A Nanosensor for TNT Detection Based on Molecularly Imprinted Polymers and Surface Enhanced Raman Scattering

Holthoff, Ellen L.; Stratis‐Cullum, Dimitra N.; Hankus, Mikella E.

doi:10.3390/s110302700

Cited by 188 publications

(135 citation statements)

References 32 publications

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“…3 Various analytical and spectroscopic methods have been developed for sensitive detection of NA compounds. [4][5][6][7] These instrumental techniques are mostly expensive and not portable for use in the field. The detection of NA explosives using fluorescent-based sensors has been extensively studied because of their sensitivity, portability, and short response time.…”

mentioning

confidence: 99%

Extremely fast and highly selective detection of nitroaromatic explosive vapours using fluorescent polymer thin films

2013

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A novel sensing material based on pyrene doped polyethersulfone worm-like structured thin film is developed using a facile technique for detection of nitroaromatic explosive vapours. The formation of p-p stacking in the thin fluorescent film allows a highly sensitive fluorescence quenching which is detectable by the naked eye in a response time of a few seconds.Nitroaromatic (NA) explosives are the primary constituents of many unexploded land mines worldwide.1,2 Selective, fast and low-cost detection of NA explosives, such as trinitrotoluene (TNT) and dinitrotoluene (DNT), is crucial for military operations, homeland security, and environmental safety. 3 Various analytical and spectroscopic methods have been developed for sensitive detection of NA compounds. [4][5][6][7] These instrumental techniques are mostly expensive and not portable for use in the field. The detection of NA explosives using fluorescent-based sensors has been extensively studied because of their sensitivity, portability, and short response time. [8][9][10][11][12][13] The most important report in this field was published by Swager' group. 14 They used a conjugated polymer scaffold and improved the detection sensitivity. 14 Trogler and co-workers developed a new class of fluorescent films which were fabricated by spin-coating onto suitable solid substrates for detecting NA explosives both in the air and organic solvents. 15 The underlying explosive detection mechanism of the fluorescent polymer is photo-induced electron transfer (PET) from the polymers to the NA explosives. The key feature of this phenomenon is the presence of the p-p-stacking (excimer) between the polymer chains and chromophore groups.This p-stacked formation can significantly enhance the sensing performance of films.14,15In this report, we have fabricated a novel fluorescent thin film based on the pyrene-doped polyethersulfone (Py-PES) polymer for detection of nitro-explosive vapours using a rapid and facile method. The experimental details of the preparation of this sensing film are given in ESI. † To prepare the fluorescent polymer, we chose pyrene (Py) as the fluorescent dye because of its potential to form highly emissive excited dimers, high fluorescence yield, and known fluorescence quenching sensitivity to NA compounds. 16 The driving force for the quenching mechanism of Py-PES thin films is the formation of p-p Scheme 1 Schematic representation of the quenching mechanism for the Py-PES film by TNT based on photo-electron transfer (PET) process. The main driving force for the PET process is the energy gap between the conduction band of Py-PES films and the LUMO of NA explosives. NA explosives accept the electron from exited state of pyrene due to their low LUMO energies and as a result the fluorescent film is quenched 18 (see details in ESI †).a UNAM-National Nanotechnology Research Center, Bilkent University, 06800 Ankara, Turkey. E-mail: birlik@unam.bilkent.edu.tr b Department of Chemistry, Gazi University, Polatli, 06900, Ankara, Turkey c Institute of Materials Sc...

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confidence: 99%

Extremely fast and highly selective detection of nitroaromatic explosive vapours using fluorescent polymer thin films

2013

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“…There is, however, a significant disadvantage of antibodies when it comes to direct detection of the analyte because their relatively large size sets a large distance between the analyte and the substrate. There are other capturing molecules that are gaining some attention such as enzymes, molecularly imprinted polymers, and affimers [151][152][153]. While they hold promise for functional SERS assays, they have yet to gain momentum for both research and real-world applications.…”

Section: Functional Assaysmentioning

confidence: 99%

Fundamentals and applications of SERS-based bioanalytical sensing

et al. 2017

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Abstract:Plasmonics is an emerging field that examines the interaction between light and metallic nanostructures at the metal-dielectric interface. Surface-enhanced Raman scattering (SERS) is a powerful analytical technique that uses plasmonics to obtain detailed chemical information of molecules or molecular assemblies adsorbed or attached to nanostructured metallic surfaces. For bioanalytical applications, these surfaces are engineered to optimize for high enhancement factors and molecular specificity. In this review we focus on the fabrication of SERS substrates and their use for bioanalytical applications. We review the fundamental mechanisms of SERS and parameters governing SERS enhancement. We also discuss developments in the field of novel SERS substrates. This includes the use of different materials, sizes, shapes, and architectures to achieve high sensitivity and specificity as well as tunability or flexibility. Different fundamental approaches are discussed, such as label-free and functional assays. In addition, we highlight recent relevant advances for bioanalytical SERS applied to small molecules, proteins, DNA, and biologically relevant nanoparticles. Subsequently, we discuss the importance of data analysis and signal detection schemes to achieve smaller instruments with low cost for SERS-based point-of-care technology developments. Finally, we review the main advantages and challenges of SERS-based biosensing and provide a brief outlook.

