Electrochemical Method for the Determination of Enantiomeric Excess of Binol Using Redox-Active Boronic Acids as Chiral Sensors

Mirri, Giorgio; Bull, Steven D.; James, Tony D.; Male, Louise; Tucker, James H. R.

doi:10.1021/ja103462x

Cited by 88 publications

(60 citation statements)

References 31 publications

(12 reference statements)

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“…[9] Fort he above reasons we have decided to develop as ensitive and HTS-amenable assay for chiral amines and their derivatives.W et ake advantage of at ernary system comprising an a-chiral primary amine,2 -formylphenylboronic acid (FPBA), and enantiomerically pure 1,1'-bi-2-naphthol (BINOL), which assemble rapidly and lead to characteristic 1 HNMR spectroscopic shifts for each enantiomer of the amine (Scheme 1). [10] This system has also been employed for determination of ee values by using electrochemical [11] or CD methods. [12] Our assumption is that the twist angle of the fluorescent BINOL ligand, is affected by the chirality of the analyte during the assembly,t hereby resulting in detectable fluorescence changes (i.e.i ntensity changes and spectral shifts).…”

Section: Introductionmentioning

confidence: 99%

Determination of Enantiomeric Excess in Amine Derivatives with Molecular Self‐Assemblies

et al. 2015

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Abstract:We report the first fluorescence-based assayf or the rapid determination of the ee value of amines,amino alcohols, and amino acid esters.The method uses the self-assembly of 2-formylphenylboronic acid with achiral diol and achiral amine or derivatives (of unknown chirality) to produce two diastereomeric iminoboronates that differ in their fluorescence intensity and polarization. The approach allows for the accurate determination of the ee value of chiral amines with errors of just 1-2 %. We believe that this application of orthogonal dynamic covalent self-assembly in the determination of the enantioselectivity will lead to the development of high-throughput procedures for the determination of chirality.

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Section: Introductionmentioning

confidence: 99%

Determination of Enantiomeric Excess in Amine Derivatives with Molecular Self‐Assemblies

et al. 2015

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“…Attractive because little discriminatory power is needed for signal generation, these lessons from nature have been successfully applied to several chemosensor systems. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] The bottleneck of this approach is the establishment of multiple molecular recognition frameworks, which are necessary to generate patterns. So far, this has not been possible with synthetic sensing systems that work, like olfactory receptors, in lipid bilayer membranes.…”

Section: Introductionmentioning

confidence: 99%

Pattern generation with synthetic sensing systems in lipid bilayer membranes

et al. 2011

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The objective of this study was to introduce differential sensing techniques to synthetic systems that act, like olfactory receptors, as transporters in lipid bilayer membranes. Routine with most alternative chemosensing ensembles, pattern generation has, quite ironically, remained inaccessible in lipid bilayers because the number of available crossresponsive sensor components has been insufficient. To address this challenge, we here report on the use of cationic hydrazides that can react in situ with hydrophobic analytes to produce cationic amphiphiles which in turn can act as countercation activators for polyanionic transporters in fluorogenic vesicles. To expand the dimension of signals generated by this system, a small collection of small peptides containing a positive charge (guanidinium, ammonium) and one to three reactive hydrazides are prepared. Odorants are used as examples for hydrophobic analytes, perfumes to probe compatibility with complex matrices, and counterion-activated calf-thymus DNA as representative polyion–counterion transport system. Principal component and hierarchical cluster analysis of the obtained multidimensional patterns are shown to differentiate at least 21 analytes in a single score plot, discriminating also closely related structures such as enantiomers, cis–trans isomers, single-atom homologs, as well as all tested perfumes. Inverse detection provides access to analytes as small as acetone. The general nature of the introduced methodology promises to find diverse applications in current topics in biomembrane research

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“…[1][2][3][4][5][6][7][8][9] Fluorescent chiral boronic acid sensors are of particular interest due to the covalent bonding nature of the enantioselective interaction between the sensor and the analytes (such as tartaric acids, sugar, sugar alcohol, and sugar acids), which ensures their applicability for the analysis of biological samples. [10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] We have long been interested in chiral fluorescent boronic acid sensors.…”

Section: Introductionmentioning

confidence: 99%

Chiral Donor Photoinduced‐Electron‐Transfer (d‐PET) Boronic Acid Chemosensors for the Selective Recognition of Tartaric Acids, Disaccharides, and Ginsenosides

Guo

Zhang

et al. 2011

Chemistry A European J

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A modular approach was proposed for the preparation of chiral fluorescent molecular sensors, in which the fluorophore, scaffold, and chirogenic center can be connected by ethynyl groups, and these modules can easily be changed to other structures to optimize the molecular sensing performance of the sensors. This modular strategy to assembly chiral sensors alleviated the previous restrictions of chiral boronic acid sensors, for which the chirogenic center, fluorophore, and scaffold were integrated, thus it was difficult to optimize the molecular structures by chemical modifications. We demonstrated the potential of our new strategy by the preparation of a sensor with a larger scaffold. The photoinduced electron-transfer (PET) effect is efficient even with a large distance between the N atom and the fluorophore core. Furthermore, the rarely reported donor-PET (d-PET) effect, which was previously limited to carbazole, was extended to phenothiazine fluorophore. The contrast ratio, that is, PET efficiency of the new d-PET sensor, is increased to 8.0, compared to 2.0 with the previous carbazole d-PET sensors. Furthermore, the ethynylated phenothiazine shows longer excitation wavelength (centered at 380 nm) and emission wavelength (492 nm), a large Stokes shift (142 nm), and high fluorescence quantum yield in aqueous solution (Φ=0.48 in MeOH/water, 3:1 v/v). Enantioselective recognition of tartaric acid was achieved with the new d-PET boronic acid sensors. The enantioselectivity is up to 10 (ratio of the binding constants toward D- and L-tartaric acid, k(D)/k(L)). A consecutive fluorescence enhancement/decrease was observed, thus we propose a transition of the binding stoichiometry from 1:1 to 1:2 as the analyte concentration increases, which is supported by mass spectra analysis. The boronic acid sensors were used for selective and sensitive recognition of disaccharides and glycosylated steroids (ginsenosides).

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Electrochemical Method for the Determination of Enantiomeric Excess of Binol Using Redox-Active Boronic Acids as Chiral Sensors

Cited by 88 publications

References 31 publications

Determination of Enantiomeric Excess in Amine Derivatives with Molecular Self‐Assemblies

Determination of Enantiomeric Excess in Amine Derivatives with Molecular Self‐Assemblies

Pattern generation with synthetic sensing systems in lipid bilayer membranes

Chiral Donor Photoinduced‐Electron‐Transfer (d‐PET) Boronic Acid Chemosensors for the Selective Recognition of Tartaric Acids, Disaccharides, and Ginsenosides

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