Chiral Recognition Effect Research Articles

A free carboxyl-decorated metal-organic framework with 3D helical chirality for highly enantioselective recognition

With the judicious selection of a designed polycarboxylate derived from L-phenylalanine, (S)-5-(((1-carboxy-2-phenylethyl)amino)methyl)isophthalic acid (H3L), a novel homochiral metal-organic framework decorated with a free carboxyl, {[Cu2(HL)2(bipy)]∙2H2O}n (Cu-MOF), has been designed and synthesized in a solvothermal process. The result of single crystal X-ray diffraction analysis showed that Cu-MOF had the character of a three-dimensional structure with helical chirality. As we expected, in Cu-MOF, one accessible free carboxylic acid group on H3L pointed toward the spiral channels, and the other two –COOH groups were utilized in bonding. The enantioseparation performance of Cu-MOF was thoroughly investigated and the results showed that Cu-MOF can specifically recognize S-1-(1-naphthyl) ethanol (S-NE) with enantiomeric excess (ee) value of 99.35 %, which was much higher than the other three racemates. The appropriate size together with suitable interaction sites played an important role in enantioseparations. Inspired by the excellent chiral recognition effects towards S-NE, the chiral recognition mechanism was experimentally clarified. A fully agreement observed in 13C CP MAS NMR analysis as well as the X-ray photoelectron spectroscopy (XPS) determination revealed that a strong hydrogen bonding interaction forces existed between the hydroxyl of the optical S-NE and the decorated –COOH in the chiral framework. The control experiment further identified the decisive role of the uncoordinated carboxyl group in Cu-MOF. In addition, the strong intermolecular off-set π-π interactions between the phenyl ring involved with the coordinated COO− groups in Cu-MOF and the naphthyl ring of S-NE, was the another important factor for the specifical enantioseparation of S-enantiomer. On the basis of strong intermolecular hydrogen bonding, NE racemates were enantioselective discriminated and enantiomeric purity can be determined by means of Raman scattering spectroscopy.

Design and Electrochemical Chiral Sensing of the Robust Sandwich Chiral Composite d-His-ZIF-8@Au@ZIF-8.

In the pursuit of chiral materials with significant chiral recognition effects and stability, various strategies have been explored, among which the integration of metal nanoparticles and chiral metal-organic frameworks (CMOFs) is highly promising. However, metal nanoparticles (MNPs)/CMOFs show high chiral properties but inferior stabilities due to the MNPs being easily detached from the outside layer under certain conditions. Sandwich MOFs@MNPs@CMOF chiral materials can overcome this dilemma because the sandwich structure can maximize the regulation of the chiral interface activity, while the controlled outer layer can stop the MNPs from falling off in the procedure of chiral recognition. Here, a novel sandwich chiral material (d-His-ZIF-8@Au@ZIF-8) was synthesized by a ligand-assisted strategy with a well-defined sandwich morphology and chiral recognition capabilities. The electrochemical chiral recognition showed that d-His-ZIF-8@Au@ZIF-8 was the most efficient for the enantiomer of phenylalanine (Phe). This experiment presents a novel perspective for the fabrication of a chiral electrochemical sensing platform based on a solid sandwich chiral nanocomposite.

Lactate‐based ionic liquids as chiral solvents for cellulose

AbstractWe report the first example of a chiral polymer—cellulose—being dissolved in both enantiomers of a chiral solvent. We synthesized six room temperature ionic liquids (ILs) based on imidazolium and 1,2,3‐triazolium cations and lactate as chiral anion. Some of them have not been described before. We characterize the dissolution of cellulose in the ILs, which are found to be relatively good cellulose solvents with a solubility of up to 18.5 wt.‐%. At the same time, we find solubility differences of up to a factor of 3 between the enantiomers of the solvent, which is a very pronounced chiral recognition effect. Interestingly, the racemate of the solvent dissolves significantly less cellulose than either enantiopure form, which is a significant deviation from ideal mixing behavior. We also report the physicochemical properties of the six ILs (density, viscosity, decomposition temperature, NMR and circular dichroism spectra). Based on molecular dynamics simulations of the solutions and a model which we have published before, we attempt a semi‐quantitative prediction of the cellulose solubility, which yields solid results for the enantiopure solvents. From the simulation results, we obtain microscopic insight into the hydrogen bond network of the complex mixtures in which many different hydrogen bond donors and acceptors compete.

