Characterization of per- and polyfluoroalkyl substances on fire suppression system piping and optimization of removal methods.

Fire suppression systems are known to be impacted with residual, entrained per- and polyfluoroalkyl substances (PFASs) because of historical use of aqueous film forming foam (AFFF) and fluoroprotein foam. Amphiphilic PFASs aggregate at liquid:solid interfaces creating a hydrophobic layer which reduces the effectiveness of water to remove PFAS from layered surfaces. When fire suppression systems are transitioned to fluorine free foam (F3) without appropriate cleaning, residual PFASs associated with the surfaces of the fire suppression system can contaminate the replacement F3. Release of residual PFASs from fire suppression systems into F3 has been documented; however, little is known about the residual PFASs associated with the surfaces of the fire suppression systems. More information is needed to develop methods to appropriately remove PFASs from fire suppression systems to prevent costly and inefficient foam transitioning and preserve the PFAS-free benefit of F3. The objective of this work was to evaluate the distribution and composition of PFASs on hangar piping exposed to PFAS-containing firefighting foam for a prolonged period. Two assessment methods were used: 1) extractions with methanol, water, and a proprietary aqueous organic solvent (Fluoro Fighter™); and 2) direct imaging methods of the surface. Extractions were analyzed with mass spectrometry and combustion ion chromatography. Results indicate pipe in contact with PFAS-containing firefighting foam can amass approximately 10 µg/cm2 of surface-associated PFAS residual following decades of exposure. Fluoro Fighter demonstrated higher PFAS removal per surface area of pipe than methanol (p = 0.007) or water extraction (p < 0.0001). Scanning electron microscope (SEM) images of the hangar piping reveal deposits suspected to be self-assembled PFAS layers, as evidenced by examination of pipe surfaces using X-ray photoelectron spectroscopy (XPS), which revealed atomic fluorine on the surface of the pipe.

Field-Scale Demonstration of PFAS Leachability Following In Situ Soil Stabilization.

A field-scale validation is summarized comparing the efficacy of commercially available stabilization amendments with the objective of mitigating per- and polyfluoroalkyl substance (PFAS) leaching from aqueous film-forming foam (AFFF)-impacted source zones. The scope of this work included bench-scale testing to evaluate multiple amendments and application concentrations to mitigate PFAS leachability and the execution of field-scale soil mixing in an AFFF-impacted fire-training area with nearly 2.5 years of post-soil mixing monitoring to validate reductions in PFAS leachability. At the bench scale, several amendments were evaluated and the selection of two amendments for field-scale evaluation was informed: FLUORO-SORB Adsorbent (FS) and RemBind (RB). Five ∼28 m3 test pits (approximately 3 m wide by 3 m long by 3 m deep) were mixed at a site using conventional construction equipment. One control test pit (Test Pit 1) included Portland cement (PC) only (5% dry weight basis). The other four test pits (Test Pits 2 through 5) compared 5 and 10% ratios (dry weight basis) of FS and RB (also with PC). Five separate monitoring events included two to three sample cores collected from each test pit for United States Environmental Protection Agency (USEPA) Method 1315 leaching assessment. After 1 year, a mass balance for each test pit was attempted comparing the total PFAS soil mass before, during, and after leach testing. Bench-scale and field-scale data were in good agreement and demonstrated >99% decrease in total PFAS leachability (mass basis; >98% mole basis) as confirmed by the total oxidizable precursor assay, strongly supporting the chemical stabilization of PFAS.

The cost of a single concussion in American high school football: a retrospective cohort study.

