A rationally designed perfluorinated host for the extraction of PFOA from water utilising non-covalent interactions

Omorodion, Harrison; Palenzuela, Miguel; Ruether, Manuel; Twamley, Brendan; Platts, James Alexis; Baker, Robert J.

doi:10.1039/c7nj03026f

Cited by 16 publications

(14 citation statements)

References 167 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Supramolecular chemistry represents an elegant approach to construct multifunctional materials for challenging applications 33,34 , with the virtues of molecular recognition and self-assembly. Macrocyclic hosts, such as crown ether 35 , cyclodextrin 36 , calixarene 37–40 , pillararene 41,42 , cucurbituril 43,44 , and others 45,46 , are families of well-studied artificial receptors with a cavity that can be selective for the recognition of particular guests. Efficient molecular recognition by macrocycles in aqueous media has been demonstrated for various applications, including the detection 44,47 and absorption 48,49 of pollutants.…”

Section: Introductionmentioning

confidence: 99%

Guanidinocalix[5]arene for sensitive fluorescence detection and magnetic removal of perfluorinated pollutants

et al. 2019

View full text Add to dashboard Cite

Perfluorinated alkyl substances, such as perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA), are toxic materials that are known to globally contaminate water, air, and soil resources. Strategies for the simultaneous detection and removal of these compounds are desired to address this emerging health and environmental issue. Herein, we develop a type of guanidinocalix[5]arene that can selectively and strongly bind to PFOS and PFOA, which we use to demonstrate the sensitive and quantitative detection of these compounds in contaminated water through a fluorescent indicator displacement assay. Moreover, by co-assembling iron oxide nanoparticle with the amphiphilic guanidinocalix[5]arene, we are able to use simple magnetic absorption and filtration to efficiently remove PFOS and PFOA from contaminated water. This supramolecular approach that uses both molecular recognition and self-assembly of macrocyclic amphiphiles is promising for the detection and remediation of water pollution.

show abstract

Section: Introductionmentioning

confidence: 99%

Guanidinocalix[5]arene for sensitive fluorescence detection and magnetic removal of perfluorinated pollutants

et al. 2019

View full text Add to dashboard Cite

show abstract

“…The C=O (carbonyl) bond length is 1.23 and C-O (hydroxyl) 1.289 Å, which is well comparable to anhydrous PDFO, [49] with 4 molecules in the asymmetric unit, where the corresponding bond lengths range from 1.228 to 1.241 and from 1.288 to 1.331, respectively. The C-C distances in the PDFO chain are all very close to 1.56 Å (from 1.557 to 1.565 Å), which is in average a little longer than the average in the anhydrous PDFO (1.54 Å), but well within the range found therein (1.510 to 1.576 Å).…”

Section: Resultsmentioning

confidence: 55%

“…The fit improved considerably (Rwp dropped from 12.7 to 8.5 %), but subsequent crystallochemical analysis of the refined structure and calculation of its energy revealed that the structure was in fact "spoiled" by the described refinement procedure. Although the molecules were moved only slightly, the H-bonds pattern was destroyed (disregarding the positions of hydrogen atoms) and also the intermolecular F-F contacts in the hydrophobic part of the structure were less similar to those in the related structures (for example anhydrous PDFO [49] ). This was more or less expected due to the limited quality of the powder pattern, as described above.…”

Section: Resultsmentioning

confidence: 99%

“…While the majority of optimizations were performed in a fixed unit cell using cell parameters acquired by diffraction, in some cases the cell parameters were also subject to optimization. The above described methodology was validated for the related system of anhydrous PDFO of which the crystal structure was published recently, [49] as well as of oxalic acid dihydrate, [14] yielding very good agreement between the optimized and measured structure. However, in the case of oxalic acid dihydrate VASP exhibits a tendency of overestimating the shortness of the H-bond by about 0.02 Å.…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Structure Determination by Joint Effort of X-ray Powder Diffraction and Quantum Calculations: Crystal Structure and Short Hydrogen Bonding in Pentadecafluorooctanoic Acid Hydrate

