High salt compatible oxyanion receptors by dual ion imprinting

Shinde, Sudhirkumar; Mansour, Mona; İncel, Anıl; Mavliutova, Liliia; Wierzbicka, Celina; Sellergren, Börje

doi:10.1039/c9sc06508c

Cited by 7 publications

(14 citation statements)

References 32 publications

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“… 6 Several synthetic receptors have been developed for this purpose but so far only few receptors offer effective anion recognition in water and even more rare are those functioning in high ionic strength media. Through further improvements of the imprinted receptors, such as incorporation of dual receptors 62 , 63 or other scaffolds, we hope to sufficiently boost affinity and selectivity for the MIPs to offer a viable alternative host for these purposes.…”

Section: Final Discussionmentioning

confidence: 99%

Urea-Based Imprinted Polymer Hosts with Switchable Anion Preference

Shinde,

Incel,

Mansour

et al. 2020

J. Am. Chem. Soc.

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The design of artificial oxyanion receptors with switchable ion preference is a challenging goal in host–guest chemistry. We here report on molecularly imprinted polymers (MIPs) with an external phospho-sulpho switch driven by small molecule modifiers. The polymers were prepared by hydrogen bond-mediated imprinting of the mono- or dianions of phenyl phosphonic acid (PPA), phenyl sulfonic acid (PSA), and benzoic acid (BA) using N -3,5-bis-(trifluoromethyl)-phenyl- Ń -4-vinylphenyl urea ( 1 ) as the functional host monomer. The interaction mode between the functional monomer and the monoanions was elucidated by 1 H NMR titrations and 1 H– 1 H NMR NOESY supported by molecular dynamic simulation, which confirmed the presence of high-order complexes. PPA imprinted polymers bound PPA with an equilibrium constant K eq = 1.8 × 10 5 M –1 in acetonitrile (0.1% 1,2,2,6,6-pentamethylpiperidine) and inorganic HPO 4 2– and SO 4 2– with K eq = 2.9 × 10 3 M –1 and 4.5 × 10 3 M –1 , respectively, in aqueous buffer. Moreover, the chromatographic retentivity of phosphonate versus sulfonate was shown to be completely switched on this polymer when changing from a basic to an acidic modifier. Mechanistic insights into this system were obtained from kinetic investigations and DSC-, MALDI-TOF-MS-, 1 H NMR-studies of linear polymers prepared in the presence of template. The results suggest the formation of template induced 1–1 diad repeats in the polymer main chain shedding unique light on the relative contributions of configurational and conformational imprinting.

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Section: Final Discussionmentioning

confidence: 99%

Urea-Based Imprinted Polymer Hosts with Switchable Anion Preference

Shinde,

Incel,

Mansour

et al. 2020

J. Am. Chem. Soc.

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“…The results contrast moreover with our studies of neutral urea-based receptors where Na18C6 counterions resulted in the strongest interactions. 32 This is reasonable given the lack of ion-exchange reactions in this case. Based on these results we decided to proceed with 2Br as functional monomer for sialic acid imprinting.…”

Section: Resultsmentioning

confidence: 77%

Discrimination between sialic acid linkage modes using sialyllactose-imprinted polymers

et al. 2021

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“… 25 When combined with polymerizable crown ethers, the MIP urea receptors could be engineered to simultaneously recognize the oxyanion and its counterion. 26 This concept was used to prepare phosphate receptors compatible with high-salt media. Inspired by these interesting results, we have probed here in more depth the parameters controlling receptor affinity and selectivity, notably the acidity and solubility of the urea monomer and the matrix polarity and means to stabilize or replace the counterion.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, we reported these receptors to exhibit a unique sulfo/phospho-switching function of potential utility in phosphate/sulfate separations and scavenging . When combined with polymerizable crown ethers, the MIP urea receptors could be engineered to simultaneously recognize the oxyanion and its counterion . This concept was used to prepare phosphate receptors compatible with high-salt media.…”

Section: Introductionmentioning

confidence: 99%

Oxoanion Imprinting Combining Cationic and Urea Binding Groups: A Potent Glyphosate Adsorber

et al. 2021

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The use of polymerizable hosts in anion imprinting has led to powerful receptors with high oxyanion affinity and specificity in both aqueous and non-aqueous environments. As demonstrated in previous reports, a carefully tuned combination of orthogonally interacting binding groups, for example, positively charged and neutral hydrogen bonding monomers, allows receptors to be constructed for use in either organic or aqueous environments, in spite of the polymer being prepared in non-competitive solvent systems. We here report on a detailed experimental design of phenylphosphonic and benzoic acid-imprinted polymer libraries prepared using either urea- or thiourea-based host monomers in the presence or absence of cationic comonomers for charge-assisted anion recognition. A comparison of hydrophobic and hydrophilic crosslinking monomers allowed optimum conditions to be identified for oxyanion binding in non-aqueous, fully aqueous, or high-salt media. This showed that recognition improved with the water content for thiourea-based molecularly imprinted polymers (MIPs) based on hydrophobic EGDMA with an opposite behavior shown by the polymers prepared using the more hydrophilic crosslinker PETA. While the affinity of thiourea-based MIPs increased with the water content, the opposite was observed for the oxourea counterparts. Binding to the latter could however be enhanced by raising the pH or by the introduction of cationic amine- or Na + -complexing crown ether-based comonomers. Use of high-salt media as expected suppressed the amine-based charge assistance, whereas it enhanced the effect of the crown ether function. Use of the optimized receptors for removing the ubiquitous pesticide glyphosate from urine finally demonstrated their practical utility.

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High salt compatible oxyanion receptors by dual ion imprinting

Abstract: Imprinting of an ion-pair in presence of mutually compatible anion and cation host monomers leads to polymers showing enhanced ion uptake in competitive high ionic strength buffers.

Cited by 7 publications

References 32 publications

Urea-Based Imprinted Polymer Hosts with Switchable Anion Preference

Urea-Based Imprinted Polymer Hosts with Switchable Anion Preference

Discrimination between sialic acid linkage modes using sialyllactose-imprinted polymers

Oxoanion Imprinting Combining Cationic and Urea Binding Groups: A Potent Glyphosate Adsorber

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