Resolving unknown isomers of emerging per- and polyfluoroalkyl substances (PFASs) in environmental samples using COSMO-RS-derived retention factor and mass fragmentation patterns

Guardian, Mary Grace E.; Antle, Jonathan P.; Vexelman, Paul A.; Aga, Diana S.; Simpson, Scott

doi:10.1016/j.jhazmat.2020.123478

Cited by 12 publications

(7 citation statements)

References 64 publications

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“…Determination, optimization of lowest energy conformers, and calculation of polarizability values along with other COSMO-RS derived thermodynamic properties of each of the compounds were performed according to one of our previously published method. , The quantum chemical software package, TURBOMOLE was utilized in all Density functional theory (DFT) calculations throughout this study . The BP86 GGA functional, and a def2-TZVPD basis set were used for each element for the optimization of all conformer geometries. − Solubility calculations were carried based on solvents used in chromatographic mobile phases of the LC-Orbitrap separation methodology.…”

Section: Methodsmentioning

confidence: 99%

“…Despite these recent advances, it is challenging to predict the identification of a broad spectrum of compounds. Approaches of obtaining physiochemical properties reports computational packages such as EPI Suite, ClogP, and SPARC lack quantum chemical treatment of the studied molecules. − Here-in we employ COSMOtherm, an emerging in-silico model for the validation of chemical compounds based on the “conductor-like screening model for real solvents” (COSMO-RS) theory and TURBOMOLE to derive a plausible QSRR model to predict the level 2 confirmed compounds of this study. For the prediction of thermodynamic properties of a molecule, COSMO-RS utilizes screening charge density calculated through quantum-chemical methods .…”

Section: Introductionmentioning

confidence: 99%

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In Silico Supported Nontarget Analysis of Contaminants of Emerging Concern: Increasing Confidence in Unknown Identification in Wastewater and Surface Waters

et al. 2021

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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. In this study, wastewater and surface water samples from three locations in Manila, Philippines were analyzed for CECs using a nontarget analysis approach with an LC-Orbitrap. A previously optimized semiautomated workflow was used for data processing with Compound Discoverer. A total of 157 compounds were identified, with 21 confirmed with reference standards, 83 confirmed with evidence from a mass spectral library (mzCloud), and 53 tentatively identified using in silico fragmentation (MetFrag). These compounds include pharmaceuticals such as antibiotics, antifungal, and antihypertensive compounds, human metabolites, natural products, pesticides, and industrial chemicals. Compounds confirmed with reference standards include antibiotics ciprofloxacin, clarithromycin, acetyl-sulfamethoxazole, and trimethoprim (2 to 19 ng/L), and antifungal compounds carbendazim and climbazole (3–47 ng/L). The pesticides diethyltoluamide (DEET) and diuron were also detected (37 ng/L). The utility of a preliminary multivariable linear regression quality structure-retention relationship (QSRR) model based on quantum chemical molecular descriptors is demonstrated. This study demonstrates the importance of using tools and software that are helpful for annotating HRMS data and reporting detections according to a standardized classification system. The detection of several CECs in wastewater and surface water samples show the importance of performing nontarget analysis in determining occurrence of CECs in the environment.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

In Silico Supported Nontarget Analysis of Contaminants of Emerging Concern: Increasing Confidence in Unknown Identification in Wastewater and Surface Waters

et al. 2021

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“…Optimized structures of the anionic form (missing a proton) and the neutral forms were utilized in the COSMOtherm calculation. The p K a was calculated using a weighted Boltzmann distribution that accounts for all entered conformers . This COSMO-RS methodology has been tested with a variety of 64 organic and inorganic acids, and the error of the p K a values was approximated to be ±0.49 logarithmic units .…”

Section: Computational Detailsmentioning

confidence: 99%

Building Chemical Intuition about Physicochemical Properties of C8-Per-/Polyfluoroalkyl Carboxylic Acids through Computational Means

Antle,

LaRock,

Falls

et al. 2023

ACS EST Eng.

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We have predicted acid dissociation constants (pK a ), octanol−water partition coefficients (K OW ), and DMPC lipid membrane−water partition coefficients (K lipid-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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“…The emergence of more reliable methods, i.e., suspect screenings and non-targeted analyses (NTA), has improved the level of coverage in identifying new emerging PFAS and enhanced our knowledge of their distribution . New methods are used to identify new PFAS and their isomers in aqueous samples, such as COnductor-like Screening MOdel for Real-Solvents (COSMO-RS) and in silico PFAS fragmentation modeling together with data mining software …”

Section: Introductionmentioning

confidence: 99%

Computational Investigation of Structure–Function Relationship in Fluorine-Functionalized MOFs for PFOA Capture from Water

et al. 2023

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A strategy that can be used to develop metal− organic frameworks (MOFs) to capture per-and poly-fluoroalkyl substances (PFAS) from water is functionalizing them with fluorine moieties. We investigated different fluorine-functionalization strategies and their performance in removing PFAS from water using molecular simulations. Perfluorooctanoic acid (PFOA), one of the most widely encountered PFAS in water sources, was used as the probe molecule. Our simulations show that fluorine functionalization by incorporating fluorinated anions as bridging ligands in MOFs creates additional binding sites for PFOA; however, the same sites also attract water molecules, which casts doubt on their potential use. In contrast, trifluoromethyl or fluorine substitution of the MOF ligands results in higher hydrophobicity. However, the pores fluorinated with this method should have the optimum size to accommodate PFOA. Likewise, post-synthetic fluorine functionalization of MOFs through grafting of perfluorinated alkanes showed increased PFOA affinity. Fluorine-functionalized MOFs with high hydrophobicity and optimized pore sizes can effectively capture PFOA from water at very low concentrations of PFOA.

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Resolving unknown isomers of emerging per- and polyfluoroalkyl substances (PFASs) in environmental samples using COSMO-RS-derived retention factor and mass fragmentation patterns

Cited by 12 publications

References 64 publications

In Silico Supported Nontarget Analysis of Contaminants of Emerging Concern: Increasing Confidence in Unknown Identification in Wastewater and Surface Waters

In Silico Supported Nontarget Analysis of Contaminants of Emerging Concern: Increasing Confidence in Unknown Identification in Wastewater and Surface Waters

Building Chemical Intuition about Physicochemical Properties of C8-Per-/Polyfluoroalkyl Carboxylic Acids through Computational Means

Computational Investigation of Structure–Function Relationship in Fluorine-Functionalized MOFs for PFOA Capture from Water

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