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“…The integrated MIP for explosives detection has shown that it is selective to 2,4-DNT and has demonstrated reliable reversibility and stability. 18 In this work, the gas sensing experiment was performed with the noise-squeezing controller at a concentration of 0.93 parts-per-billion (ppb) 2,4-DNT. Figure 5 presents the change in the natural frequency of the microbeam sensor over time as it is challenged with 2,4-DNT.…”

Section: Mip Integration and Sensor Performancementioning

confidence: 99%

“…16,17 In this work, molecularly imprinted xerogel thin films have demonstrated selectivity and stability in combination with a fixed-fixed beam MEMS cantilever. 18,19 Traditionally, mass sensing using MEMS resonators has been achieved based on the natural frequency shift due to an increase in resonator mass; however, noise has set the limit of detection for linear sensing. 20 As an alternative to using changes in the natural frequency, nonlinear dynamics induced by parametric excitation have led to successful cantilever-based sensor designs.…”

Section: Introductionmentioning

confidence: 99%

A Molecularly Imprinted Polymer (MIP)-Coated Microbeam MEMS Sensor for Chemical Detection

Holthoff¹,

Li²,

Hiller³

et al. 2015

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A reprint from Proc. of SPIE Vol. 9455 94550W-1.Approved for public release; distribution unlimited. NOTICES DisclaimersThe findings in this report are not to be construed as an official Department of the Army position unless so designated by other authorized documents.Citation of manufacturer's or trade names does not constitute an official endorsement or approval of the use thereof.Destroy this report when it is no longer needed. Do not return it to the originator. Respondents should be aware that notwithstanding any other provision of law, no person shall be subject to any penalty for failing to comply with a collection of information if it does not display a currently valid OMB control number. ARL-RP-0536 PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. REPORT DATE (DD-MM-YYYY)Sep 2015 SPONSOR/MONITOR'S REPORT NUMBER(S) DISTRIBUTION/AVAILABILITY STATEMENTApproved for public release; distribution unlimited. SUPPLEMENTARY NOTESA reprint from Proc. of SPIE Vol. 9455 94550W-1. ABSTRACTRecently, microcantilever-based technology has emerged as a viable sensing platform due to its many advantages such as small size, high sensitivity, and low cost. However, microcantilevers lack the inherent ability to selectively identify hazardous chemicals (e.g., explosives, chemical warfare agents). The key to overcoming this challenge is to functionalize the top surface of the microcantilever with a receptor material (e.g., a polymer coating) so that selective binding between the cantilever and analyte of interest takes place. Molecularly imprinted polymers (MIPs) can be utilized as artificial recognition elements for target chemical analytes of interest. Molecular imprinting involves arranging polymerizable functional monomers around a template molecule followed by polymerization and template removal. The selectivity for the target analyte is based on the spatial orientation of the binding site and covalent or noncovalent interactions between the functional monomer and the analyte. In this work, thin films of sol-gel-derived xerogels molecularly imprinted for TNT and dimethyl methylphosphonate (DMMP), a chemical warfare agent stimulant, have demonstrated selectivity and stability in combination with a fixed-fixed beam microelectromechanical systems (MEMS)-based gas sensor. The sensor was characterized by parametric bifurcation noise-based tracking. ABSTRACT Recently, microcantilever-based technology has emerged as a viable sensing platform due to its many advantages such as small size, high sensitivity, and low cost. However, microcantilevers lack the inherent ability to selectively identify hazardous chemicals (e.g., explosives, chemical warfare agents). The key to overcoming this challenge is to functionalize the top surface of the microcantilever with a receptor material (e.g., a polymer coating) so that selective binding between the cantilever and analyte of interest takes place. Molecularly imprinted polymers (MIPs) can be utilized as artificial recognition elements for target chemical analytes of interest. Molecular...

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A Nanosensor for TNT Detection Based on Molecularly Imprinted Polymers and Surface Enhanced Raman Scattering

Cited by 188 publications

References 32 publications

Extremely fast and highly selective detection of nitroaromatic explosive vapours using fluorescent polymer thin films

Extremely fast and highly selective detection of nitroaromatic explosive vapours using fluorescent polymer thin films

Fundamentals and applications of SERS-based bioanalytical sensing

A Molecularly Imprinted Polymer (MIP)-Coated Microbeam MEMS Sensor for Chemical Detection

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