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1. Membrane-supported metal organic framework based nanopacked bed for protection against toxic vapors and gases

   https://doi.org/https://doi.org/10.1016/j.seppur.2020.117406  

   Song, Yufeng; Chau, John; Sirkar, Kamalesh K.; Peterson, Gregory W.; Beuscher, Uwe (July 2020, Separation and purification technology)

   null (Ed.)

   Defense against small molecule toxic gases is an important aspect of protection against chemical and biological threat as well as chemical releases from industrial accidents. Current protective respirators/garments cannot effectively block small molecule toxic gases and vapors and retain moisture transmission capability without a heavy burden. Here, we developed a nanopacked bed of nanoparticles of UiO-66-NH₂ metal organic framework (MOF) by synthesizing them in the pores of microporous expanded polytetrafluoroethylene (ePTFE) membranes. The submicron scale size of membrane pores ensures a large surface area of MOF nanoparticles which can capture/adsorb and react with toxic gas molecules efficiently. It was demonstrated that the microporous ePTFE membrane with UiO-66-NH₂ MOF grown inside and around the membrane can defend against ammonia for a significant length of time while allowing passage of moisture and nitrogen. It was also demonstrated that the MOF-loaded ePTFE membrane could provide significant protection from Cl₂ intrusion as well as intrusion from 2-chloroethyl ethyl sulfide (CEES) (a simulant for sulfur mustard). Such MOF-filled membranes exhausted by NH₃ breakthrough experiments were regenerated conveniently by heating at 60 °C for one week under vacuum for further/repeated use; a single regenerated membrane could block NH₃ for 200–300 min. The moisture permeability of such a membrane/nanopacked bed was considerably above the breathability threshold value of 2000 g/m² -day. The results suggest that microporous membranes filled with reactive MOF nanoparticles could be designed as protective barriers against toxic gases/vapors, e.g., NH₃ and Cl₂ and yet be substantially permeable to H₂O and air. 

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2. 1-Alkyl-3-Methylimidazolium Cation Binding Preferences in Hexafluorophosphate Ionic Liquid Clusters Determined Using Competitive TCID Measurements and Theoretical Calculations

   https://doi.org/10.1039/D1CP02928B  

   Roy, Harrison A.; Rodgers, Mary (January 2021, Physical Chemistry Chemical Physics)

   null (Ed.)

   Ionic liquids (ILs) exhibit unique properties that have led to their development and widespread use for a variety of applications. Development efforts have generally focused on achieving desired macroscopic properties via tuning of the IL through variation of the cations and anions. Both the macroscopic and microscopic properties of an IL influence its tunability and thus feasibility of use for selected applications. Works geared toward a microscopic understanding of the nature and strength of the intrinsic cation-anion interactions of ILs have been limited to date. Specifically, the intrinsic strength of the cation-anion interactions in ILs is largely unknown. In previous work, we employed threshold collision-induced dissociation (TCID) approaches supported and enhanced by electronic structure calculations to determine the bond dissociation energies (BDEs) and characterize the nature of the cation-anion interactions in a series of four 2:1 clusters of 1-alkyl-3-methylimidazolium cations with the hexafluorophosphate anion, [2C n mim:PF 6 ] + . To examine the effects of the 1-alkyl chain on the structure and energetics of binding, the cation was varied over the series: 1-ethyl-3-methylimidazolium, [C 2 mim] + , 1-butyl-3-methylimidazolium, [C 4 mim] + , 1-hexyl-3-methylimidazolium, [C 6 mim] + , and 1-octyl-3-methylimidazolium, [C 8 mim] + . The variation in the strength of binding among these [2C n mim:PF 6 ] + clusters was found to be similar in magnitude to the average experimental uncertainty in the measurements. To definitively establish an absolute order of binding among these [2C n mim:PF 6 ] + clusters, we extend this work again using TCID and electronic structure theory approaches to include competitive binding studies of three mixed 2:1 clusters of 1-alkyl-3-methylimidazolium cations and the hexafluorophosphate anion, [C n-2 mim:PF 6 :C n mim] + for n = 4, 6, and 8. The absolute BDEs of these mixed [C n-2 mim:PF 6 :C n mim] + clusters as well as the absolute difference in the strength of the intrinsic binding interactions as a function of the cation are determined with significantly improved precision. By combining the thermochemical results of the previous independent and present competitive measurements, the BDEs of the [2C n mim:PF 6 ] + clusters are both more accurately and more precisely determined. Comparisons are made to results for the analogous [2C n mim:BF 4 ] + and [C n-2 mim:PF 6 :C n mim] + clusters previously examined to elucidate the effects of the [PF 6 ] - and [BF 4 ] - anions on the binding. 

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3. High-performance ammonia-selective MFI nanosheet membranes

   https://doi.org/10.1039/D0CC07217F  

   Duan, Xuekui; Kim, Donghun; Narasimharao, Katabathini; Al-Thabaiti, Shaeel; Tsapatsis, Michael (January 2021, Chemical Communications)

   null (Ed.)