Contribution of molecular chiral mesoporous silica nanoparticles in delivering drugs with chiral recognition ability

Among massive study of mesoporous silica nanoparticles, molecular chiral mesoporous silica nanoparticles (MC-MSN) enjoy great interests recently as it may exert special functions in chiral environment. To elucidate its potential abilities as drug carriers, the present work focused on its prominent advantage of chiral recognition in adsorbing and delivering drug molecules, which mainly covered molecular recognition of racemic drugs and chiral delivery of achiral drug by triggering chiral responses in biological environment. The result turned out that the loading capacity of L-alanine was 1.56-fold higher than that of DL-alanine, reminding that MC-MSN had effective molecular recognition function due to its chirality. Furthermore, the peak area ratio of levorotary ofloxacin/dextral ofloxacin from loaded ofloxacin was obviously higher than ofloxacin, confirming that MC-MSN can molecularly recognize levorotary drug. After loading poorly water-soluble drug indometacin (IMC) into MC-MSN, the carrier delivered IMC with improved anti-inflammation effect based on its chiral recognition effect.

Induction of chiral polymers from metal-organic framework for stereoselective recognition

So far, the fabrication of chiral metal-organic framework (CMOF) is difficult to predict and the chiral functionality mainly comes from the building blocks that is a part of the frameworks. The induction effect in the chiral nanochannels of the metal-organic framework (MOF) makes achiral polymers have chiral properties, which has not been well explored. Therefore, CMOFs with chiral nanochannels or chiral pores appear to have special functions. Herein, CMOFs (D-his-ZIF-8) with chiral micropores or chiral nanochannels are prepared through a simple 2-methyl imidazolate in-situ substitution by d-histidine. The unmodified polyaniline with chirality (c-PANI) was synthesized in chiral nanochannels and pores of CMOF, which brought about chiral induction from the chiral nanochannels and pores of CMOF to c-PANI chains. The circular dichroism shows that the c-PANI chains released from the chiral nanochannel still maintains the chiral properties even leaves the chiral nanochannel. It can be seen from the electrochemical results that c-PANI has excellent conductivity, and the conductivity of CMOF is very poor. Electrochemical recognition showed that both CMOF and c-PANI have certain chiral recognition effects for L-Trp and D-Trp, from which the optimal recognition effect was obtained from c-PANI chains. This shows that the excellent conductivity of c-PANI not only expands the electrochemical signal, but also the helical structure of the c-PANI chains accelerates the distinction of chiral molecules. This study provides a novel perspective to induce chiral polymer chains with better conductivity in the nanochannels of CMOF.

Light-Induced Modulation of Chiral Functions in G-Quadruplex-Photochrome Systems.

The design of artificially engineered chiral structures has received much attention, but the implementation of dynamic functions to modulate the chiroptical response of the systems is less explored. Here, we present a light-responsive G-quadruplex (G4)-based assembly in which chirality enrichment is induced, tuned, and fueled by molecular switches. In particular, the mirror-image dependence on photoactivated azo molecules, undergoing trans-to-cis isomerization, shows chiral recognition effects on the inherent flexibility and conformational diversity of DNA G4s having distinct handedness (right- and left-handed). Through a detailed experimental and computational analysis, we bring compelling evidence on the binding mode of the photochromes on G4s, and we rationalize the origin of the chirality effect that is associated with the complexation event.

Ab Initio Study of Chiral Discrimination in the Glycidol Dimer.

Chiral discrimination, the ability of a chiral molecule to exhibit different weak intermolecular interactions than its mirror image, is investigated for dimers of oxiranemethanol (glycidol). In this regard, high-level ab initio calculations were performed to study the chiral recognition effects in the homochiral and heterochiral dimers of glycidol. Fourteen dimer structures, seven homochiral and seven heterochiral, were studied: they all feature two intermolecular O-H···O hydrogen bonds. These structures have been determined with the second-order Møller-Plesset perturbation theory (MP2) using the aug-cc-pVTZ basis set and verified to pertain to actual local minima. The benchmark interaction energy values were computed using MP2 extrapolated from the aug-cc-pVQZ and aug-cc-pV5Z bases with a higher-level correction from a coupled-cluster calculation in the aug-cc-pVTZ basis. The global minimum structure is a homochiral one, with the two hydrogen bonds forming a part of a ring with eight heavy atoms. A similar heterochiral structure has a binding energy smaller by about 0.6 kcal/mol. The largest diastereomeric energy difference is about 1.0 kcal/mol. Further insight into the origins of chiral discrimination was provided by symmetry-adapted perturbation theory (SAPT) and a functional-group SAPT (F-SAPT) difference analysis to investigate the direct and indirect effects of two -H/-CH2OH substitutions leading from an achiral ethylene oxide dimer to the chiral glycidol dimer. Last but not least, harmonic frequency shifts relative to a noninteracting glycidol molecule were calculated and analyzed for all conformations to get insight into the origins of chiral discrimination. It is found that the largest frequency shifts are related to the effect of hydrogen bonding on the O-H stretch mode, the stability of the ring involving both hydrogen bonds, and the transition between two nonequivalent minima of the glycidol molecule.

