Direct Measurement of the Thermodynamics of Chiral Recognition in Bile Salt Micelles

Anderson, Shauna Lynn; Rovnyak, David; Strein, Timothy G.

doi:10.1002/chir.22580

Cited by 21 publications

(18 citation statements)

References 38 publications

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“…In recent work, the difference in the enthalpy of binding of R‐ vs. S‐BNDHP to bile salts was measured to be about 1 kJ per mole, whereas it was not possible to detect the difference in the enthalpy of binding of R‐ vs. S‐BN to bile aggregates . Whereas Figure showed that weak intermoleculear NOEs could be observed for R,S‐BNDHP binding to respective edge locations of bile acid aggregates, it was not possible to detect NOEs from R,S‐BN to the bile carbon‐7 or carbon‐12 edges, which is consistent with weaker binding of R,S‐BN to bile aggregates.…”

Section: Resultsmentioning

confidence: 93%

“…[7][8][9][10][11][12] Despite the fact that the majority of carbon atoms in bile acids such as cholate and deoxycholate exhibit exclusive chirality in nature, the potential physiological significance of bile acid guest-host chiral recognition remains unknown. Recently, the thermodynamics of chirally selective guest-host binding have been characterized by isothermal titration calorimetry, 13 but the structural mechanism by which bile aggregates selectively interact with enantiomers of guest compounds is not known.…”

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confidence: 99%

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An Edge Selection Mechanism for Chirally Selective Solubilization of Binaphthyl Atropisomeric Guests by Cholate and Deoxycholate Micelles

et al. 2016

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Combining micellar electrokinetic capillary chromatography (MEKC) and nuclear magnetic resonance (NMR) experimentation, we shed light on the structural basis for the chirally selective solubilization of atropisomeric binaphthyl compounds by bile salt micelles comprised of cholate (NaC) or deoxycholate (NaDC). The model binaphthyl analyte R,S-BNDHP exhibits chirally selective interactions with primary micellar aggregates of cholate and deoxycholate, as does the closely related analyte binaphthol (R,S-BN). Chiral selectivity was localized, by NMR chemical shift analysis, to the proton at the C12 position of these bile acids. Correspondingly, MEKC results show that the 12α-OH group of either NaC or NaDC is necessary for chirally selective resolution of these model binaphthyl analytes by bile micelles, and the S isomer is more highly retained by the micelles. With NMR, the chemical shift of 12β-H was perturbed more strongly in the presence of S-BNDHP than R-BNDHP. Intermolecular NOEs demonstrate that R,S-BNDHP and R,S-BN interact with a similar hydrophobic planar pocket lined with the methyl groups of the bile salts, and are best explained by the existence of an antiparallel dimeric unit of bile salts. Finally, chemical shift data and intermolecular NOEs support different interactions of the enantiomers with the edges of dimeric bile units, indicating that R,S-BNDHP enantiomers sample the same binding site preferentially from opposite edges of the dimeric bile unit. Chirality 28:525-533, 2016. © 2016 Wiley Periodicals, Inc.

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Section: Resultsmentioning

confidence: 93%

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confidence: 99%

An Edge Selection Mechanism for Chirally Selective Solubilization of Binaphthyl Atropisomeric Guests by Cholate and Deoxycholate Micelles

et al. 2016

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“…23 The ΔH demic of these bile salt micelle systems is observable and strongly temperature dependent, allowing the determination of ΔCp demic . Timothy G. Strein et al reported on the application of ITC to the process of bile salt demicellization (demic in short) and its chiral binding recognition.…”

Section: Guest-host Chiral Binding Interactionsmentioning

confidence: 99%

“…Timothy G. Strein et al reported on the application of ITC to the process of bile salt demicellization (demic in short) and its chiral binding recognition. 23 The ΔH demic of these bile salt micelle systems is observable and strongly temperature dependent, allowing the determination of ΔCp demic . The chiral selectivity of guest-host binding of model chiral racemic compounds to the bile salt micelles was investigated.…”

Section: Guest-host Chiral Binding Interactionsmentioning

confidence: 99%

Isothermal titration calorimetry for chiral chemistry

Werber

Mastai

2018

Chirality

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One of the most powerful techniques that are currently available to measure thermodynamic parameters such as enthalpy (ΔH), Gibbs free energy (ΔG), entropy changes (ΔS), and binding affinity in chemical reactions is isothermal titration calorimetry (ITC). Recent advances in instrumentation have facilitated the development of ITC as a very essential analytical tool in biology and chemistry. In this article, we will focus on a review of the literature on the application of ITC for the study of chiral systems and chiral interactions. We present studies in which the ITC technique is used to study chiral interactions, for instance in chiral solutions, chiral organometallic complexes, guest-host chiral binding interactions, and biological macromolecules. Finally, we put strong emphasis on the most recent application of ITC for the study of chirality in nanosystems and at the nanoscale.

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“…[16] The primary micelles of bile acid salts at lower temperatures are formed due to hydrophobic effect (movement of water molecules, during the association, from the convex hydrophobic surface of the monomer into the interior of the solutionentropically driven), whereas at higher temperatures, the micelles are formed due to hydrophobic interactions between the convex surfaces of the steroid skeleton (enthalpically driven). [17,18] Kawamura et al gave a model similar to Small, where bile acid anions were aligned on the surface of the disc in such a manner that the orientation of the carboxylate groups (down, up) was successively changed, giving minimal electrostatic repulsions. [19] At concentrations several times higher than the CMC (for some bile acid anions), the primary micelles are bonded to each other by hydrogen bonds-Small's secondary micelles.…”

Section: Introductionmentioning

confidence: 99%

Hydrophobicity and self‐association (micellization) of bile salts with a lactone or lactam group in a steroid skeleton

Poša

Tepavčević

Grbović

et al. 2020

J of Physical Organic Chem

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Bile acid salts are amphiphiles that have planar polarity: the convex surface (the β side) of their steroid skeleton is hydrophobic, whereas the concave surface (the α side) is hydrophilic. Lactone and lactam derivatives of bile acid salts have reduced hydrophobicity on the convex surface (β side) of the steroid skeleton, but they are still able to build micelles. In the vicinity of their critical micellar concentration (CMC), they probably form Small's primary micelles. In this work, it is shown that retention capacities (reverse-phase highperformance liquid chromatography) are linearly dependent on temperature, for each tested bile acid. The parameters of this linear dependence (intercept and slope) can be used to describe the hydrophobicity of the analyzed bile acid salts. The first and the second principal components, derived from the covariance matrix of temperature dependence of retention capacity, can also be used as hydrophobicity parameters of the analyzed bile acid salts. There is a strong correlation between the CMC values and the values of the hydrophobicity parameters of the convex surface (the β side) of the steroid skeleton: the CMC values decrease as the hydrophobicity of the β side of the steroid skeleton decreases.

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Direct Measurement of the Thermodynamics of Chiral Recognition in Bile Salt Micelles

Cited by 21 publications

References 38 publications

An Edge Selection Mechanism for Chirally Selective Solubilization of Binaphthyl Atropisomeric Guests by Cholate and Deoxycholate Micelles

An Edge Selection Mechanism for Chirally Selective Solubilization of Binaphthyl Atropisomeric Guests by Cholate and Deoxycholate Micelles

Isothermal titration calorimetry for chiral chemistry

Hydrophobicity and self‐association (micellization) of bile salts with a lactone or lactam group in a steroid skeleton

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