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Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH ARTICLE (Open Access)

Correlating vapour uptake with the luminescence quenching of poly(dendrimer)s for the detection of nitro group-containing explosives

Kinitra L. Hutchinson A , Beta Z. Poliquit A , Andrew J. Clulow https://orcid.org/0000-0003-2037-853X A , Paul L. Burn https://orcid.org/0000-0003-3405-3517 A * , Ian R. Gentle A and Paul E. Shaw A
+ Author Affiliations
- Author Affiliations

A Centre for Organic Photonics & Electronics, School of Chemistry and Molecular Biosciences, The University of Queensland, Qld 4072, Australia.

* Correspondence to: p.burn2@uq.edu.au

Handling Editor: Curt Wentrup

Australian Journal of Chemistry - https://doi.org/10.1071/CH23131
Submitted: 4 July 2023  Accepted: 8 August 2023   Published online: 6 September 2023

© 2023 The Author(s) (or their employer(s)). Published by CSIRO Publishing. This is an open access article distributed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License (CC BY-NC-ND)

Abstract

Thin films of two poly(dendrimer)s were studied for the detection of trace quantities of nitro-based taggants and explosives. The poly(dendrimer) structures consist of side chain-conjugated triphenylamine-based dendritic chromophores attached to a non-conjugated polymer backbone. The poly(dendrimer)s differ in terms of the conjugation length, steric bulk and surface groups of the chromophores and we investigated the effects of these differences on sensing performance. We found that the addition of first-generation biphenyl-based dendrons to the chromophores of one of the polymers, P2, resulted in greater photoluminescence quenching, sensitivity and recovery to pulses of the vapours of the nitroaliphatic taggant 2,3-dimethyl-2,3-dinitrobutane (DMNB) and the nitroaromatic analyte 2,4-dinitrotoluene (2,4-DNT) compared with the other polymer, P1. We employed neutron reflectometry to characterise the vapour uptake of both poly(dendrimer)s and a structurally similar triphenylamine-based dendrimer D1 for comparison. The results show that the P2 has a mass density of 0.91 ± 0.01 v. 1.01 ± 0.01 g cm−3 for both P1 and D1 and can absorb at least twice the amount of 2,4-DNT. These results show how increasing the dendritic character of the poly(dendrimer) architecture provides a route for optimising vapour uptake and improving sensing performance in the solid state.

Keywords: dendrimers, explosive detection, luminescence, neutron reflectometry, photoinduced electron transfer, polymers, sensitivity, thin films.


References

[1]  Y Salinas, R Martínez-Máñez, MD Marcos, F Sancenón, AM Costero, M Parra, S Gil, Optical chemosensors and reagents to detect explosives. Chem Soc Rev 2012, 41, 1261.
         | Optical chemosensors and reagents to detect explosives.Crossref | GoogleScholarGoogle Scholar |

[2]  X Sun, Y Wang, Y Lei, Fluorescence based explosive detection: from mechanisms to sensory materials. Chem Soc Rev 2015, 44, 8019.
         | Fluorescence based explosive detection: from mechanisms to sensory materials.Crossref | GoogleScholarGoogle Scholar |

[3]  T Caron, M Guillemot, P Montméat, F Veignal, F Perraut, P Prené, F Serein-Spirau, Ultra trace detection of explosives in air: development of a portable fluorescent detector. Talanta 2010, 81, 543.
         | Ultra trace detection of explosives in air: development of a portable fluorescent detector.Crossref | GoogleScholarGoogle Scholar |

[4]  DS Moore, Instrumentation for trace detection of high explosives. Rev Sci Instruments 2004, 75, 2499.
         | Instrumentation for trace detection of high explosives.Crossref | GoogleScholarGoogle Scholar |

[5]  JS Yang, TM Swager, Fluorescent porous polymer films as TNT chemosensors: electronic and structural effects. J Am Chem Soc 1998, 120, 11864.
         | Fluorescent porous polymer films as TNT chemosensors: electronic and structural effects.Crossref | GoogleScholarGoogle Scholar |

[6]  PE Shaw, PL Burn, Real-time fluorescence quenching-based detection of nitro-containing explosive vapours: what are the key processes? Phys Chem Chem Phys 2017, 19, 29714.
         | Real-time fluorescence quenching-based detection of nitro-containing explosive vapours: what are the key processes?Crossref | GoogleScholarGoogle Scholar |

[7]  SW Thomas, GD Joly, TM Swager, Chemical sensors based on amplifying fluorescent conjugated polymers. Chem Rev 2007, 107, 1339.
         | Chemical sensors based on amplifying fluorescent conjugated polymers.Crossref | GoogleScholarGoogle Scholar |

[8]  Q Zhou, TM Swager, Fluorescent chemosensors based on energy migration in conjugated polymers: the molecular wire approach to increased sensitivity. J Am Chem Soc 1995, 117, 12593.
         | Fluorescent chemosensors based on energy migration in conjugated polymers: the molecular wire approach to increased sensitivity.Crossref | GoogleScholarGoogle Scholar |

[9]  PE Shaw, H Cavaye, SSY Chen, M James, IR Gentle, PL Burn, The binding and fluorescence quenching efficiency of nitroaromatic (explosive) vapors in fluorescent carbazole dendrimer thin films. Phys Chem Chem Phys 2013, 15, 9845.
         | The binding and fluorescence quenching efficiency of nitroaromatic (explosive) vapors in fluorescent carbazole dendrimer thin films.Crossref | GoogleScholarGoogle Scholar |