Chiral Templating of Polycarbonate Membranes by Pinene Using the Modified Atomic Layer Deposition Approach.

In this article, chiral templating of a polycarbonate (PC) membrane by (-)-α-pinene using the atomic layer deposition (ALD) approach is investigated. The templating with the enantiomer of (-)-α-pinene, used as a case compound, was performed either on the original commercial PC membrane or on the PC membrane with a beforehand deposited Al2O3 layer. The efficiency of the templating was assessed by a difference in the membrane ability to adsorb/absorb (-)-α-pinene, (+)-α-pinene, and their racemic mixture, using a very sensitive gas sorption analyzer. The results clearly show that the solution-diffusion mechanism rather than the sieving mechanism applied for adsorption/absorption of (-/+)-α-pinene enantiomers, which have the same size of the molecule. The PC membrane with the predeposited Al2O3 before the (-)-α-pinene templating shows significantly higher sorption of (-)-α-pinene compared to (+)-α-pinene and racemate, which clearly demonstrates the presence of a chiral recognition effect.

N-acetyl-L-cysteine modified CuFe2O4@SiO2 core-shell nanoparticles as chiral probes for recognition of chiral tyrosine

Chiral recognition exhibits the important practical significance. In this paper, the magnetic CuFe2O4@SiO2 was firstly synthesized by co-precipitation. Then, the core-shell chiral nanomaterial CuFe2O4@SiO2-NALC (NALC = N-acetyl-L-cysteine) was futher prepared by reflow in a flask. It is worth mention that the chiral nanomaterials are obtained by simple synthetic methods and using inexpensive materials. Chiral recognition effect of CuFe2O4@SiO2-NALC on L-/D-tyrosine was confirmed by UV-Vis absorption spectroscopy. CuFe2O4@SiO2-NALC is easy to separate due to the magnetic hull, which has great development prospects of the field of chiral separation.

Improved chiral electrochemical recognition of tryptophan enantiomers based on three-dimensional molecularly imprinted overoxidized polypyrrole/MnO2 /carbon felt composites.

A three-dimensional molecularly imprinted overoxidized polypyrrole/MnO2 /carbon felt (MIOPPy/MnO2 /CF) composites were fabricated, which results in increased active area of the surface of the molecularly imprinted polymers film and greatly improved electrochemical chiral recognition effect for tryptophan isomers. The composites were characterized by field emission scanning electron microscope, transmission electron microscope, X-ray diffractometer, UV-visible spectra, N2 adsorption-desorption isotherms, and electrochemical methods. The manuscript provides a proof of concept and shows promising potential of the prepared composites for chiral recognition.

Gold Nanorod@Chiral Mesoporous Silica Core–shell Nanoparticles with Unique Optical Properties

The design and fabrication of chiral nanostructures is a promising approach to realize enantiomeric recognition and separation. In our work, gold nanorod@chiral mesoporous silica core-shell nanoparticles (GNR@CMS NPs) have been successfully synthesized. This novel material exhibits strong and tunable circular dichroism signals in the visible and near-infrared regions due to the optical coupling between the CMS shells and the GNR cores. When chiral cysteine molecules are loaded in the porous shells, the corresponding surface enhanced Raman scattering spectroscopy demonstrates a distinct chiral recognition effect, which can be used to semiquantitatively measure the composition of chiral enantiomers. A detailed sensing mechanism has been disclosed by density functional theory calculations.

In situ synthesis of twelve dialkyltartrate–boric acid complexes and two polyols–boric acid complexes and their applications as chiral ion-pair selectors in nonaqueous capillary electrophoresis

In this paper, twelve dialkyltartrate–boric acid complexes and two polyols–boric acid complexes were in situ synthesized by the reaction of different dialkyltartrates or polyols with boric acid in methanol containing triethylamine. All of the twelve dialkyltartrate–boric acid complexes were found to have relatively good chiral separation performance in nonaqueous capillary electrophoresis (NACE). Their chiral recognition effects in terms of both enantioselectivity (α) and resolution (Rs) were similar when the number of carbon atoms was below six in the alkyl group of alcohol moiety. The dialkyltartrates containing alkyl groups of different structures but the same number of carbon atoms, i.e. one of straight chain and one of branched chain, also provided similar chiral recognition effects. Furthermore, it was demonstrated for the first time that two methanol insoluble polyols, d-mannitol and d-sorbitol, could react with boric acid to prepare chiral ion-pair selectors using methanol as the solvent medium.