AIM: The potential financial burden of American football-related concussions (FRC) is unknown. Our objective was to describe the healthcare costs associated with an FRC and determine factors associated with increased costs. METHODOLOGY/RESULTS: A retrospective cohort study of concussed high school football players presenting between November 2017 and March 2020 was undertaken; 144 male high school football players were included. Total costs were about $115,000, for an average direct healthcare cost of $800.10/concussion. Visiting the emergency department (ß = 502.29, 95% CI: 105.79-898.61; p = 0.01), the initial post-concussion symptom scale score (ß = 0.39, 95% CI: 0.11-0.66; p = 0.01) and a post-concussion syndrome diagnosis (ß = 670.37, 95% CI: 98.96-1241.79; p = 0.02) were each independently associated with total costs. CONCLUSION: A granular understanding of cost-driving factors associated with FRC is the first step in understanding the cost-effectiveness of prevention and treatment methods.

Synthesis and Photophysical Properties of T-Shaped Coinage-Metal Complexes.

The photophysical properties of a series of T-shaped coinage d10 metal complexes, supported by a bis(mesoionic carbene)carbazolide (CNC) pincer ligand, are explored. The series includes a rare new example of a tridentate T-shaped AgI complex. Post-complexation modification of the AuI complex provides access to a linear cationic AuI complex following ligand alkylation, or the first example of a cationic square planar AuIII -F complex from electrophilic attack on the metal centre. Emissions ranging from blue (CuI ) to orange (AgI ) are obtained, with variable contributions of thermally-dependent fluorescence and phosphorescence to the observed photoluminescence. Green emissions are observed for all three gold complexes (neutral T-shaped AuI , cationic linear AuI and square planar cationic AuIII ). The higher quantum yield and longer decay lifetime of the linear gold(I) complex are indicative of increased phosphorescence contribution.

Synthesis of heterobimetallic gold(i) ferrocenyl-substituted 1,2,3-triazol-5-ylidene complexes as potential anticancer agents.

1,2,3-Triazol-5-ylidene (trz) complexes of gold(i) containing a ferrocenyl substituent on the C4-position of the trz ring were synthesized to yield the neutral heterobimetallic gold(i) trz chlorido (2), gold(i) trz phenyl (3), and the cationic gold(i) trz triphenylphospine (5) complexes. In order to compare the effect of silver(i) as central metal vs. gold(i), [Ag(trz)2]+ (4) was also prepared, while variation of the C4-1,2,3-triazol-5-ylidene substituent from a ferrocenyl to a phenyl group was done to prepare the monometallic analogue of 5, namely the cationic Au(i) trz triphenylphosphine complex 6. The complexes were characterised with spectroscopic and electrochemical methods, and the single crystal X-ray structures of 2-6 were determined. NMR stability studies of 5 as a representative example of the series of complexes were performed to confirm the stability of the complexes in the solvent dimethylsulfoxide and in aqueous solution. The anti-cancer potential of 5 was evaluated against the lung cancer cell lines A549 and H1975, and the human embryonic kidney cell line (HEK-293) was used as a non-cancer model. IC50 values of 0.89, 0.23 and 5.43 µM, respectively, were obtained for A549, H1975 and HEK-293, respectively, indicating the activity and selectivity of 5 for cancer cells. Fluorescence microscopy experiments as a preliminary mode-of-action study evidenced an apoptotic cell death mechanism rather than necrotic cell death.

Mono-, di- and tetrarhenium Fischer carbene complexes with thienothiophene substituents.

