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  1. We have predicted acid dissociation constants (pKa), octanol-water partition coefficients (KOW), and DPMC lipid membrane-water partition coefficients (Klipid-w) of 150 different 8-carbon containing poly-/per-fluoroalkyl carboxylic acids (C8-PFCAs) utilizing COMSO-RS theory. Different trends associated with functionalization, degree of fluorination, degree of saturation, degree of chlorination, and branching are discussed based upon the predicted values for the partition coefficients. In general, functionalization closest to the carboxylic head group had the greatest impact on the value of the predicted physicochemical properties. 
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  2. We have predicted acid dissociation constants (pKa), octanol–water partition coefficients (KOW), and DMPC lipid membrane–water partition coefficients (Klipid-w) of 150 different eight-carbon-containing poly-/perfluoroalkyl carboxylic acids (C8-PFCAs) utilizing the COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS) theory. Different trends associated with functionalization, degree of fluorination, degree of saturation, degree of chlorination, and branching are discussed on the basis of the predicted values for the partition coefficients. In general, functionalization closest to the carboxylic headgroup had the greatest impact on the value of the predicted physicochemical properties. 
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    Free, publicly-accessible full text available January 12, 2025
  3. Nontarget analysis using liquid chromatography–high resolution mass spectrometry (LC–HRMS) is a valuable approach in characterizing for contaminants of emerging concern (CECs) in the environment. However, identification of these analytes can be quite costly or taxing without proper analytical standards. To circumvent this problem we utilize Quantitative structure-retention relationships (QSRR) models to predict elution order and retention times. Properties calculated from density functional theory (DFT) and the conductor-like screening model for real solvents (COSMO-RS) theory are used to produce our QSRR models, which can be calculated for virtually any analyte. We show that this methodology has been successful in identification of per- /poly-fluoroalkyl substances (PFAS) and other contaminants. Nontarget analysis using liquid chromatography– high resolution mass spectrometry (LC–HRMS) is a valuable approach in characterizing for contaminants of emerging concern (CECs) in the environment. However, identification of these analytes can be quite costly or taxing without proper analytical standards. To circumvent this problem we utilize Quantitative structureretention relationships (QSRR) models to predict elution order and retention times. Properties calculated from density functional theory (DFT) and the conductor-like screening model for real solvents (COSMO-RS) theory are used to produce our QSRR models, which can be calculated for virtually any analyte. We show that this methodology has been 
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  4. Per-and polyfluoroalkyl substances (PFAS) are a class of contaminants of emerging concern frequently used in products like aqueous firefighting foams and non-stick coatings due to their stability and surfactant-like qualities. The lack of analytical standards for many emerging PFAS have severely limited our ability to comprehensively identify unknown PFAS contaminants in the environment, especially those that occur as isomers. Annotation of small molecules and identification of unknowns based only on elemental composition and mass fragmentation patterns remain major challenges in nontarget analysis employing liquid chromatography with high-resolution mass spectrometry (LC-HRMS). In this study, chromatographic retention factors (k) and mass spectral fragmentation patterns of 32 known PFAS were determined using our optimized parameters in LC-HRMS. The same method was then used to analyze previously unidentified PFAS in actual environmental samples. Using characteristic ions observed in the MS fragmentation of PFAS, the most probable isomeric structures of the detected PFAS were predicted. To increase confidence in the predicted molecular structure, Density Functional Theory and Conductor-like Screening Model for Realistic Solvents (COSMO-RS) calculations were used to predict physicochemical properties of different constitutional isomers. The DFT calculations facilitated geometric optimization, determination of polarizability, and calculation of the chemical potential the isomers. COSMO-RS uses the chemical potential to predict thermodynamic properties of molecules such as pKa, solubility, and Kow. These properties were then used to make a multi-variable linear regression to predict k values. The model was trained using 32 known PFAS. The properties used were log Kow of the neutral and anion species of the PFAS, and their polarizability. The model was specific enough to predict significantly different k values of unknown compounds with similar structures, which facilitated assignment of isomeric structures of PFAS. 
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  5. Chromatographic retention times and mass spectrometral fragmentation of per- and polyfluoroalkyl substances (PFASs) standards were determined using the optimized parameters obtained for liquid chromatography with tandem high-resolution mass spectrometry (LC-HRMS) analysis. Characteristic fragment ions obtained at various collision energies (MS2 fragmentation) were used for structural elucidation to predict the identities of newly discovered (emerging) PFASs detected in environmental samples. Moreover, the COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS) was used to calculate the octanol-water partition coefficients (Kow) and mean isotropic polarizabilities of known PFASs, and the values were plotted against their chromatographic retention factors (k) to obtain a multivariable regression model that can be used to predict k values of unknown PFASs. Retention factor values of different structural isomers of the unknown PFASs were calculated and compared to the experimental k. For all the unknown PFASs, the predicted k value for the isomer that matches the corresponding MS2 fragmentation was found to be within 5% of the experimentally measured k value. This study demonstrates the applicability of a simple approach that combines the use of computationally-derived log Kow and polarizabilities, experimentally-determined k values, together with observed MS2 fragmentation patterns, in assigning the structures of emerging PFASs at environmentally relevant conditions when no reference standards are available. 
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  6. null (Ed.)
    A series of five coordinated iron bis(dithiolene) complexes [Fe(NHC)(S 2 C 2 R 2 ) 2 ] (R = C 6 H 5 or C 6 H 4 - p -OCH 3 ) containing N-heterocyclic carbene (NHC) (NHC = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene or 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene) were isolated in high yield (84–92%). The iron complexes were characterized by NMR spectroscopy and confirmed by single crystal X-ray diffraction studies. The combination of cyclic voltammetry and spectroelectrochemical analysis revealed that iron complexes undergo Fe–C NHC bond cleavage and release NHC upon subjection to electrochemical reduction. The electrochemically released NHC was trapped using 1-naphthylisothiocyanate and the adduct was isolated in nearly quantitative yield (∼99%). As a proof of concept, the electrochemically released NHC was subsequently used as a catalyst for synthesis of γ-butyrolactones from commercially available cinnamaldehydes. 
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