Attogram sensing of trinitrotoluene with a self-assembled molecular gelator.

Detection of explosives is of utmost importance due to the threat to human security as a result of illegal transport and terrorist activities. Trinitrotoluene (TNT) is a widely used explosive in landmines and military operations that contaminates the environment and groundwater, posing a threat to human health. Achieving the detection of explosives at a sub-femtogram level using a molecular sensor is a challenge. Herein we demonstrate that a fluorescent organogelator exhibits superior detection capability for TNT in the gel form when compared to that in the solution state. The gel when coated on disposable paper strips detects TNT at a record attogram (ag, 10(-18) g) level (∼12 ag/cm(2)) with a detection limit of 0.23 ppq. This is a simple and low-cost method for the detection of TNT on surfaces or in aqueous solutions in a contact mode, taking advantage of the unique molecular packing of an organogelator and the associated photophysical properties.

[1]  Ana M. Costero,et al.  Optical chemosensors and reagents to detect explosives. , 2012, Chemical Society reviews.

[2]  Haibo Zhou,et al.  Instant visual detection of trinitrotoluene particulates on various surfaces by ratiometric fluorescence of dual-emission quantum dots hybrid. , 2011, Journal of the American Chemical Society.

[3]  Manoj Kumar,et al.  Triazole-modified triphenylene derivative: self-assembly and sensing applications. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[4]  T. Swager,et al.  Porous Shape Persistent Fluorescent Polymer Films: An Approach to TNT Sensory Materials , 1998 .

[5]  H. Puschmann,et al.  Synthesis and structure of 4,4′-bis(2,3,4,5,6-pentafluorostyryl)stilbene, a self-assembling J aggregate based on aryl–fluoroaryl interactions , 2001 .

[6]  K. Gleason,et al.  Synthesis of Poly(4‐vinylpyridine) Thin Films by Initiated Chemical Vapor Deposition (iCVD) for Selective Nanotrench‐Based Sensing of Nitroaromatics , 2010 .

[7]  Zhengguo Zhu,et al.  Sensitivity gains in chemosensing by lasing action in organic polymers , 2005, Nature.

[8]  Chengyi Zhang,et al.  Organic nanofibrils based on linear carbazole trimer for explosive sensing. , 2010, Chemical communications.

[9]  D. Moore Instrumentation for trace detection of high explosives , 2004 .

[10]  Ho-Joong Kim,et al.  Responsive nanostructures from aqueous assembly of rigid-flexible block molecules. , 2011, Accounts of chemical research.

[11]  William C. Trogler,et al.  Efficient blue-emitting silafluorene–fluorene-conjugated copolymers: selective turn-off/turn-on detection of explosives , 2008 .

[12]  Sang-Don Jung,et al.  Enhanced emission and its switching in fluorescent organic nanoparticles. , 2002, Journal of the American Chemical Society.

[13]  A. Ajayaghosh,et al.  Solvent-directed self-assembly of pi gelators to hierarchical macroporous structures and aligned fiber bundles. , 2009, Chemistry, an Asian journal.

[14]  Subi J. George,et al.  Molecular wire encapsulated into pi organogels: efficient supramolecular light-harvesting antennae with color-tunable emission. , 2007, Angewandte Chemie.

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

[16]  A. Ajayaghosh,et al.  Pi-organogels of self-assembled p-phenylenevinylenes: soft materials with distinct size, shape, and functions. , 2007, Accounts of chemical research.

[17]  Peter Müller,et al.  Interrupted energy transfer: highly selective detection of cyclic ketones in the vapor phase. , 2011, Journal of the American Chemical Society.

[18]  G. Kwak,et al.  Fluoroalkylated Polysilane Film as a Chemosensor for Explosive Nitroaromatic Compounds , 2005 .

[19]  T. Swager,et al.  Three-dimensional electronic delocalization in chiral conjugated polymers. , 2002, Angewandte Chemie.

[20]  A Fainberg,et al.  Explosives Detection for Aviation Security , 1992, Science.

[21]  Meaghan E Germain,et al.  Optical explosives detection: from color changes to fluorescence turn-on. , 2009, Chemical Society reviews.

[22]  Subi J. George,et al.  Self-assembled pi-nanotapes as donor scaffolds for selective and thermally gated fluorescence resonance energy transfer (FRET). , 2006, Journal of the American Chemical Society.

[23]  Ling Zang,et al.  One-dimensional self-assembly of planar pi-conjugated molecules: adaptable building blocks for organic nanodevices. , 2008, Accounts of chemical research.

[24]  R. Capelli,et al.  A potential J aggregate molecular system: crystal packing and optical properties of 4,4'-bis(2,3,4,5,6-pentafluorostyryl)stilbene , 2003 .

[25]  D. Olson,et al.  A luminescent microporous metal-organic framework for the fast and reversible detection of high explosives. , 2009, Angewandte Chemie.

