Preferential Solvation within Hydrophilic Nanocavities and Its Effect on the Folding of Cholate Foldamers

Zhao, Yan; Zhong, Zhenqi; Ryu, Eui-Hyun

doi:10.1021/ja0671159

Cited by 60 publications

(67 citation statements)

References 15 publications

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“…[26] In nonpolar solvents that contained a few percent of a polar solvent, such as MeOH or DMSO, the oligocholate folded into a helix that contained a concentrated pool of the polar solvent (Figure 2). This arrangement was favorable for two main reasons: First, the hydrophilic amide and hydroxy groups of the oligocholate were efficiently solvated by the entrapped polar solvent in a largely nonpolar medium.…”

Section: Synthetic Examples Of Cooperatively Enhanced Receptorsmentioning

confidence: 99%

Cooperatively Enhanced Receptors for Biomimetic Molecular Recognition

Zhao

2013

ChemPhysChem

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The concept of preorganization suggests that organizing a receptor around its guest during binding is detrimental, because the cost of conformational change is assumed to be paid out of the binding energy. Although this concept has historically guided the synthesis of a great many synthetic hosts, in recent years, chemists have begun to synthesize receptors that resemble proteins in their cooperative conformational changes. Such changes could enhance the host-guest interactions, in particular if the binding of the guest triggers previously unengaged noncovalent interactions within the host. These hosts, referred to as cooperatively enhanced receptors, corroborate with their biological counterparts to support the approach of creating high-affinity receptors through the combined strategies of cooperativity and preorganization. Solvents, often the invisible participants of any solution-based supramolecular process, should be properly considered in the design of synthetic receptors, whether preorganized or cooperatively enhanced.

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Section: Synthetic Examples Of Cooperatively Enhanced Receptorsmentioning

confidence: 99%

Cooperatively Enhanced Receptors for Biomimetic Molecular Recognition

Zhao

2013

ChemPhysChem

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“…There is an expansive list of foldamers designed for a wide range of applications, including cell permeation, membrane disruption, discrete molecular recognition, and selective reaction with encapsulated guests [58][59][60][61][62][63]. Likewise, a wide variety of subunits have been used to build foldamers, including steroids [64][65][66], aromatic oligoamides [67], β-peptides [58,61,62], and m-phenylene ethynylenes [63,[68][69][70]. There are many examples of foldamers that are water soluble [62,[71][72][73][74], but in terms of hosts designed to bind guest molecules, they are relatively few.…”

Section: Common Classes Of Water-soluble Hostsmentioning

confidence: 99%

“…There are many examples of foldamers that are water soluble [62,[71][72][73][74], but in terms of hosts designed to bind guest molecules, they are relatively few. Indeed recent efforts in this area have focused on the reverse: that is, the encapsulation of polar molecules for solubilization in organic solvents or transport across bilayers [64,67,75,76]. An example of the creation of a hydrophobic pocket in a foldamer from the Moore group is the m-phenylene ethynylene 1.…”

Section: Common Classes Of Water-soluble Hostsmentioning

confidence: 99%

Van Der Waals Interactions and the Hydrophobic Effect

Gibb

2011

Chemosensors

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“…3 FRET has the benefit of measuring much larger distances than NOE and spin coupling and was found to work extremely well for the oligocholates. [12][13][14] Oligocholates 1 and 2 both contain a salt bridge; their difference lies in the number of cholate units in between the arginine and glutamic acid. Three cholates make one turn in the helix in the folded oligocholates; 12 thus, the absolute distance between the arginine and glutamic acid in the folded conformer is quite similar in 1 and 2.…”

Section: Resultsmentioning

confidence: 99%

Environmental Effects Dominate the Folding of Oligocholates in Solution, Surfactant Micelles, and Lipid Membranes

Cho

Zhao

2010

J. Am. Chem. Soc.

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Oligocholate foldamers with different numbers and locations of guanidinium−carboxylate salt bridges were synthesized. The salt bridges were introduced by incorporating arginine and glutamic acid residues into the foldamer sequence. The conformations of these foldamers were studied by fluorescence spectroscopy in homogeneous solution, anionic and nonionic micelles, and lipid bilayers. Environmental effects instead of inherent foldability were found to dominate the folding. As different noncovalent forces become involved in the conformations of the molecules, the best folder in one environment could turn into the worst in another. Preferential solvation was the main driving force for the folding of oligocholates in solution. The molecules behaved very differently in micelles and lipid bilayers, with the most critical factors controlling the folding−unfolding equilibrium being the solvation of ionic groups and the abilities of the surfactants/lipids to compete for the salt bridge. Because of their ability to fold into helices with a nonpolar exterior and a polar interior, the oligocholates could transport large hydrophilic molecules such as carboxyfluorescein across lipid bilayers. Both the conformational properties of the oligocholates and their binding with the guest were important to the transport efficiency. Abstract:Oligocholate foldamers with different numbers and locations of guanidinium-carboxylate salt bridges were synthesized. The salt bridges were introduced by incorporating arginine and glutamic acid residues into the foldamer sequence. The conformations of these foldamers were studied by fluorescence spectroscopy in homogeneous solution, anionic and nonionic micelles, and lipid bilayers. Environmental effects instead of inherent foldability were found to dominate the folding. As different noncovalent forces become involved in the conformations of the molecules, the best folder in one environment could turn into the worst in another. Preferential solvation was the main driving force for the folding of oligocholates in solution. The molecules behaved very differently in micelles and lipid bilayers, with the most critical factors controlling the folding-unfolding equilibrium being the solvation of ionic groups and the abilities of the surfactants/lipids to compete for the salt bridge. Because of their ability to fold into helices with a nonpolar exterior and a polar interior, the oligocholates could transport large hydrophilic molecules such as carboxyfluorescein across lipid bilayers. Both the conformational properties of the oligocholates and their binding with the guest were important to the transport efficiency.

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Preferential Solvation within Hydrophilic Nanocavities and Its Effect on the Folding of Cholate Foldamers

Cited by 60 publications

References 15 publications

Cooperatively Enhanced Receptors for Biomimetic Molecular Recognition

Cooperatively Enhanced Receptors for Biomimetic Molecular Recognition

Van Der Waals Interactions and the Hydrophobic Effect

Environmental Effects Dominate the Folding of Oligocholates in Solution, Surfactant Micelles, and Lipid Membranes

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