Binding studies of a protonated dioxatetraazamacrocycle with carboxylate substrates

Carvalho, Sílvia; Delgado, Rita; Drew, Michael G. B.; Calisto, Vânia; Félix, Vı́tor

doi:10.1016/j.tet.2008.03.002

Cited by 19 publications

(23 citation statements)

References 39 publications

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“…Given that this entropic penalty is omitted from our computations, it is perhaps not surprising that our computations overestimate the stability of this complex relative to the other complexes. Therefore, we thought it might be possible to release the carboxylates from their complexes with the bis-(acetylguanidinium)ferrocene cation 1 via addition of CB [7]. It was anticipated that CB [7] would bind ferrocene compound 1 more tightly than any of the carboxylates used in the study.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…It was anticipated that CB [7] would bind ferrocene compound 1 more tightly than any of the carboxylates used in the study. We exploited the strength of the association of the ferrocene compound to CB [7] to allow us to monitor the release of the carboxylate guests via NMR. Figure 6d shows the NMR spectra of ferrocene compound 1 mixed with 10.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…49 Here, we show that 1 forms tight complexes to dicarboxylates in pure water and that additional electrostatic interactions as well as the size and shape complementarity of the carboxylate to the ferrocene salt dramatically increase the stability of the complex. Through NMR studies, we find that upon addition of cucurbit [7]uril (CB [7], 10) the ferrocene cation−carboxylate complex dissociates, releasing the carboxylate to the bulk solvent, which demonstrates a noncovalent catch and release process.…”

Section: 53mentioning

confidence: 99%

“…Density functional theory computations of the binding enthalpy of the rigid carboxylates for these complexes agree well with the experimentally determined association constants. Catch and release competitive binding experiments were done by NMR for the cation-carboxylate ion-pair complexes with cucurbit [7]uril, and they show dissociation of the ion-pair complex upon addition of cucurbit [7] ABSTRACT: Association constants of a bis-(acetylguanidinium)ferrocene dication to various (di)carboxylates were determined through UV−vis titrations. Association constant values greater than 10 4 M −1 were determined for both phthalate and maleate carboxylates to the bis-(acetylguanidinium)ferrocene salt in pure water.…”

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confidence: 99%

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Noncovalent Catch and Release of Carboxylates in Water

Beck

Winter

2014

J. Org. Chem.

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Association constants of a bis-(acetylguanidinium)ferrocene dication to various (di)carboxylates were determined through UV-vis titrations. Association constant values greater than 10 4 M -1 were determined for both phthalate and maleate carboxylates to the bis-(acetylguanidinium)ferrocene salt in pure water. Density functional theory computations of the binding enthalpy of the rigid carboxylates for these complexes agree well with the experimentally determined association constants. Catch and release competitive binding experiments were done by NMR for the cation-carboxylate ion-pair complexes with cucurbit [7]uril, and they show dissociation of the ion-pair complex upon addition of cucurbit [7] ABSTRACT: Association constants of a bis-(acetylguanidinium)ferrocene dication to various (di)carboxylates were determined through UV−vis titrations. Association constant values greater than 10 4 M −1 were determined for both phthalate and maleate carboxylates to the bis-(acetylguanidinium)ferrocene salt in pure water. Density functional theory computations of the binding enthalpy of the rigid carboxylates for these complexes agree well with the experimentally determined association constants. Catch and release competitive binding experiments were done by NMR for the cation−carboxylate ion-pair complexes with cucurbit [7]uril, and they show dissociation of the ion-pair complex upon addition of cucurbit [7]uril and release of the free (di)carboxylate.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: 53mentioning

confidence: 99%

mentioning

confidence: 99%

mentioning

confidence: 99%

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Noncovalent Catch and Release of Carboxylates in Water

Beck

Winter

2014

J. Org. Chem.

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Synthetic Strategies

Bencini¹,

Llinares²

2011

Anion Coordination Chemistry

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Design of Protonated Polyazamacrocycles Based on Phenanthroline Motifs for Selective Uptake of Aromatic Carboxylate Anions and Herbicides

Cruz

Calisto

Delgado

et al. 2009

Chemistry A European J

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Three novel large polyazamacrocycles containing two 1,10-phenanthroline units connected by different polyamine spacers have been synthesised and their protonated forms used as receptors for several aromatic carboxylate anions. The receptors bind to the anions in a 1:1 stoichiometry and exhibit remarkable binding selectivity (see figure). Analysis shows that molecular recognition is governed by pi-pi stacking interactions and multiple N--HO==C hydrogen bonds.Three novel large polyazamacrocycles containing two 1,10-phenanthroline (phen) units connected by two polyamine spacers of different length, [32]phen(2)N(4), [30]phen(2)N(6) and Me(2)[34]phen(2)N(6), have been synthesised and their protonated forms used as receptors for binding studies with several aromatic carboxylate anions (benzoate (bzc(-)), 1-naphthalate (naphc(-)), 9-anthracenate (anthc(-)), pyrene-1-carboxylate (pyrc(-)), phthalate, (ph(2-)), isophthalate (iph(2-)), terephthalate (tph(2-)), 2,5-dihydroxy-1,4-benzenediacetate (dihyac(2-)) and, 1,3,5-benzenetricarboxylate (btc(3-))) and three herbicides (4-amino-3,5,6-trichloropyridine-2-carboxylate (ATCP(-)), dichlorophenoxyacetate (2,4-D(-)) and glyphosate (PMG(2-))) in water solution. The [30]phen(2)N(6) receptor was found to be the most suitable for binding the anions considered in a 1:1 stoichiometry. The three receptors exhibit a remarkable binding selectivity towards the extended aromatic anion pyrc(-) at low pH values. Their binding affinities for the monocarboxylate anions decrease with the extension of the aromatic system in the order pyrc(-)>anthc(-)>naphc(-)>bzc(-), which indicates the presence of pi-pi stacking interactions in the molecular recognition of these anions. Molecular dynamics simulations carried out for the binding of {H(4)[30]phen(2)N(6)}(4+) and {H(6)Me(2)[34]phen(2)N(6)}(6+) with pyrc(-), anthc(-), naphc(-), iph(2-) and btc(3-) in water showed that these receptors adopt a folded conformation with the anion inserted between the two phen heads and that the molecular recognition is governed by pi-pi stacking interactions and multiple N--HO==C hydrogen bonds. The binding free energies estimated theoretically are very similar to those found by potentiometric methods, which supports the proposed binding arrangement.

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Binding studies of a protonated dioxatetraazamacrocycle with carboxylate substrates

Cited by 19 publications

References 39 publications

Noncovalent Catch and Release of Carboxylates in Water

Noncovalent Catch and Release of Carboxylates in Water

Synthetic Strategies

Design of Protonated Polyazamacrocycles Based on Phenanthroline Motifs for Selective Uptake of Aromatic Carboxylate Anions and Herbicides

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