[26]  S. Shinkai,et al.  A chromo-fluorogenic tetrazole-based CoBr2 coordination polymer gel as a highly sensitive and selective chemosensor for volatile gases containing chloride. , 2011, Chemistry.

[27]  V. K. Praveen,et al.  Quadrupolar π‐Gels: Sol–Gel Tunable Red–Green–Blue Emission in Donor–Acceptor‐Type Oligo(p‐phenylenevinylene)s , 2007 .

[28]  Frances S. Ligler,et al.  On-site detection of TNT with a portable fiber optic biosensor , 1997 .

[29]  Self-amplifying semiconducting polymers for chemical sensors , 2002 .

[30]  A. Ajayaghosh,et al.  RGB Emission through Controlled Donor Self‐Assembly and Modulation of Excitation Energy Transfer: A Novel Strategy to White‐Light‐Emitting Organogels , 2009 .

[31]  Anthony W. Czarnik,et al.  A sense for landmines , 1998, Nature.

[32]  Douglas Magde,et al.  Luminescent oligo(tetraphenyl)silole nanoparticles as chemical sensors for aqueous TNT. , 2005, Chemical communications.

[33]  Itamar Willner,et al.  Imprinting of molecular recognition sites through electropolymerization of functionalized Au nanoparticles: development of an electrochemical TNT sensor based on pi-donor-acceptor interactions. , 2008, Journal of the American Chemical Society.

[34]  B. Rogers,et al.  Explosives: A microsensor for trinitrotoluene vapour , 2003, Nature.

[35]  K. Schanze,et al.  Amplified quenching of a conjugated polyelectrolyte by cyanine dyes. , 2004, Journal of the American Chemical Society.

[36]  W. Trogler,et al.  Synthesis, Luminescence Properties, and Explosives Sensing with 1,1-Tetraphenylsilole- and 1,1-Silafluorene-vinylene Polymers , 2007 .

[37]  Subi J. George,et al.  First phenylenevinylene based organogels: self-assembled nanostructures via cooperative hydrogen bonding and pi-stacking. , 2001, Journal of the American Chemical Society.

[38]  Manu Prasanna,et al.  High-sensitivity detection of TNT , 2006, Proceedings of the National Academy of Sciences.

[39]  Lisa C. Shriver-Lake,et al.  On-site detection of explosives in groundwater with a fiber optic biosensor , 2000 .

[40]  Itamar Willner,et al.  Electrified selective "sponges" made of Au nanoparticles. , 2010, Journal of the American Chemical Society.

[41]  Liping Ding,et al.  Pyrene-Containing Conjugated Polymer-Based Fluorescent Films for Highly Sensitive and Selective Sensing of TNT in Aqueous Medium , 2011 .

[42]  T Sitalaximi,et al.  Autosomal microsatellite profile of three socially diverse ethnic Tamil populations of India. , 2003, Journal of forensic sciences.

[43]  Alan J. Heeger,et al.  The exciton binding energy in luminescent conjugated polymers , 1996 .

[44]  A. Ajayaghosh,et al.  Self-assembly of oligo(para-phenylenevinylene)s through arene-perfluoroarene interactions: pi gels with longitudinally controlled fiber growth and supramolecular exciplex-mediated enhanced emission. , 2008, Chemistry.

[45]  K. Schanze,et al.  Phosphorescent platinum acetylide organogelators. , 2008, Journal of the American Chemical Society.

[46]  A. Ajayaghosh,et al.  Excitation energy migration in oligo(p-phenylenevinylene) based organogels: structure-property relationship and FRET efficiency. , 2011, Physical chemistry chemical physics : PCCP.

[47]  B. Nilsson,et al.  Complementary π-π interactions induce multicomponent coassembly into functional fibrils. , 2011, Langmuir : the ACS journal of surfaces and colloids.

[48]  Subi J. George,et al.  Self-assembled nanotapes of oligo(p-phenylene vinylene)s: sol-gel-controlled optical properties in fluorescent pi-electronic gels. , 2005, Chemistry.

[49]  Subi J. George,et al.  Gelation-assisted light harvesting by selective energy transfer from an oligo(p-phenylenevinylene)-based self-assembly to an organic dye. , 2003, Angewandte Chemie.

[50]  T. Swager,et al.  Conjugated polymer-based chemical sensors. , 2000, Chemical reviews.

[51]  A. Ajayaghosh,et al.  Reversible self-assembly of entrapped fluorescent gelators in polymerized styrene gel matrix: erasable thermal imaging via recreation of supramolecular architectures. , 2009, Journal of the American Chemical Society.

[52]  Brian Caddy,et al.  Forensic and Environmental Detection of Explosives, Jehuda Yinon. John Wiley and Sons, Chichester (1999), index, 285pp; £100.00, ISBN: 0-471-98371-3 , 1999 .

