A Colorimetric Hydrocarbon Sensor Employing a Swelling‐Induced Mechanochromic Polydiacetylene

Exceptional challenges have confronted the rational design of colorimetric sensors for saturated aliphatic hydrocarbons (SAHCs). The main reasons for this difficulty are the extremely nonpolar nature of these targets and their lack of functional groups that can interact with probes. By taking advantage of a mechanochromic conjugated polydiacetylene (PDA) and the hydrocarbon-induced swelling properties of polydimethylsiloxane (PDMS), a sensor film that enables simple, colorimetric differentiation between a variety of C5 to C14 aliphatic hydrocarbons is fabricated. The unprecedented PDA–PDMS composite sensor undergoes a blue-to-red colorimetric transition on a timescale that is dependent on the chain length of the hydrocarbon target. In addition, the development of the red color is directly proportional to the swelling ratio of the film. This straightforward approach enables naked-eye differentiation between n-pentane and n-heptane. The versatility of the sensor system is demonstrated by using it for the colorimetric determination of kerosene in adulterated diesel oil. Finally, the observation that a PDA microcrystal in the film undergoes significant expansion and tearing in concert with a blue-to-red colorimetric transition during the swelling process provides direct evidence for the mechanism for the mechanochromic behavior of the PDA.

[1]  G. Whitesides,et al.  Solvent compatibility of poly(dimethylsiloxane)-based microfluidic devices. , 2003, Analytical chemistry.

[2]  Michael F. Geer,et al.  Thermal reaction of a columnar assembled diacetylene macrocycle. , 2010, Journal of the American Chemical Society.

[3]  Joanna Aizenberg,et al.  Wetting in color: colorimetric differentiation of organic liquids with high selectivity. , 2012, ACS nano.

[4]  A. Matsumoto,et al.  Structural and Chromatic Changes of Host Polydiacetylene Crystals during Intercalation with Guest Alkylamines , 2011 .

[5]  C. Brinker,et al.  Self-assembly of mesoscopically ordered chromatic polydiacetylene/silica nanocomposites , 2001, Nature.

[6]  W. Cao,et al.  Colorimetric Sensor Based on Self‐Assembled Polydiacetylene/Graphene‐Stacked Composite Film for Vapor‐Phase Volatile Organic Compounds , 2013 .

[7]  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.

[8]  Jong-Man Kim,et al.  A soluble, low-temperature thermochromic and chemically reactive polydiacetylene. , 2013, ACS applied materials & interfaces.

[9]  S. Rondeau‐Gagné,et al.  Topochemical polymerization of phenylacetylene macrocycles: a new strategy for the preparation of organic nanorods. , 2013, Journal of the American Chemical Society.

[10]  Jinsang Kim,et al.  Multiphasic Sensory Alginate Particle Having Polydiacetylene Liposome for Selective and More Sensitive Multitargeting Detection , 2012 .

[11]  Haibo Xu,et al.  Polydiacetylene-polymethylmethacrylate/graphene composites as one-shot, visually observable, and semiquantative electrical current sensing materials. , 2013, ACS applied materials & interfaces.

[12]  D. Sandman,et al.  Structural Aspects of the Thermochromic Transition in Urethane-Substituted Polydiacetylenes , 2002 .

[13]  Yuyuan Tian,et al.  Hybrid Mechanoresponsive Polymer Wires Under Force Activation , 2013, Advanced materials.

[14]  Oktay Yarimaga,et al.  Polydiacetylenes: supramolecular smart materials with a structural hierarchy for sensing, imaging and display applications. , 2012, Chemical communications.

[15]  J. Lauher,et al.  Preparation of Poly(diiododiacetylene), an Ordered Conjugated Polymer of Carbon and Iodine , 2006, Science.

[16]  G. Ruggeri,et al.  Dye-containing polymers: methods for preparation of mechanochromic materials. , 2013, Chemical Society reviews.

[17]  S. Rondeau‐Gagné,et al.  Soluble conjugated one-dimensional nanowires prepared by topochemical polymerization of a butadiynes-containing star-shaped molecule in the xerogel state. , 2013, Langmuir : the ACS journal of surfaces and colloids.

[18]  Justin R. Kumpfer,et al.  Vapochromic and mechanochromic films from square-planar platinum complexes in polymethacrylates , 2012 .

[19]  W. Nau,et al.  Strong binding of hydrocarbons to cucurbituril probed by fluorescent dye displacement: a supramolecular gas-sensing ensemble. , 2011, Angewandte Chemie.

