Trapping of Organophosphorus Chemical Nerve Agents in Water with Amino Acid Functionalized Baskets

Ruan, Yian; Dalkılıç, Erdin; Peterson, Paul W.; Pandit, Aroh; Daştan, Arif; Brown, Jason; Polen, Shane M.; Hadad, Christopher M.; Badjić, Jovica D.

doi:10.1002/chem.201304779

Cited by 42 publications

(61 citation statements)

References 45 publications

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“…4,29 A clustering analysis of the resulting MD results gave 10 structures representing the conformational characteristics of 1 ( Figure 4A). Evidently, the amphiphilic 1 is preorganized 30 for complexing guests with three aliphatic chains at the rim extending into the water solution to create a "hydrophobic pocket".…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Recognition Characteristics of an Adaptive Vesicular Assembly of Amphiphilic Baskets for Selective Detection and Mitigation of Toxic Nerve Agents

et al. 2014

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We used isothermal titration calorimetry to investigate the affinity of basket 1 (470 Å(3)) for trapping variously sized and shaped organophosphonates (OPs) 2-12 (137-244 Å(3)) in water at 298.0 K. The encapsulation is, in each case, driven by favorable entropy (TΔS° = 2.9 kcal/mol), while the enthalpic component stays small and in some cases endothermic (ΔH° ≥ -1 kcal/mol). Presumably, a desolvation of basket 1 and OP guests permits the inclusion complexation at room temperature via a "classical" hydrophobic effect. The amphiphilic basket 1 shows a greater affinity (ΔG° ≈ -5 to -6 kcal/mol), both experimentally and computationally, for encapsulating larger organophosphonates whose size and shape correspond to VX-type agents (289 A(3)). Importantly, baskets assemble into a vesicular nanomaterial (DH ≈ 350 nm) that in the presence of neutral OP compounds undergoes a phase transition to give nanoparticles (DH ≈ 250 nm). Upon the addition of an anionic guest to basket 1, however, there was no formation of nanoparticles and the vesicles grew into larger vesicles (DH ≈ 750 nm). The interconversion of the different nanostructures is reversible and, moreover, a function of the organophosphonate present in solution. On the basis of (1)H NMR spectroscopic data, we deduced that neutral guests insert deep into the basket's cavity to change its shape and thereby promote the conversion of vesicles into nanoparticles. On the contrary, the anionic guests reside at the northern portion of the host to slightly affect its shape and geometric properties, thereby resulting in the vesicles merely transforming into larger vesicles.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Recognition Characteristics of an Adaptive Vesicular Assembly of Amphiphilic Baskets for Selective Detection and Mitigation of Toxic Nerve Agents

et al. 2014

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“…To date, only a few examples of supramolecular hosts for CWA simulants have been reported in the literature [14,15,16,17,18,19,20,21,22,23,24]. They exploit several non-covalent interactions for the recognition of the guest, such as inclusion within the hydrophobic macrocyclic cavity [14,15,16,17] or hydrogen bond-dependent gel formation [18,19,20,21,22,23,24,25].…”

Section: Introductionmentioning

confidence: 99%

“…They exploit several non-covalent interactions for the recognition of the guest, such as inclusion within the hydrophobic macrocyclic cavity [14,15,16,17] or hydrogen bond-dependent gel formation [18,19,20,21,22,23,24,25]. …”

Section: Introductionmentioning

confidence: 99%

Supramolecular Detection of a Nerve Agent Simulant by Fluorescent Zn–Salen Oligomer Receptors

et al. 2019

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We report on new Zn–Salen oligomer receptors able to recognize a nerve agent simulant, namely dimethyl methylphosphonate (DMMP), by a supramolecular approach. In particular, three Zn-Salen oligomers (Zn–Oligo–A, –B, and –C), differing by the length distribution, were obtained and characterized by NMR, Gel Permeation Chromatography (GPC), UV-Vis, and fluorescence spectroscopy. Furthermore, we investigated their recognition properties towards DMMP by using fluorescence measurements. We found that the recognition ability depends on the length of the oligomeric chain, and the Zn–Oligo–C shows a binding constant value higher than those already reported in literature for the DMMP detection.

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“…21 Baskets 1 and 2, containing glycine and (S)−alanine residues at the portal, were prepared using previously reported methods. 29 set of resonances corresponding to, on average, C 3v symmetric molecules (Figure 2A/E). The spectra were assigned with the assistance of two-dimensional 1 H− 1 H NOESY and 1 H− 13 C HMQC cross-correlations ( Figure S2).…”

Section: Introductionmentioning

confidence: 99%

Russian Nesting Doll Complexes of Molecular Baskets and Zinc Containing TPA Ligands

et al. 2016

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In this study, we examined the structural and electronic complementarities of convex 1-Zn(II), comprising functionalized tris(2-pyridylmethyl)amine (TPA) ligand, and concave baskets 2 and 3, having glycine and (S)-alanine amino acids at the rim. With the assistance of (1)H NMR spectroscopy and mass spectrometry, we found that basket 2 would entrap 1-Zn(II) in water to give equimolar 1-Zn⊂2in complex (K = (2.0 ± 0.2) × 10(3) M(-1)) resembling Russian nesting dolls. Moreover, C3 symmetric and enantiopure basket 3, containing (S)-alanine groups at the rim, was found to transfer its static chirality to entrapped 1-Zn(II) and, via intermolecular ionic contacts, twist the ligand's pyridine rings into a left-handed (M) propeller (circular dichroism spectroscopy). With molecular baskets embodying the second coordination sphere about metal-containing TPAs, the here described findings should be useful for extending the catalytic function and chiral discrimination capability of TPAs.

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Trapping of Organophosphorus Chemical Nerve Agents in Water with Amino Acid Functionalized Baskets

Cited by 42 publications

References 45 publications

Recognition Characteristics of an Adaptive Vesicular Assembly of Amphiphilic Baskets for Selective Detection and Mitigation of Toxic Nerve Agents

Recognition Characteristics of an Adaptive Vesicular Assembly of Amphiphilic Baskets for Selective Detection and Mitigation of Toxic Nerve Agents

Supramolecular Detection of a Nerve Agent Simulant by Fluorescent Zn–Salen Oligomer Receptors

Russian Nesting Doll Complexes of Molecular Baskets and Zinc Containing TPA Ligands

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