[53]  A. Xu,et al.  Plasmonic resonance energy transfer-based nanospectroscopy for sensitive and selective detection of 2,4,6-trinitrotoluene (TNT). , 2011, Chemical communications.

[54]  Eli Flaxer,et al.  Supersensitive detection of explosives by silicon nanowire arrays. , 2010, Angewandte Chemie.

[55]  Jian Yang,et al.  Hollow silica nanospheres containing a silafluorene-fluorene conjugated polymer for aqueous TNT and RDX detection. , 2010, Chemical communications.

[56]  Soon-Ki Kwon,et al.  Highly Sensitive Fluorescence Probes for Organic Vapors: On/off and Dual Color Fluorescence Switching , 2005 .

[57]  I. Willner,et al.  Ultrasensitive surface plasmon resonance detection of trinitrotoluene by a bis-aniline-cross-linked Au nanoparticles composite. , 2009, Journal of the American Chemical Society.

[58]  G. Tobin,et al.  Detection of explosive vapors with a charge transfer molecule: self-assembly assisted morphology tuning and enhancement in sensing efficiency. , 2010, Chemical communications.

[59]  M. Chruszcz,et al.  Self-assembled thermoreversible gels of nonpolar liquids by racemic propargylic alcohols with fluorinated and nonfluorinated aromatic rings. , 2008, Langmuir : the ACS journal of surfaces and colloids.

[60]  Shannon E. Stitzel,et al.  Cross-reactive chemical sensor arrays. , 2000, Chemical reviews.

[61]  Jinhuai Liu,et al.  Sunlight-induced formation of silver-gold bimetallic nanostructures on DNA template for highly active surface enhanced Raman scattering substrates and application in TNT/tumor marker detection , 2009 .

[62]  Katsuhiko Ariga,et al.  Challenges and breakthroughs in recent research on self-assembly , 2008, Science and technology of advanced materials.

[63]  S. Shanmugaraju,et al.  Supramolecular polymer for explosives sensing: role of H-bonding in enhancement of sensitivity in the solid state. , 2011, Chemical communications.

[64]  Manuel A Palacios,et al.  Simple molecule-based fluorescent sensors for vapor detection of TNT. , 2008, Organic letters.

[65]  Igor L. Medintz,et al.  A hybrid quantum dot-antibody fragment fluorescence resonance energy transfer-based TNT sensor. , 2005, Journal of the American Chemical Society.

[66]  Michael J Sailor,et al.  Detection of nitroaromatic explosives based on photoluminescent polymers containing metalloles. , 2003, Journal of the American Chemical Society.

[67]  S. W. Thomas,et al.  Chemical sensors based on amplifying fluorescent conjugated polymers. , 2007, Chemical reviews.

[68]  A. Ajayaghosh,et al.  Excited State Processes in Linear π-System-Based Organogels , 2010 .

[69]  R. Grubbs,et al.  Arene–Perfluoroarene Interactions as Physical Cross‐Links for Hydrogel Formation , 2002 .

[70]  T. Swager Iptycenes in the design of high performance polymers. , 2008, Accounts of chemical research.

[71]  A. Ajayaghosh,et al.  Organogels as scaffolds for excitation energy transfer and light harvesting. , 2008, Chemical Society reviews.

[72]  A. Ajayaghosh,et al.  Self-location of acceptors as "isolated" or "stacked" energy traps in a supramolecular donor self-assembly: a strategy to wavelength tunable FRET emission. , 2006, Journal of the American Chemical Society.

[73]  C. Schäfer,et al.  Time-resolved confocal fluorescence microscopy of trinitrobenzene-responsive organic nanofibers , 2010, Analytical and bioanalytical chemistry.

[74]  David W. Conrad,et al.  Detection of TNT in Water Using an Evanescent Wave Fiber-Optic Biosensor , 1995 .

[75]  T. Swager,et al.  Fluorescent Porous Polymer Films as TNT Chemosensors: Electronic and Structural Effects , 1998 .

[76]  Richard H. Friend,et al.  An improved experimental determination of external photoluminescence quantum efficiency , 1997 .

[77]  Jincai Zhao,et al.  Detection of explosives with a fluorescent nanofibril film. , 2007, Journal of the American Chemical Society.

[78]  C. Zheng,et al.  New microporous metal-organic framework demonstrating unique selectivity for detection of high explosives and aromatic compounds. , 2011, Journal of the American Chemical Society.

[79]  Michael J Sailor,et al.  Detection of TNT and Picric Acid on Surfaces and in Seawater by Using Photoluminescent Polysiloles. , 2001, Angewandte Chemie.

[80]  Suman Singh,et al.  Sensors--an effective approach for the detection of explosives. , 2007, Journal of hazardous materials.

[81]  Philip H. Howard,et al.  Handbook of Physical Properties of Organic Chemicals , 1997 .