Chiral recognition of binaphthyl derivatives: A chiral recognition model on the basis of chromatography, spectroscopy, and molecular mechanistic calculations for the enantioseparation of 1,1′‐binaphthyl derivatives on cholic acid‐bonded stationary phases

Vaton-Chanvrier, L.; Oulyadi, Hassan; Combret, Y.; Coquerel, Gérard; Combret, Jean‐Claude

doi:10.1002/chir.10053

Cited by 20 publications

(21 citation statements)

References 21 publications

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“…Distinctive three arc reflections at q = 0.97, 1.36, and 1.59 indicated by the black arrows in Figure b were responsible for the polycrystals of BN molecules with optically active transoid conformation . At annealing temperatures above 120 °C, the intensities of these reflections from the BN crystalline structures increased significantly and indicated the enhanced crystallization of BN molecules (Figure c).…”

Section: Resultsmentioning

confidence: 95%

Chiroptical‐Conjugated Polymer/Chiral Small Molecule Hybrid Thin Films for Circularly Polarized Light‐Detecting Heterojunction Devices

Kim

Kyhm

Han

et al. 2019

Adv Funct Materials

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Herein, a simple and facile strategy is described to obtain chiroptically active semiconductor thin films by blending of poly(3-alkylthiophene)s, which are conventional achiral polymer semiconductors, and 1,1′-binaphthyl (BN), a versatile chiral molecule. As expected, the intermolecular interaction between the two materials is important to extend the chirality of the binaphthyl molecules to the hybrid films. The controlled phase separation and crystallization of poly[3-(6-carboxyhexyl)thiophene-2,5-diyl] (P3CT) and binaphthyl hybrid films result in unique heterojunction bilayer thin-film structures that consisted of BN microcrystals at the top and a P3CT/BN mixed layer at the bottom. Such heterojunction bilayer films exhibit significantly amplified chiroptical response with weak broadened tails, which is due to the enhanced crystallization of the chiral BN molecules and formation of heteroaggregates in the hybrid films. Based on the characterization of crystalline structure and photoluminescence analysis, it is found that new electronic energy states are formed in the conduction band region of P3CTs in the P3CT/BN heteroaggregates, which contribute to chirality transfer from BN to the hybrid films. As a proof of concept, a photodiode capable of distinguishably sensing the leftand right-handed circularly polarized light is successfully fabricated by using the hybrid films with the heterojunction bilayer structure.

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Section: Resultsmentioning

confidence: 95%

Chiroptical‐Conjugated Polymer/Chiral Small Molecule Hybrid Thin Films for Circularly Polarized Light‐Detecting Heterojunction Devices

Kim

Kyhm

Han

et al. 2019

Adv Funct Materials

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“…In contrast, this CSA is less efficient than 5c for other NMR markers (there is no separation for H(2Љ), H(3Љ), H(6), and CH 3 -C(4Љ); see also This solvation model seems adequate for all the studied oxazolines except slight modifications such as, for instance, the distances of interacting groups according to steric and/or electronic effects. This hypothesis will be ascertained or refined by a molecular modeling study performed under intermolecular nuclear Overhauser effects (NOEs) constraints 39 conducted with a better performing spectrometer.…”

Section: )mentioning

confidence: 99%

Determination of the enantiomeric composition of chiral delta‐2‐oxazolines‐1,3 by ¹H and ¹⁹F NMR spectroscopy using chiral solvating agents

et al. 2003

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Studies of the perturbing effect of chiral solvating agents (CSAs) 5a and mostly of 5c upon the NMR spectra of chiral Delta(2)-oxazoline 1 demonstrated the ability of these fluoroalcohols to afford diastereomeric solvates from these solutes. Thus, for all tested Delta(2)-oxazolines 1Aa-d, 1Ba, and 1e there is at least one possibility to proceed to their enantiomeric discrimination either by (1)H or (19)F NMR using these CSAs (see Fig. 1). NMR results are discussed from substrate and CSA structure standpoints and a solvation model is proposed on the basis of the inequivalence senses generally observed. Then the method was applied to extracts of incubated locust tissues obtained by solid phase extraction (SPE) after a partial unmasking of the substrate 1.

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“…However, the steroid part with three hydroxy groups on one side is often considered to be a facial amphiphile. These hydroxy groups can have specific interactions, such as those found in inclusion compounds,1, 2 organogelators,3–6 and receptors7, 8 based on cholic acid. Furthermore, the hydroxy groups, each with a different reactivity,9 make cholic acid an ideal starting point for a synthetic procedure.…”

Section: Methodsmentioning

confidence: 99%

Micelle Formation and Antimicrobial Activity of Cholic Acid Derivatives with Three Permanent Ionic Head Groups

Willemen

Smet

Koudijs

et al. 2002

Angew. Chem. Int. Ed.

