Rationally Designed Cooperatively Enhanced Receptors To Magnify Host–Guest Binding in Water

Gunasekara, Roshan W.; Zhao, Yan

doi:10.1021/ja510823h

Cited by 25 publications

(30 citation statements)

References 57 publications

(70 reference statements)

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“…[3] Electrostatic attractions,a so bserved in ion-pair binding, [4] and maximization of hydrophobic effects in container molecules [5] can also lead to positive allosteric cooperativity.Nevertheless,positive allosteric cooperativity has rarely been achieved through activating relatively weak non-covalent interactions. [6] However,this effect is applied to synthetic molecular recognition [7] and is also common in biological assemblies. [8] Herein, we report an ew molecular tube-based ternary complex with as trong positive cooperativity (a = 580).…”

mentioning

confidence: 99%

Achieving Strong Positive Cooperativity through Activating Weak Non‐Covalent Interactions

Valkonen

et al. 2017

Angew Chem Int Ed

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Positive cooperativity achieved through activating weak non-covalent interactions is common in biological assemblies but is rarely observed in synthetic complexes. Two new molecular tubes have been synthesized and the syn isomer binds DABCO-based organic cations with high orientational selectivity. Surprisingly, the ternary complex with two hosts and one guest shows a high cooperativity factor (α=580), which is the highest reported for synthetic systems without involving ion-pairing interactions. The X-ray single-crystal structure revealed that the strong positive cooperativity likely originates from eight C-H⋅⋅⋅O hydrogen bonds between the two head-to-head-arranged syn tube molecules. These relatively weak hydrogen bonds were not observed in the free hosts and only emerged in the complex. Furthermore, this complex was used as a basic motif to construct a robust [2+2] cyclic assembly, thus demonstrating its potential in molecular self-assembly.

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confidence: 99%

Achieving Strong Positive Cooperativity through Activating Weak Non‐Covalent Interactions

Valkonen

et al. 2017

Angew Chem Int Ed

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“…12,13 The environmentally sensitive aminonaphthalenesulfonate is also important, as it could serve as a spectroscopic reporter to indicate its migration from an aqueous phase to a more hydrophobic membrane. 30,32 In this work, we synthesized two additional bischolates, 3 and 4. Molecule 3 is identical to 1 in every aspect except that the ionic aminonaphthalenesulfonate was replaced by another environmentally sensitive NBD fluorophore.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…According to our previous studies, bischolate 1 folds hydrophobically in water through the interactions of the β-faces of the cholates. 30 Although 3 and 4 have some significant differences from 1 (in terms of the orientation and nonionic nature of the fluorescent label), they are expected to fold in water similarly through the hydrophobic interactions of the cholate β-faces. This is because, for any hydrophobic molecules to be soluble in water, they need to minimize unfavorable solvent contact for their hydrophobic surfaces, and the largest and most hydrophobic surfaces are the cholate β-faces.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Conformationally Switchable Water-Soluble Fluorescent Bischolate Foldamers as Membrane-Curvature Sensors

Gunasekara

Zhao

2015

Langmuir

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Membrane curvature is an important parameter in biological processes such as cellular movement, division, and vesicle fusion and budding. Traditionally, only proteins and protein-derived peptides have been used as sensors for membrane curvature. Three water-soluble bischolate foldamers were synthesized, all labeled with an environmentally sensitive fluorophore to report their binding with lipid membranes. The orientation and ionic nature of the fluorescent label were found to be particularly important in their performance as membrane-curvature sensors. The bischolate with an NBD group in the hydrophilic α-face of the cholate outperformed the other two analogues as a membrane-curvature sensor and responded additionally to the lipid composition including the amounts of cholesterol and anionic lipids in the membranes. Disciplines Chemistry CommentsReprinted (adapted) with permission from Langmui 31 (2015) ABSTRACT: Membrane curvature is an important parameter in biological processes such as cellular movement, division, and vesicle fusion and budding. Traditionally, only proteins and protein-derived peptides have been used as sensors for membrane curvature. Three water-soluble bischolate foldamers were synthesized, all labeled with an environmentally sensitive fluorophore to report their binding with lipid membranes. The orientation and ionic nature of the fluorescent label were found to be particularly important in their performance as membrane-curvature sensors. The bischolate with an NBD group in the hydrophilic α-face of the cholate outperformed the other two analogues as a membrane-curvature sensor and responded additionally to the lipid composition including the amounts of cholesterol and anionic lipids in the membranes.

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“…Our group has been very interested in the creation of biomimetic receptors capable of functioning in aqueous environments . Recently, we designed and synthesized doubly cross‐linkable surfactants such as 1 (Scheme ) .…”

Section: Introductionmentioning

confidence: 99%

“…[29][30][31][32][33][34] Our group has been very interested in the creation of biomimetic receptors capable of functioning in aqueous environments. [35][36][37] Recently, we designed and synthesized doubly cross-linkable surfactants such as 1 (Scheme 1). 38 The compound has a tripropargylammonium headgroup that allows us to cross-link its micelle on the surface by the well-known copper-catalyzed alkyneazide click reaction.…”

Section: Introductionmentioning

confidence: 99%

Tuning surface‐cross‐linking of molecularly imprinted cross‐linked micelles for molecular recognition in water

Zhang

Zhao

2018

J of Molecular Recognition

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Molecular recognition in water is an important challenge in supramolecular chemistry. Surface‐core double cross‐linking of template‐containing surfactant micelles by the click reaction and free radical polymerization yields molecularly imprinted nanoparticles (MINPs) with guest‐complementary binding sites. An important property of MINP‐based receptors is the surface‐cross‐linking between the propargyl groups of the surfactants and a diazide cross‐linker. Decreasing the number of carbons in between the two azides enhanced the binding affinity of the MINPs, possibly by keeping the imprinted binding site more open prior to the guest binding. The depth of the binding pocket can be controlled by the distribution of the hydrophilic/hydrophobic groups of the template and was found to influence the binding in addition to electrostatic interactions between oppositely charged MINPs and guests. Cross‐linkers with an alkoxyamine group enabled two‐stage double surface‐cross‐linking that strengthened the binding constants by an order of magnitude, possibly by expanding the binding pocket of the MINP into the polar region. The binding selectivity among very similar isomeric structures also improved.

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Rationally Designed Cooperatively Enhanced Receptors To Magnify Host–Guest Binding in Water

Cited by 25 publications

References 57 publications

Achieving Strong Positive Cooperativity through Activating Weak Non‐Covalent Interactions

Achieving Strong Positive Cooperativity through Activating Weak Non‐Covalent Interactions

Conformationally Switchable Water-Soluble Fluorescent Bischolate Foldamers as Membrane-Curvature Sensors

Tuning surface‐cross‐linking of molecularly imprinted cross‐linked micelles for molecular recognition in water

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