   Nanosheet-based MFI membranes, known to be highly selective for hydrocarbon isomer separations, exhibit an NH 3 /N 2 mixture separation factor of 2236 with NH 3 permeance of 1.1 × 10 −6 mol m −2 s −1 Pa −1 , and NH 3 /H 2 separation factor of 307 with NH 3 permeance of 2.3 × 10 −6 mol m −2 s −1 Pa −1 at room temperature. Consistent with a competitive sorption-based separation, lower operating temperatures and higher pressures result in increased separation factor. At 323 K, with an equimolar mixed feed of NH 3 /N 2 , the fluxes and separation factors at 3 and 7 bar are 0.13 mol m −2 s −1 and 191, and 0.26 mol m −2 s −1 and 220, respectively. This performance compares favorably with that of other membranes and suggests that MFI membranes can be used in separation and purification processes involving mixtures of NH 3 /N 2 /H 2 encountered in ammonia synthesis and utilization. The membranes also exhibit high performance for the separation of ethane, n -propane and n -butane from H 2 . 

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4. Effect of methylene versus ethylene linkers on structural properties of tert -butyl and mesityl bis(imidazolium) bromide salts

   https://doi.org/10.1107/S2056989022008003  

   Thompson, Emily S.; Olivas, Elisa M.; Torres, Adrian; Arreaga, Briana C.; Alarcon, Hector L.; Dolberry, Deandrea; Brannon, Jacob P.; Stieber, S. Chantal (September 2022, Acta Crystallographica Section E Crystallographic Communications)

   The crystal structures of ligand precursor bis(imidazolium) salts 1,1′-methylenebis(3- tert -butylimidazolium) dibromide monohydrate, C 15 H 26 N 4 + ·2Br − ·H 2 O or [ t Bu NHC 2 Me][Br] 2 ·H 2 O, 1,1′-(ethane-1,2-diyl)bis(3- tert -butylimidazolium) dibromide dihydrate, C 16 H 28 N 4 + ·2Br − ·2H 2 O or [ t Bu NHC 2 Et][Br] 2 ·2H 2 O, 1,1′-methylenebis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide dihydrate, C 25 H 30 N 4 2+ ·2Br − ·2H 2 O or [ Mes NHC 2 Me][Br] 2 ·2H 2 O, and 1,1′-(ethane-1,2-diyl)bis[3-(2,4,6-trimethylphenyl)imidazolium] dibromide tetrahydrate, C 26 H 32 N 4 2+ ·2Br − ·4H 2 O or [ Mes NHC 2 Et][Br] 2 ·4H 2 O, are reported. At 293 K, [ t Bu NHC 2 Me][Br] 2 ·H 2 O crystallizes in the P 2 1 / c space group, while [ t Bu NHC 2 Et][Br] 2 ·2H 2 O crystallizes in the P 2 1 / n space group at 100 K. At 112 K, [ Mes NHC 2 Me][Br] 2 ·2H 2 O crystallizes in the orthorhombic space group Pccn while [ Mes NHC 2 Et][Br] 2 ·4H 2 O crystallizes in the P 2 1 / c space group at 100 K. Bond distances and angles within the imidazolium rings are generally comparable among the four structures. All four bis(imidazolium) salts co-crystallize with one to four molecules of water. 

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5. Clarifying the structures of imidines: using crystallographic characterization to identify tautomers and localized systems of π-bonding

   https://doi.org/10.1107/S2053229623002036  

   Aristov, Michael M.; Geng, Han; Harris, James W.; Berry, John F. (April 2023, Acta Crystallographica Section C Structural Chemistry)

   Nitrogen heterocycles are a class of organic compounds with extremely versatile functionality. Imidines, HN[C(NH) R ] 2 , are a rare class of heterocycles related to imides, HN[C(O) R ] 2 , in which the O atoms of the carbonyl groups are replaced by N—H groups. The useful synthesis of the imidine compounds succinimidine and glutarimidine, as well as their partially hydrolyzed imino–imide congeners, was first described in the mid-1950s, though structural characterization is presented for the first time in this article. In the solid state, these structures are different from the proposed imidine form: succinimidine crystallizes as an imino–amine, 2-imino-3,4-dihydro-2 H -pyrrol-5-amine, C 4 H 7 N 2 ( 1 ), glutarimidine as 6-imino-3,4,5,6-tetrahydropyridin-2-amine methanol monosolvate, C 5 H 9 N 3 ·CH 3 OH ( 2 ), and the corresponding hydrolyzed imino–imide compounds as amino–amides 5-amino-3,4-dihydro-2 H -pyrrol-2-one, C 4 H 6 N 2 O ( 3 ), and 6-amino-4,5-dihydropyridin-2(3 H )-one, C 5 H 8 N 2 O ( 4 ). Imidine 1 was also determined as the hydrochloride salt solvate 5-amino-3,4-dihydro-2 H -pyrrol-2-iminium chloride–2-imino-3,4-dihydro-2 H -pyrrol-5-amine–water (1/1/1), C 4 H 8 N 3 + ·Cl − ·C 4 H 7 N 3 ·H 2 O ( 1 ·HCl). As such, 1 and 2 show alternating short and long C—N bonds across the molecule, revealing distinct imino (C=NH) and amine (C—NH 2 ) groups throughout the C—N backbone. These structures provide definitive evidence for the predominant imino–amine tautomer in the solid state, which serves to enrich the previously proposed imidine-focused structures that have appeared in organic chemistry textbooks since the discovery of this class of compounds in 1883. 

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