Stare¹,

Meden²,

Hadži³

2018

Croat. Chem. Acta

View full text Add to dashboard Cite

A precise X-ray crystal structure determination of systems that exist in a polycrystalline form often poses a challenge due to several factors that limit the resolution of the diffraction measurement. The location of atoms is usually determined at significantly lower precision than the unit cell parameters, rendering the complete characterization of the structure difficult. This is particularly pronounced when precise location of hydrogen atoms is required, for instance in ionizable biomolecules or in hydrogen bonds. In such cases periodic quantum (DFT) calculations may crucially assist structure determination, because they can reliably predict the location of atoms, provided that the unit cell parameters, the space group and tentative atomic positions are known. In this work we present DFT-assisted structure determination of pentadecafluorooctanoic acid hydrate, a benchmark system featuring short hydrogen bonds (RO...O ≈ 2.5 Å) between acid and water molecules. While Rietveld refinement based solely on powder diffraction data cannot reliably resolve the location of crystal water molecules and even less so the position of hydrogen atoms in the network of hydrogen bonds, periodic DFT optimization yields several minimum energy structures suitable for further refinement. Due to the low experimental resolution and similarity, comparison between model and experimental powder diffraction pattern can barely distinguish between certain structure candidates provided by DFT calculations, but it can rule out those featuring larger misfits. The proposed structure solution is delivered from a tandem application of structure determination from powder diffraction data and DFT optimization, the former providing the unit cell parameters and estimated atomic positions that are finely tuned by DFT. The present strategy can in principle be generalized to other examples of structure determination at relatively low resolution, such as is often the case with biological macromolecules.

show abstract

“…Given the findings of Omorodion et al, who studied the nature of non-covalent interactions in calixarene-PFOA hostguest complexes, 29 we speculated that the primary interaction responsible for the successful adsorption of PFOA by the polymers is the hydrogen bond between the carboxylic group of PFOA and a hydroxyl oxygen of the calixarene. We also surmise that additional stabilization may be achieved by C-F••••F-C interactions 39 between PFOA and the fluorinated linkers in FCX4-P and FCX4-BP.…”

Section: Resultsmentioning

confidence: 81%

Rapid and Efficient Removal of Perfluorooctanoic Acid from Water with Fluorine-Rich Calixarene-Based Porous Polymers

Shetty

Jahović²,

Škorjanc³

et al. 2020

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

On account of its non-biodegradable nature and persistence in the environment, perfluorooctanoic acid (PFOA) accumulates in water resources and poses serious environmental issues in many parts of the world. Here, we present the development of two fluorine-rich calix[4]arene-based porous polymers, FCX4-P and FCX4-BP, and demonstrate their utility for the efficient removal of PFOA from water. These materials featured BET surface areas of up to 450 m 2 g -1 , which is slightly lower than their non-fluorinated counterparts (up to 596 m 2 g -1 ). FCX4-P removes PFOA at environmentally relevant concentrations with a high rate constant of 3.80 g mg -1 h -1 and reaches an exceptional maximum PFOA uptake capacity of 188.7 mg g -1 . In addition, it can be regenerated by simple methanol wash and reused without a significant decrease in performance. ASSOCIATED CONTENT Supporting InformationThe Supporting Information is available free of charge on the ACS Publications website.

show abstract

A rationally designed perfluorinated host for the extraction of PFOA from water utilising non-covalent interactions

Abstract: Three hosts for the encapsulation of perfluorooctanoic acid have been synthesized. The host:guest complexes have been characterized by multinuclear NMR spectroscopy in solution and the solid state.

Cited by 16 publications

References 167 publications

Guanidinocalix[5]arene for sensitive fluorescence detection and magnetic removal of perfluorinated pollutants

Guanidinocalix[5]arene for sensitive fluorescence detection and magnetic removal of perfluorinated pollutants

Structure Determination by Joint Effort of X-ray Powder Diffraction and Quantum Calculations: Crystal Structure and Short Hydrogen Bonding in Pentadecafluorooctanoic Acid Hydrate

Rapid and Efficient Removal of Perfluorooctanoic Acid from Water with Fluorine-Rich Calixarene-Based Porous Polymers

Contact Info

Product

Resources

About