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Cholic acid, a main bile acid, is a biosurfactant involved in the digestion of dietary lipids. With the carboxylate group as the ionic head group it resembles a ™classical∫ surfactant. However, the steroid part with three hydroxy groups on one side is often considered to be a facial amphiphile. These hydroxy groups can have specific interactions, such as those found in inclusion compounds, [1,2] organogelators, [3±6] and receptors [7,8] based on cholic acid. Furthermore, the hydroxy groups, each with a different reactivity, [9] make cholic acid an ideal starting point for a synthetic procedure. The polarity of the hydroxy groups can be increased to emphasize the facial amphiphilicity of the steroid unit. The resulting facial amphiphiles have many applications in ion transport, [10,11] combinatorial chemistry, [12] vesicle fusion, [13] and improvement of membrane permeability. [14] Even facial amphiphiles with three ionic groups are reported. [15,16] However, the properties of these cationic (NH 3 þ ) or anionic (COO À ) facial amphiphiles are dependent on the pH of the solution. Herein, a series of new facial amphiphiles with a permanent ionic character is presented. Three cationic trimethylammonium groups were attached to cholic acid and the carboxylate group was esterified, to yield a new class of three-headed surfactants.We know of only one other example of a surfactant with three permanent ionic head groups and only one hydrophobic tail. [17] We report on the aggregation of this new type of surfactant into spherical micelles and on its antimicrobial activity.Synthesis of this series of ionic facial amphiphiles was completed in three steps from cholic acid (Scheme 1). First, the carboxylate group was esterified with a long alkyl group.Then, a spacer was attached to all three hydroxy groups using an w-bromoalkanoic chloride. Finally, the bromine atoms were substituted by trimethylamine to give trimethylammonium groups on 1. Variation was made in the length of the alkyl tail (n ¼ 8, 10, 12, or 16) and in the length of the spacer (m ¼ 3, 4, 5, or 7).These new compounds are very hygroscopic. Solutions with accurately defined concentration were therefore prepared from lyophilized solutions. Because of the long aliphatic tail, aggregation occurs at rather low concentrations, about 1 mm, depending on the length of both the alkyl tail and the spacer.Evidence for micelle formation was obtained from cryo-TEM measurements. For several compounds, cryo-TEM images were recorded of aqueous solutions (1 wt %, about 8 mm). Two examples are shown in Figure 1. The images show small aggregates with an average diameter of 3±6 nm. The aggregates formed from 1 a (n ¼ 8, m ¼ 3) are smaller than from 1 g (n ¼ 16, m ¼ 3; 3±4 nm and 5±6 nm respectively), which demonstrates the influence of the alkyl tail length on micellar size. No elliptical or bar-shaped aggregates are COMMUNICATIONS

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Chiral recognition of binaphthyl derivatives: A chiral recognition model on the basis of chromatography, spectroscopy, and molecular mechanistic calculations for the enantioseparation of 1,1′‐binaphthyl derivatives on cholic acid‐bonded stationary phases

Cited by 20 publications

References 21 publications

Chiroptical‐Conjugated Polymer/Chiral Small Molecule Hybrid Thin Films for Circularly Polarized Light‐Detecting Heterojunction Devices

Chiroptical‐Conjugated Polymer/Chiral Small Molecule Hybrid Thin Films for Circularly Polarized Light‐Detecting Heterojunction Devices

Determination of the enantiomeric composition of chiral delta‐2‐oxazolines‐1,3 by ¹H and ¹⁹F NMR spectroscopy using chiral solvating agents

Micelle Formation and Antimicrobial Activity of Cholic Acid Derivatives with Three Permanent Ionic Head Groups

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Chiral recognition of binaphthyl derivatives: A chiral recognition model on the basis of chromatography, spectroscopy, and molecular mechanistic calculations for the enantioseparation of 1,1′‐binaphthyl derivatives on cholic acid‐bonded stationary phases

Cited by 20 publications

References 21 publications

Chiroptical‐Conjugated Polymer/Chiral Small Molecule Hybrid Thin Films for Circularly Polarized Light‐Detecting Heterojunction Devices

Chiroptical‐Conjugated Polymer/Chiral Small Molecule Hybrid Thin Films for Circularly Polarized Light‐Detecting Heterojunction Devices

Determination of the enantiomeric composition of chiral delta‐2‐oxazolines‐1,3 by 1H and 19F NMR spectroscopy using chiral solvating agents

Micelle Formation and Antimicrobial Activity of Cholic Acid Derivatives with Three Permanent Ionic Head Groups

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Determination of the enantiomeric composition of chiral delta‐2‐oxazolines‐1,3 by ¹H and ¹⁹F NMR spectroscopy using chiral solvating agents