Sensing Chemical Warfare Agent Simulants via Photonic Crystals of the <i>Morpho didius</i> Butterfly

Kittle, Joshua D.; Fisher, Benjamin P.; Esparza, Anthony J.; Morey, Aimee; Iacono, Scott T.

doi:10.1021/acsomega.7b01680

Cited by 22 publications

(39 citation statements)

References 48 publications

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“…Similarly, the broader peak and x-y shift for methanol in Figure 2 relative to the other spectra give rise to a broad peak in the differential spectra in Figure 3c centered near 600 nm. In Figure 2, ethanol shows a higher peak maxima than methanol and water, in line with predictions in our earlier work and consistent with refractive index trends [31]. However, the overall spectral difference ∆R for ethanol is lower than that of methanol or water as judged by the area of the curves in Figure 3a-c.…”

Section: Resultssupporting

confidence: 90%

“…Nitrogen was run between analytes. Similar to previous work [31], a brief run with 0.15 P 0 water vapor aided in quickly returning the response to the initial nitrogen baseline. The ∆R spectra were mean-centered in IgorPro, followed by PCA.…”

Section: Methodsmentioning

confidence: 73%

“…Light from a halogen source (Ocean Optics, HL-2000) was reflected off the center of the surface and collected via a spectrophotometer (Ocean Optics, HR2000+). A schematic of the experiment is provided in our previous work [31]. For all vapor measurements, a total gas flowrate of 400 mL•min −1 was used.…”

Section: Methodsmentioning

confidence: 99%

“…The use of both natural and synthetic PhCs as vapor sensors has been widely explored over the last twenty years [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23], though relatively few studies have examined their viability as CWA simulant detectors [24][25][26][27][28][29][30][31][32]. Typically, these studies have involved synthetic PhCs composed of porous silicon.…”

Section: Introductionmentioning

confidence: 99%

“…A recent study by our group examined the viability of a natural PhC found in the wing scales of the Morpho didius butterfly to selectively distinguish CWA simulant vapors from other common vapors. The study showed that each of the five vapors analyzed yielded unique reflectance profiles, with sensitivity in the low hundreds of parts per million (ppm) [31]. Though an increasing number of works have examined both natural and synthetic PhCs as vapor sensors, very few works have studied the selectivity of PhCs to binary and tertiary vapor mixtures [11,12,23].…”

Section: Introductionmentioning

confidence: 99%

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Vapor Selectivity of a Natural Photonic Crystal to Binary and Tertiary Mixtures Containing Chemical Warfare Agent Simulants

Kittle

Fisher

Kunselman

et al. 2019

Sensors

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Vapor sensing via light reflected from photonic crystals has been increasingly studied as a means to rapidly identify analytes, though few studies have characterized vapor mixtures or chemical warfare agent simulants via this technique. In this work, light reflected from the natural photonic crystals found within the wing scales of the Morpho didius butterfly was analyzed after exposure to binary and tertiary mixtures containing dimethyl methylphosphonate, a nerve agent simulant, and dichloropentane, a mustard gas simulant. Distinguishable spectra were generated with concentrations tested as low as 30 ppm and 60 ppm for dimethyl methylphosphonate and dichloropentane, respectively. Individual vapors, as well as mixtures, yielded unique responses over a range of concentrations, though the response of binary and tertiary mixtures was not always found to be additive. Thus, while selective and sensitive to vapor mixtures containing chemical warfare agent simulants, this technique presents challenges to identifying these simulants at a sensitivity level appropriate for their toxicity.

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Section: Resultssupporting

confidence: 90%

Section: Methodsmentioning

confidence: 73%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Vapor Selectivity of a Natural Photonic Crystal to Binary and Tertiary Mixtures Containing Chemical Warfare Agent Simulants

Kittle

Fisher

Kunselman

et al. 2019

Sensors

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Advances in Functional Solution Processed Planar 1D Photonic Crystals