The oxidative cleaving of a rhenium-rhenium bond by bromine in binuclear Fischer carbene complexes proves to be an effective method to prepare mononuclear bromido-carbene complexes. The reaction of mono- and dilithiated thieno[2,3-b]thiophene (2,3-b-TTH2) and thieno[3,2-b]thiophene (3,2-b-TTH2) with [Re2(CO)10] affords dirhenium nonacarbonyl ethoxycarbene complexes, [Re2(CO)9{C(OEt)2,3-b-TTH}] (1a) and [Re2(CO)9{C(OEt)3,2-b-TTH}] (1b), and the tetrarhenium bis(ethoxycarbene) complexes from the dilithiated thiophene substrates, [Re2(CO)9-µ-{C(OEt)-2,3-b-TT-C(OEt)}Re2(CO)9] (2a) and [Re2(CO)9-µ-{C(OEt)-3,2-b-TT-C(OEt)}Re2(CO)9] (2b) featuring bridging thiophene linkers. Rhenium-rhenium bond cleavage by bromine of the monocarbene complexes yielded the scarce class of monorhenium bromido-carbene complexes, cis-[Re(CO)4{C(OEt)2,3-b-TTH}Br] (3a) and cis-[Re(CO)4{C(OEt)3,2-b-TTH}Br] (3b), while the corresponding reaction of the biscarbene tetrarhenium carbonyl complex of thieno[2,3-b]thiophene afforded the cleaving of both metal-metal bonds to give the novel dirhenium biscarbene dibromido complex with a thienothiophene spacer, [Re(CO)4Br-µ-{C(OEt)-2,3-b-TT-C(OEt)}Re(CO)4Br] (4a). A new indirect aminolysis route is described to prepare the chlorido dimethylaminocarbene complex 5acis-[Re(CO)4{C(NMe2)2,3-b-TTH}Cl], with unexpected cleavage of the Re-Re bond. Single crystal X-ray diffraction studies were performed on 1a, 2a, 3a, 5a, 1b and 3b. Spectroscopic and electrochemical methods are employed to investigate the electronic effect of the different conjugation pathways in the different thienothiophenyl carbene substituents, and the replacement of the rhenium pentacarbonyl fragment with a bromido ligand.

A Hemilabile and Cooperative N-Donor-Functionalized 1,2,3-Triazol-5-Ylidene Ligand for Alkyne Hydrothiolation Reactions.

A series of novel cationic and neutral Rh complexes with an N-donor-functionalized 1,2,3-triazol-5-ylidene (TRZ) ligand (in which the pendant N donor is NHBoc, NH2 , or NMe2 ) is described. The catalytic activity of these complexes was evaluated in the hydrothiolation of alkynes. Among the catalysts, a neutral dicarbonyl complex featuring the tethered-NBoc amido-TRZ ligand proved very selective for alkyne hydrothiolation with an aryl thiol. Remarkably, the reaction could be carried out in the absence of pyridine or base additive. In addition, during the reaction, no evidence for oxidative addition of the thiol S-H bond was observed, strongly suggesting a reaction pathway in which a bifunctional ligand is involved. Experimental and theoretical mechanistic investigations suggest a ligand-assisted deprotonation of thiol, hemilabile dissociation of amine from the metal, and thiolate coordination, which is indicative of a different reaction mechanism to those previously reported for related alkyne hydrothiolation reactions.

Nucleophilic T-Shaped (LXL)Au(I)-Pincer Complexes: Protonation and Alkylation.

We report the synthesis and reactivity of unusual T-shaped (LXL)Au(I)-pincer complexes, based on a carbazole framework flanked by two mesoionic carbenes (MICs). In contrast to other Au(I) complexes, these complexes react with electrophiles. Protonation and alkylation occur either at the metal or the ligand, depending on steric factors. Of particular interest, protonation at gold leads to an unprecedented cationic Au(III) hydride, which gives a 1H NMR resonance at δ -8.34 ppm. The reactivity of this "hydride", however, shows protic and not hydridic behavior.

A rhodium(I)-oxygen adduct as a selective catalyst for one-pot sequential alkyne dimerization-hydrothiolation tandem reactions.

An air-stable rhodium(I)-oxygen adduct featuring a CNC-pincer ligand, based on 1,2,3-triazol-5-ylidenes, catalyzes the homo-dimerization and hydrothiolation of alkynes, affording the gem-enyne and α-vinyl sulfide isomers, respectively, with excellent selectivity. A one-pot stepwise strategy allows the selective catalytic preparation of non-symmetric bis-vinyl sulfides, as well as the alkyne dimerization-hydrothiolation tandem reactions.