Effect of molecular structure of tartrates on chiral recognition of tartrate–boric acid complex chiral selectors in chiral microemulsion electrokinetic chromatography

Eight l-tartrates and a d-tartrate with different alcohol moieties were used as chiral oils to prepare chiral microemulsions, which were utilized in conjunction with borate buffer to separate the enantiomers of β-blockers or structurally related compounds by the chiral microemulsion electrokinetic chromatography (MEEKC) method. Among them, six were found to have a relatively good chiral separation performance and their chiral recognition effect in terms of both enantioselectivity and resolution increases linearly with the number of carbon atoms in the alkyl group of alcohol moiety. The tartrates containing alkyl groups of different structures but the same number of carbon atoms, i.e. one of straight chain and one of branched chain, provide similar enantioseparations. The trend was elucidated according to the changes in the difference of the steric matching between the molecules of two enantiomers and chiral selector. Furthermore, it was demonstrated for the first time that a water insoluble solid compound, di- i-butyl l-tartrate (mp. 73.5 °C), can be used as an oil to prepare a stable microemulsion to be used in the chiral MEEKC successfully. And a critical effect of the microemulsion for chiral separation, which has never been reported before, was found in this experiment, namely providing a hydrophobic environment to strengthen the interactions between the chiral selector and enantiomers.

OH-Stretching Red Shifts in Bulky Hydrogen-Bonded Alcohols: Jet Spectroscopy and Modeling

The available database for OH-stretching bands of jet-cooled aliphatic alcohol dimers is extended to systems including 1-adamantanol and 2-adamantanol, using a heated pulsed nozzle coupled to an FTIR spectrometer. This database is used to simplify and parametrize the standard Wang et al. AMBER/parm99.dat force field for the prediction of hydrogen-bond-induced red shifts, as it avoids complications due to mode coupling and cooperativity. Apart from subtle chiral recognition effects, the performance of the simple model in describing steric, electronic, and conformational influences on the red shifts is remarkable, as exemplified by predictions for mixed-alcohol dimers. The resulting semiempirical approach can complement quantum chemical calculations, in particular for larger systems, although the good performance is rather specific to red shift predictions.

Complex formation of D-mannonaphto-18-crown-6-ether and enantiomers of phenylalanine in water studied by different physochemical methods

Complex formation of D-mannonaphto-18-crown-6-ether 1 with D- and L-phenylalanine (Phe) and their derivatives was studied using conduction and titration microcalorimetry in aqueous solution, and solvent–solvent (water–chloroform) extraction. The thermal effects accompanying the complexation process were determined, but the chiral recognition effects were very small. The chiral differentiation of amino acid was observed in the experiments of the extraction from water to chloroform phase containing chiral receptor.

Ab initio study of chiral recognition in the propylene imine·hydrogen peroxide complex

High level ab initio calculations were employed to study the chiral recognition effect in several chiral molecular pairs that consist of the propylene imine and hydrogen peroxide molecules. The potential energy surfaces for the complexes formed between S-cis-1,2-propylene imine and the two enantiomeric forms of hydrogen peroxide were constructed, using the calculated interaction energies at different separations and orientations. The energy calculations were done using the MOLPRO suite of programs with CCSD(T)/cc-pVDZ. The energies were counterpoise corrected at every point to eliminate the basis set superposition error. Complete geometry optimizations were further carried out for the molecular complexes consisting of the cis- or trans-propylene imine isomers and the two enantiomeric forms of hydrogen peroxide. The geometry optimizations were done using the Gaussian 98 and 03 suites of programs, with MP2/aug-cc-pVDZ being the highest level used. Altogether, eight stable complexes were identified, and the corresponding dissociation energies were calculated with MP2/aug-cc-pVTZ. The largest chirodiastaltic energy is found at 0.74 kcal mol(-1) for the (syn)trans-propylene imine.hydrogen peroxide complexes, where hydrogen peroxide acts as a hydrogen donor and is on the opposite side of the ring from the methyl group. The rotational constants, dipole moments, and harmonic frequencies of the complexes are presented to assist future spectroscopic investigations.