , 2010, Angewandte Chemie.