Synthesis and properties of mono- and dimetal Fischer multicarbene complexes derived from thiophene and thieno[2,3-b]thiophene.

Access to multicarbene complexes of a fused thienothiophene substrate was obtained by the use of the tetrabrominated thieno[2,3-b]thiophene precursor in a lithium-bromide exchange reaction, followed by nucleophilic attack on metal hexacarbonyls (M = Cr, W). Subsequent alkylation afforded unique triscarbene complexes [M(CO)4{{C(OEt)}2C6H1S2C(OEt)}M(CO)5] (M = Cr 12, W 13) featuring three non-equivalent carbene ligands on a single thiophene linker, as well as the bischelated tetracarbene complexes [M(CO)4{{C(OEt)}2C6S2{C(OEt)}2}M(CO)4] (M = Cr 14, W 15). The triscarbene complexes 12 and 13 are the first examples of multi-alkoxycarbene complexes featuring three non-equivalent carbene ligands. The reaction also afforded the chelated mononuclear biscarbene complexes [M(CO)4{C(OEt)}2C6H2S2] (M = Cr 10, W 11) in low yields. Similarly, employing tetrabromothiophene as precursor yielded the mononuclear chelate biscarbene complexes [M(CO)4{C(OEt)}2C4H2S] (M = Cr 6, W 7) and the dinuclear tetracarbene complexes [M(CO)4{{C(OEt)}2C4S{C(OEt)}2}M(CO)4] (M = Cr 8, W 9). Modification of the classic Fischer carbene synthetic methodology to a process of stepwise additions of lithiating agent and metal carbonyls to thieno[2,3-b]thiophene, facilitates the formation of the mixed metal biscarbene complex [W(CO)5C(OEt){C6H2S2}C(OEt)Cr(CO)5] 5, as analogue of the homonuclear biscarbene complexes [M(CO)5C(OEt){C6H2S2}C(OEt)M(CO)5], (M = Cr 3, W 4). The monocarbene complexes [M(CO)5{C(OEt)C6H3S2}], (M = Cr 1, W 2) were also obtained in high yields, and the molecular structures of the tungsten complexes, with the exception of 9 and 11, were confirmed by single crystal X-ray diffraction studies.

Design, synthesis and anticancer activity of Michael-type thiol adducts of α-santonin analogue with exocyclic methylene.

A series of Michael-type analogues were generated on the C-ring of α-santonin (α-methylene-γ-butyrolactone) upon reaction with various thiols. All the thiol adducts synthesized were evaluated for their anticancer activity against four human cancer cell lines (PC-3, HCT-15, A-549 and MCF-7). Bioassay results indicated that even though most of the synthesized compounds exhibited a good anticancer activity against various cancer cells in vitro, some of the compounds like 9e, 9g and 9q were found to be the most promising analogues in this series, with compound 9e showing IC50 values of 1.5 µM, 0.6 µM, 2.4 µM and 1.2 µM on PC-3, MCF-7, A-549 and HCT-116 cell lines respectively. Further, flow cytometry studies showed that MCF-7 cells treated with the compounds 9e, 9g and 9q were arrested in the sub G1 phase of the cell cycle in a concentration dependent manner. These lead molecules were further studied for NF-κB, p65 transcription factor inhibitory activity which confirmed concentration dependent inhibition against NF-κB, p65 with analogue 9e showing 57% inhibition at 2 µM, 9g showing 62% inhibition at 3 µM and 9q showing 54% inhibition at 2 µM concentration.

Isolation of a potassium bis(1,2,3-triazol-5-ylidene)carbazolide: a stabilizing pincer ligand for reactive late transition metal complexes.

The synthesis and X-ray crystal structure of a potassium adduct of a monoanionic CNC-pincer ligand featuring two mesoionic carbenes is reported. Owing to the peculiar electronic and steric properties of this ligand, the first neutral stable Ni(II)-hydride, and an unusual Cu(II) complex displaying a seesaw geometry, have been isolated.