[20]  M. Sukwattanasinitt,et al.  Odd–Even and Hydrophobicity Effects of Diacetylene Alkyl Chains on Thermochromic Reversibility of Symmetrical and Unsymmetrical Diyndiamide Polydiacetylenes , 2012 .

[21]  Jong-Man Kim,et al.  A Combinatorial Approach for Colorimetric Differentiation of Organic Solvents Based on Conjugated Polymer‐Embedded Electrospun Fibers , 2009 .

[22]  C. Rao,et al.  High-sensitivity hydrocarbon sensors based on tungsten oxide nanowires , 2006 .

[23]  J. Tovar,et al.  Polydiacetylene-peptide 1D nanomaterials. , 2013, Macromolecular rapid communications.

[24]  J. Tovar,et al.  Synthesis and alignment of discrete polydiacetylene-peptide nanostructures. , 2012, Journal of the American Chemical Society.

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

[26]  Radu Ionescu,et al.  Polycyclic aromatic hydrocarbon for the detection of nonpolar analytes under counteracting humidity conditions. , 2012, ACS applied materials & interfaces.

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

[28]  G. Kwak,et al.  Fluorescent Viscosity Sensor Film of Molecular-Scale Porous Polymer with Intramolecular π-Stack Structure , 2011 .

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

[30]  D. Bloor Dissolution and Spectroscopic Properties of the Polydiacetylene Poly(10,12‐docosadiyne‐1,12‐diol‐bisethylurethane) , 2001 .

[31]  G. Clavier,et al.  Reversible quenching of a chromophore luminescence by color transition of a polydiacetylene. , 2013, ACS applied materials & interfaces.

[32]  D. Sasaki,et al.  First observation of mechanochromism at the nanometer scale , 2000 .

[33]  Andrea Pucci,et al.  Mechanochromic polymer blends , 2011 .

[34]  S. Holder,et al.  Mechanochromic systems for the detection of stress, strain and deformation in polymeric materials , 2011 .

[35]  R. Chance Chromism in Polydiacetylene Solutions and Crystals , 1980 .

[36]  G. Wegner Topochemical polymerization of monomers with conjugated triple bonds , 1972 .

[37]  Rakchart Traiphol,et al.  Controlling the reversible thermochromism of polydiacetylene/zinc oxide nanocomposites by varying alkyl chain length. , 2013, Journal of colloid and interface science.

[38]  R. A. Nallicheri,et al.  Investigations of the mechanochromic behavior of poly(urethane-diacetylene) segmented copolymers , 1991 .

[39]  G. Schatz,et al.  Self-assembly and photopolymerization of sub-2 nm one-dimensional organic nanostructures on graphene. , 2012, Journal of the American Chemical Society.

[40]  E. W. Meijer,et al.  Mechanically induced chemiluminescence from polymers incorporating a 1,2-dioxetane unit in the main chain. , 2012, Nature chemistry.

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

[42]  Jong-Man Kim,et al.  A protective layer approach to solvatochromic sensors , 2013, Nature Communications.

[43]  Juyoung Yoon,et al.  Polydiacetylene-based colorimetric and fluorescent chemosensor for the detection of carbon dioxide. , 2013, Journal of the American Chemical Society.

[44]  R. Baughman,et al.  Comments on the optical properties of fully conjugated polymers: Analogy between polyenes and polydiacetylenes , 1976 .

[45]  A. Porgador,et al.  Array-based disease diagnostics using lipid/polydiacetylene vesicles encapsulated in a sol-gel matrix , 2012, 2012 12th IEEE International Conference on Nanotechnology (IEEE-NANO).

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

[47]  P. Lu,et al.  Smart polydiacetylene nanowire paper with tunable colorimetric response , 2012 .

[48]  M. Sukwattanasinitt,et al.  Tuning Down of Color Transition Temperature of Thermochromically Reversible Bisdiynamide Polydiacetylenes , 2010 .

[49]  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.

[50]  J. Aizenberg,et al.  Bio-Inspired Band-Gap Tunable Elastic Optical Multilayer Fibers , 2013, Advanced materials.

[51]  R. Simha,et al.  Deformation-Induced Color Changes in Mechanochromic Polyethylene Blends , 2007 .

[52]  Edwin L. Thomas,et al.  Mechanochromic Photonic Gels , 2013, Advanced materials.

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

[54]  Juyoung Yoon,et al.  Biosensors and chemosensors based on the optical responses of polydiacetylenes. , 2012, Chemical Society reviews.

[55]  Mitchell T. Ong,et al.  Force-induced activation of covalent bonds in mechanoresponsive polymeric materials , 2009, Nature.

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