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Despite the recent surge of interest in two-dimensional (2D) inorganic nanosheets derived from photoactive coordination polymers of lanthanide ions having interesting optical properties, research in this area is still in its infancy. Luminescent lanthanide ions, Eu(iii) or/and Tb(iii), as well as a bis-terpyridine ligand (L), were used in this study as the building blocks for the synthesis of the archetypical layered structure of coordination polymers (CPs) (L·Eu/L·Tb). 2D-nanosheets were obtained through exfoliation of the layered precursor of CPs in a suitable solvent system following a sonication-assisted strategy. These nanosheets exhibit lateral sizes on the micrometer scale (0.3-1 μm) and an ultrathin thickness of 2-6.5 nm. 1,1-Diamino-2,2-dinitroethene or FOX-7 is an insensitive high explosive; in a binder mixture, it exhibits a slightly superior detonation velocity of 8870 m s in comparison to RDX. The insensitive nature of FOX-7 makes it a key component for the development of low vulnerable high explosive compositions for further application in weaponry. The growing demand for FOX-7, for use as a suitable replacement of conventional explosives, is of serious concern to human security. Achieving rapid and efficient detection of this unexplored explosive is a challenging task. In the present study, the developed luminescent nanosheets were used for the first time for micromolar level detection of FOX-7 both in solution and in the solid state. A visually distinct color change of the nanosheets from red (L·Eu) and green (L·Tb) to colorless was witnessed upon UV light irradiation during the detection process. Notably, the solid-state detection technique could be exploited for developing a commercial spray kit for quick onsite screening of this important explosive.
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http://dx.doi.org/10.1039/c9sc05403k | DOI Listing |
J Phys Chem A
September 2023
Department of Chemistry, University of Hawaii, Honolulu, Hawaii 96822, United States.
FOX-7 (1,1-diamino-2,2-dinitroethylene) was photolyzed with 202 nm photons to probe reaction energies, leading to the decomposition of this energetic material and to compare results from irradiations using lower-energy 532 and 355 nm photons as well as higher-energy electrons. The photolysis occurred at 5 K to suppress thermal reactions, and the solid samples were monitored using Fourier transform infrared spectroscopy (FTIR), which observed carbon dioxide (CO), carbon monoxide (CO), cyanide (CN), and cyanate (OCN) after irradiation. During warming to 300 K, subliming products were detected using electron-impact quadrupole mass spectrometry (EI-QMS) and photoionization time-of-flight mass spectrometry (PI-ReTOF-MS).
View Article and Find Full Text PDFJ Phys Chem A
April 2023
Department of Chemistry, University of Hawaii, Honolulu, Hawaii 96822, United States.
Solid FOX-7 (1,1-diamino-2,2-dinitroethylene), an energetic material of interest due to its high stability and low shock/thermal sensitivity, was exposed to energetic electrons at 5 K to explore the fundamental mechanisms leading to decomposition products and provide a better understanding of the reaction pathways involved. As a result of the radiation exposure, infrared spectroscopy revealed carbon dioxide (CO) and carbon monoxide (CO) trapped in the FOX-7 matrix, while these compounds along with water (HO), nitrogen monoxide (NO), and cyanogen (CN) were detected exploiting quadrupole mass spectrometry both during irradiation and during the warming phase from 5 to 300 K. Photoionization reflectron time-of-flight mass spectrometry detected small molecules such as ammonia (NH), nitrogen monoxide (NO), and nitrogen dioxide (NO) as well as more complex molecules up to 96 amu.
View Article and Find Full Text PDFJ Phys Chem A
July 2022
Department of Chemistry, University of Hawaii, Honolulu, Hawaii 96822, United States.
The UV photolysis of solid FOX-7 at 5 K with 355 and 532 nm photons was investigated to unravel initial isomerization and decomposition pathways. Isomer-selective single photon ionization coupled with reflectron time-of-flight mass spectrometry (ReTOF-MS) documented the nitric oxide (NO) loss channel at 355 nm along with a nitro-to-nitrite isomerization, which was observed by using infrared spectroscopy, representing the initial reaction pathway followed by O─NO bond rupture of the nitrite moiety. A residual gas analyzer detected molecular oxygen for the 355 and 532 nm photolysis at a ratio of 4.
View Article and Find Full Text PDFMolecules
June 2022
School of Environment and Safety Engineering, North University of China, Taiyuan 030051, China.
The crystal and molecular structures, intermolecular interactions, and energy of CL-20, HATO, and FOX-7 were comparatively predicted based on molecular dynamic (MD) simulations. By comparison, the 2D fingerprint plot, Hirshfeld surface, reduced density gradient isosurface, and electrostatic potential surface were studied to detect the intermolecular interactions. Meanwhile, the effects of vacuum and different solvents on the crystal habit of CL-20, HATO, and FOX-7 were studied by AE and MAE model, respectively.
View Article and Find Full Text PDFAnal Chim Acta
February 2022
School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China. Electronic address:
The fluorescent properties of conjugated microporous polyphenylene (CMPs) were tuned through a wide range by inclusion of small amount of comonomer as chromophore in the network. The multi-color CMPs were used for explosives sensing and demonstrated broad sensitivity (ranging from -0.01888 μM to -0.
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