Fischer-type gold(I) carbene complexes stabilized by aurophilic interactions.

The synthesis and structure of rare acyclic alkoxy- and aminocarbene complexes of gold(i) are reported, including a novel ferrocenophane dinuclear biscarbene complex. X-Ray diffraction analyses and DFT calculations reveal that these complexes are stabilized by genuine aurophilic interactions.

Substituent effects on the electrochemical, spectroscopic, and structural properties of Fischer mono- and biscarbene complexes of chromium(0).

A series of ten ferrocenyl, furyl, and thienyl mono- and biscarbene chromium(0) complexes were synthesized and characterized spectroscopically and electrochemically. The single crystal structure of the biscarbene complex [(CO)5Cr═C(OEt)-Fu'-(OEt)C═Cr(CO)5] (4a) was determined: C20H12Cr2O13; triclinic; P1; a = 6.2838(5), b = 12.6526(9), c = 29.1888(19) Å, α = 89.575(2), ß = 88.030(2), γ = 87.423(2)°; Z = 4. Results from an electrochemical study in CH2Cl2 were mutually consistent with a computational study in showing that the carbene double bond of 1-6 is reduced to an anion radical, (-)Cr-C• at formal reduction potentials < -1.7 V vs FcH/FcH(+). The Cr centers are oxidized in two successive one electron transfer steps to Cr(II) via the Cr(I) intermediate. Only Cr(I) oxidation is electrochemically irreversible. Dicationic Cr(II) species formed upon two consecutive one-electron oxidation processes are characterized by a peculiar bonding situation as they are stabilized by genuine CH···Cr agostic interactions. With respect to aryl substituents, carbene redox processes occurred at the lowest potentials for ferrocene derivatives followed by furan complexes. Redox process in the thiophene derivatives occurred at the highest potentials. This result is mutually consistent with a (13)C NMR study that showed the Cr═C functionality of furyl complexes were more shielded than thienyl complexes. The NHBu carbene substituent resulted in carbene complexes showing redox processes at substantially lower redox potentials than carbenes having OEt substituents.

Electrochemical illumination of thienyl and ferrocenyl chromium(0) Fischer carbene complexes.

A series of ferrocenyl and thienyl mono- and biscarbene chromium(0) complexes 1-6 were synthesised. The complexes were characterised both spectroscopically and electrochemically, and the single crystal X-ray structure of 3 was determined. Electrochemical measurements in CH2Cl2 revealed that the carbene double bond of 1-6 is reduced to an anion radical, (-)Cr-C˙ at formal reduction potentials <-1.7 V vs. FcH/FcH(+). A computational study on 1, 3 and 4 (B3LYP/def2-SVP level) is consistent with electrochemical results in showing that electrochemically generated chromium(I) species may be further electrochemically irreversibly oxidised to chromium(II) at Epa > 0.95 V. The reactivity towards follow-up chemical reactions of the anodically produced Cr(II) species is much higher than the reactivity of the cathodically produced radical anions as the latter was still observably reoxidised to the parent Cr=C species at fast scan rates. The ferrocenyl group is oxidised electrochemically reversibly to ferrocenium at larger potentials than the electrochemically reversible oxidation of the Cr(0) centre to Cr(I). That all redox centres in 1-6 are involved in one-electron transfer steps was confirmed by comparing the ferrocenyl voltammetric wave with those of the other redox centres in linear sweep voltammetric experiments. The ferrocenyl group was electrochemically shown to stabilise the Cr=C centre almost as much as the NHBu, and much more than the ethoxy and thienyl groups.

3,6-Diaza-octane-1,8-diaminium diiodide.

