A pyrene-based metal-organic framework (MOF) NU-1000 was used as a heterogeneous photocatalyst for the degradation of a sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). Using irradiation from a commercially available and inexpensive ultraviolet (UV) light-emitting diode (LED), singlet oxygen (1O2) is generated by NU-1000 and selectively oxidizes CEES to the nontoxic product 2-chloroethyl ethyl sulfoxide (CEESO). More importantly, this method was tested on the warfare agent sulfur mustard (HD) for the first time using 1O2 and a MOF catalyst, and this method proved to be effective in oxidizing sulfur mustard to nontoxic products without forming the toxic sulfone by-product.
A fullerene-based photosensitizer is incorporated postsynthetically into a Zr -based MOF, NU-1000, for enhanced singlet oxygen production. The structural organic linkers in the MOF platform also act as photosensitizers which contribute to the overall generation of singlet oxygen from the material under UV irradiation. The singlet oxygen generated by the MOF/fullerene material is shown to oxidize sulfur mustard selectively to the less toxic bis(2-chloroethyl)sulfoxide with a half-life of only 11 min.
The vapor pressures of four lower alkyl phosphonate compounds, dimethyl phosphonate (DMHP, CAS 868-85-9), dimethyl methylphosphonate (DMMP, CAS 756-79-6), diethyl methylphosphonate (DEMP, CAS 683-08-9), and diisopropyl methylphosphonate (DIMP, CAS 1445-75-6), have been measured by complementary methods that allow data collection at ambient and high temperatures by use of gas saturation and differential scanning calorimetry, respectively. Kosolapoff (J. Chem. Soc.195529642965) reported vapor pressure data above 200 Pa for several of these compounds measured by use of isoteniscope, although the lowest data points were deemed to be “not trustworthy” by the author. Our report extends the low end of the measured data range by 2 to 3 orders of magnitude in pressure. Antoine correlations, normal boiling temperatures, temperature-dependent enthalpies of vaporization, and volatility have been derived based on the measured data reported herein. The advantages of using complementary methodology and measuring, as opposed to extrapolating, data have been demonstrated in this work.
Zirconium-based
metal organic frameworks (Zr-MOFs) are highly chemically
and thermally stable and have been of particular interest as reactive
sorbents for chemical warfare agent (CWA) removal due to their fast
and selective reactivity toward CWAs reported in buffer solutions.
However, we find that decontamination of neat CWAs directly on Zr-MOFs,
UiO-66, UiO-66-NH2, and NU-1000 is rather slow, and the
reactivity trend and products generated are very different from those
in solution. Furthermore, we show that their decontamination rates
are affected by the amount of moisture present in the MOFs. Although
the effects are minor for UiO-66-NH2 and NU-1000, the hydrolytic
activity of UiO-66 toward CWAs dramatically improves as the amount
of water present increases. Specifically, the initial hydrolysis rate
of methyl paraoxon by UiO-66 increases from 6 μmol/d with 0
wt % water loading to 140 μmol/d with 400 wt % water
loading. The results reported here suggest that decontamination of
CWAs by Zr-MOFs in solid phase behaves very differently than solution
decontamination. Additionally, we present for the first time a digestion
method for analyzing and quantifying solid-phase decontamination,
which is a daunting challenge itself due to the lack of a convenient
analytical method.
Sulfur mustard is one of the most toxic chemical warfare agents worldwide. We report the use of 4,4-difluoro-4-bora-3a,4a-diaza- s-indacene (BODIPY) photosensitizers as a fast and effective sulfur mustard decontaminant and their incorporation into various polymer coatings and fabrics, including army combat uniform. These BODIPY-embedded materials are capable of generating singlet oxygen under visible light irradiation and effectively detoxifying sulfur mustard by converting it into nontoxic sulfoxides as the major products. The rate of decontamination is found to be affected by the photosensitizer structure and concentration as well as the excitation wavelength. The most effective BODIPY-embedded self-decontamination material observed in this study shows a half-life of only 0.8 min. In comparison to the current methods, which use activated carbon as the adsorbent layer, these self-detoxifying coatings and fabrics provide constant destruction of and real-time protection against sulfur mustard.
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