[10]  Y Geng, MA Ali, AJ Clulow, S Fan, PL Burn, IR Gentle, P Meredith, PE Shaw, Unambiguous detection of nitrated explosive vapours by fluorescence quenching of dendrimer films. Nat Commun 2015, 6, 8240.
         | Unambiguous detection of nitrated explosive vapours by fluorescence quenching of dendrimer films.Crossref | GoogleScholarGoogle Scholar |

[11]  MA Ali, Y Geng, H Cavaye, PL Burn, IR Gentle, P Meredith, PE Shaw, Molecular versus exciton diffusion in fluorescence-based explosive vapour sensors. Chem Commun 2015, 51, 17406.
         | Molecular versus exciton diffusion in fluorescence-based explosive vapour sensors.Crossref | GoogleScholarGoogle Scholar |

[12]  SM Russell, J Jang, AM Brewer, DM Stoltzfus, EV Puttock, PL Burn, A red emissive poly(dendrimer) for solution processed organic light-emitting diodes. Organic Electronics 2020, 78, 105594.
         | A red emissive poly(dendrimer) for solution processed organic light-emitting diodes.Crossref | GoogleScholarGoogle Scholar |

[13]  AS Loch, DM Stoltzfus, PL Burn, PE Shaw, High-sensitivity poly(dendrimer)-based sensors for the detection of explosives and taggant vapors. Macromolecules 2020, 53, 1652.
         | High-sensitivity poly(dendrimer)-based sensors for the detection of explosives and taggant vapors.Crossref | GoogleScholarGoogle Scholar |

[14]  KL Hutchinson, DM Stoltzfus, PL Burn, PE Shaw, Luminescent poly(dendrimer)s for the detection of explosives. Mater Adv 2020, 1, 837.
         | Luminescent poly(dendrimer)s for the detection of explosives.Crossref | GoogleScholarGoogle Scholar |

[15]  H Cavaye, PE Shaw, X Wang, PL Burn, SC Lo, P Meredith, Effect of dimensionality in dendrimeric and polymeric fluorescent materials for detecting explosives. Macromolecules 2010, 43, 10253.
         | Effect of dimensionality in dendrimeric and polymeric fluorescent materials for detecting explosives.Crossref | GoogleScholarGoogle Scholar |

[16]  JM Lupton, IDW Samuel, PL Burn, S Mukamel, Control of intrachromophore excitonic coherence in electroluminescent conjugated dendrimers. J Phys Chem B 2002, 106, 7647.
         | Control of intrachromophore excitonic coherence in electroluminescent conjugated dendrimers.Crossref | GoogleScholarGoogle Scholar |

[17]  SW Thomas III, JP Amara, RE Bjork, TM Swager, Amplifying fluorescent polymer sensors for the explosives taggant 2,3-dimethyl-2,3-dinitrobutane (DMNB). Chem Commun 2005, 36, 4572.
         | Amplifying fluorescent polymer sensors for the explosives taggant 2,3-dimethyl-2,3-dinitrobutane (DMNB).Crossref | GoogleScholarGoogle Scholar |

[18]  AJ Clulow, PL Burn, P Meredith, PE Shaw, Fluorescent carbazole dendrimers for the detection of nitroaliphatic taggants and accelerants. J Mater Chem 2012, 22, 12507.
         | Fluorescent carbazole dendrimers for the detection of nitroaliphatic taggants and accelerants.Crossref | GoogleScholarGoogle Scholar |

[19]  H Cavaye, ARG Smith, M James, A Nelson, PL Burn, IR Gentle, SC Lo, P Meredith, Solid-state dendrimer sensors: probing the diffusion of an explosive analogue using neutron reflectometry. Langmuir 2009, 25, 12800.
         | Solid-state dendrimer sensors: probing the diffusion of an explosive analogue using neutron reflectometry.Crossref | GoogleScholarGoogle Scholar |

[20]  H Cavaye, PE Shaw, ARG Smith, PL Burn, IR Gentle, M James, SC Lo, P Meredith, Solid state dendrimer sensors: effect of dendrimer dimensionality on detection and sequestration of 2,4-dinitrotoluene. J Phys Chem C 2011, 115, 18366.
         | Solid state dendrimer sensors: effect of dendrimer dimensionality on detection and sequestration of 2,4-dinitrotoluene.Crossref | GoogleScholarGoogle Scholar |

[21]  OV Mikhnenko, PWM Blom, TQ Nguyen, Exciton diffusion in organic semiconductors. Energy Environ Sci 2015, 8, 1867.
         | Exciton diffusion in organic semiconductors.Crossref | GoogleScholarGoogle Scholar |

[22]  NC Greenham, IDW Samuel, GR Hayes, RT Phillips, YARR Kessener, SC Moratti, AB Holmes, RH Friend, Measurement of absolute photoluminescence quantum efficiencies in conjugated polymers. Chem Phys Lett 1995, 241, 89.
         | Measurement of absolute photoluminescence quantum efficiencies in conjugated polymers.Crossref | GoogleScholarGoogle Scholar |

[23]  M James, A Nelson, SA Holt, T Saerbeck, WA Hamilton, F Klose, The multipurpose time-of-flight neutron reflectometer ‘Platypus’ at Australia’s OPAL reactor. Nucl Instru Meth Phys Res Sect A 2011, 632, 112.
         | The multipurpose time-of-flight neutron reflectometer ‘Platypus’ at Australia’s OPAL reactor.Crossref | GoogleScholarGoogle Scholar |

[24]  A Nelson, Co-refinement of multiple-contrast neutron/X-ray reflectivity data using MOTOFIT. J Appl Crystallogr 2006, 39, 273.
         | Co-refinement of multiple-contrast neutron/X-ray reflectivity data using MOTOFIT.Crossref | GoogleScholarGoogle Scholar |