Lova

Manfredi

Comoretto

2018

Advanced Optical Materials

156

226

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photonic states (PDOS), [2][3][4] which helps explaining the photoluminescence (PL) changes of materials when embedded in the PhC structure.Traditionally, PhCs have been made carving bulky inorganic dielectrics or sem iconductors. These structures are still a hot topic in photonics for optical fibers, light emitting diodes (LEDs), sensors, photo voltaic devices, lasers, discrete and integrated optical components, lightening, and quantum computing. [6] However, new solution processable photoactive materials (e.g., organic semiconductors, quantum dots, hybrid perovskites, and selfassem bling supramolecular systems) stimulated the development of PhCs grown with organic and colloidal materials by solution and melt processes. [7] Among PhCs, distributed Bragg reflectors (DBRs) are cur rently the most interesting owing to their planar structure which generates a simple optical response that represents a playground to understand deep physical concepts, as described in Sections 2.4 and 4. DBRs are indeed made of alternated thin films of different dielectric materials. This simplicity makes them the only PhCs that can take advantage of large area growths (see Section 3.1). [8] Such fabrication methods are unconceivable with bulky inorganic DBRs and might reduce processing costs and enhance customizability, also on industrial scale, thus adding unprecedented market opportunities. Figure 1 illustrates the evolution and fabrications of solution and melt processed DBRs. The top of the Figure displays three wellknown natural DBRs belonging to animal and plant reigns: the mother of pearl, [9] the Panamanian Tortoise beetle exoskel eton, [10] and the Pollia Condensata skin, [11] whose growth is driven by the thermodynamics of spinodal phase separation. [12] The interest in these natural structures leads to their emulation until the development of solutionbased fabrication methods for flexible synthetic DBRs made of polymers and inorganic nanoparticles (Figure 1). At the base of Figure 1, we also show some applications arose only in the last decades. From left to right: the use of DBRs in functional architecture, in enhance ment of photon absorption for photovoltaic cells and modules, emission control, lasing, and sensing. [7c,13] In this paper we will first briefly review the properties of DBRs and then focus on the reasons that guided the research toward new solutionbased and largearea fabrications, describing current processes used both at the laboratory and largearea scales. We will then review the main applications of these structures comparing the performances of mesoporous inorganic and polymer devices. An overview on the properties and applications of polymer and inorganic planar 1D photonic crystals fabricated from solution is provided here. In the last decades, photonic crystals became technologically relevant for light management, photovoltaics, sensing, and lasing. Such structures are traditionally produced by lithographic and vacuum techniques, but the need to reduce costs and to scale-up the fabrication have lea...

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Ditopic Chemodosimeter for Selective Detection of Nerve Agent Tabun Simulant DCNP

2022

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Selective optical detection of highly toxic nerve agents and their mimics like diethyl cyanophosphate (DCNP) is of paramount importance for armed forces and first responders in order to decide the suitable medical countermeasures. The reported optical chemical sensors for DCNP suffered from poor selectivity due to their single point covalent interaction with analyte. To overcome this limitation, we herein, report a novel protocol utilizing a ditopic chemodosimeter which, in presence of tetrabutylammonium hydroxide (TBAOH), underwent dual interaction with reactive subunits of DCNP, viz., electrophilic phosphorus and cyanide, to induce unique changes in its fluorescence as well as colorimetric properties. Other interfering analytes could not trigger the similar optical response in the sensing probe due to the absence of electrophilic phosphorus and cyanide. A truth table was constructed to reveal that only DCNP but not other analytes could induce changes in both fluorescence as well as colorimetric properties of sensing probe. The linearity range of the proposed method was found to be 30-70 μM while chromogenic limit of detection (LOD) was calculated to be 99 nM which are comparable to the reported methods. Thus, use of indigenously available 2-hydroxy-1-naphthaldehyde as sensing probe without requiring further chemical manipulation represented a significant improvement over the literature methods for DCNP sensing.

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Sensing Chemical Warfare Agent Simulants via Photonic Crystals of the Morpho didius Butterfly

Cited by 22 publications

References 48 publications

Vapor Selectivity of a Natural Photonic Crystal to Binary and Tertiary Mixtures Containing Chemical Warfare Agent Simulants

Vapor Selectivity of a Natural Photonic Crystal to Binary and Tertiary Mixtures Containing Chemical Warfare Agent Simulants

Advances in Functional Solution Processed Planar 1D Photonic Crystals

Ditopic Chemodosimeter for Selective Detection of Nerve Agent Tabun Simulant DCNP

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