The asymmetric unit of the title salt, C(6)H(20)N(4) (2+)·2I(-), comprises half a 3,6-diaza-octane-1,8-diaminium dication plus an I(-) anion. The dications are symmetrical and lie across crystallographic centres of inversion. In the crystal, the ions form a network involving mainly weak N-H⋯I inter-molecular inter-actions: two H atoms of the ammonium group form inter-actions with two I(-) anions and the H atom of the secondary amine forms a weak inter-action with a third I(-) cation. The third ammonium H atom is hydrogen bonded to a secondary amine of an adjacent cation. The backbone of the cation does not form a uniformly trans chain, but is 'kinked' [C-N-C-C torsion angle = 71.5 (2)°], probably to accommodate the direct hydrogen bond between the ammonium group and the secondary amine in an adjacent cation.

2,2'-(Piperazine-1,4-di-yl)diethanaminium bis-(2-hy-droxy-benzoate).

The asymmetric unit of the title salt, C(8)H(22)N(4) (2+)·2C(7)H(5)O(3) (-), comprises half a 2,2'-(piperazine-1,4-di-yl)diethan-aminium dication plus a 2-hy-droxy-benzoate anion. In the crystal, the anions and cations are linked by N-H⋯O and O-H⋯O hydrogen bonds to form infinite two-dimensional networks parallel with the a unit-cell face. The conformation adopted by the cation in the crystal is very similar to that adopted by the same cation in the structures of the nitrate and tetra-hydrogen penta-borate salts.

2,2'-(Piperazine-1,4-di-yl)diethanaminium dibenzoate.

The asymmetric unit of the title salt C(8)H(22)N(4) (2+)·2C(7)H(5)O(2) (-), comprises two independent pairs of half a 2,2'-(piperazine-1,4-di-yl)diethanaminium dication plus a benzoate anion. The dications are symmetrical and lie across crystallographic centres of inversion. The crystal structure was refined as a two-component pseudo-merohedral twin using the twin law 001 0-10 100 [he domain fractions are 0.8645 (8) and 0.1355 (8)]. The anions and cations are linked by N-H⋯O hydrogen bonds and weak N-H⋯O inter-molecular inter-actions to form infinite two-dimensional networks parallel to [101]. The conformation adopted by the cation in the crystal structure is very similar to that adopted by the same cation in the structures of the 2-hy-droxy-benzoate [Cukrowski et al. (2012 ▶). Acta Cryst, E68, o2387], the nitrate and the tetra-hydrogen penta-borate salts.

[N,N'-Bis(2,4,6-trimethyl-phen-yl)ethane-1,2-diimine-κ(2)N,N']tetra-carbonyl-chromium(0).

The octa-hedral coordination of the Cr(0) atom in the title compound, [Cr(C(20)H(24)N(2))(CO)(4)], displays some distortion. This is manifested by an exocyclic torsion angle C(mesitylene)-N-Cr-C(carbon-yl) that deviates by more than 20° from planarity. Another structural feature is the significant distortion from linearity of the Cr-C-O angles of the two carbonyl groups that inter-act with both ortho-methyl groups of the two mesitylene rings. The remaining two carbonyl groups overlap with the centres of the mesitylene rings themselves and are linear within <3°.

{µ-5-[1,3-Bis(2,4,6-trimethyl-phen-yl)-3H-imidazolium-2-yl]-2-(2-oxoethenyl-1κC)furan-3-yl-2κC}-µ-hydrido-bis(tetra-carbonyl-rhenium) tetra-hydro-furan 0.67-solvate.

The title complex, [Re(2)(C(27)H(25)N(2)O(2))H(CO)(8)]·0.67C(4)H(8)O, was formed as a product in the reaction of a rhenium(I)-Fischer carbene complex with a free NHC carbene. The coordination environment about the two Re atoms is slightly distorted octahedral, including a bridging H atom. The imidazolium and furan groups are almost coplanar, whereas the mesityl substituents show an almost perpendicular arrangement with respect to both heterocyclic units. Mol-ecules of the complex pack in such a way as to form channels parallel with the bc unit-cell face diagonal running through the unit face diagonal. These channels are partially occupied by tetra-hydro-furan solvent mol-ecules.