Project description:Enantiomers share nearly identical physical properties but have different chiral geometries, making their identification and separation difficult. Here we show that when exposed to a rotating electric field, the left- and right-handed chiral molecules rotate with the field and act as microscopic propellers; moreover, owing to their opposite handedness, they propel along the axis of field rotation in opposite directions. We introduce a new molecular parameter called hydrodynamic chirality to characterize the coupling of rotational motion of a chiral molecule into its translational motion and quantify the direction and velocity of such motion. We demonstrate >80% enrichment level of counterpart enantiomers in solution without using chiral selectors or circularly polarized light. We expect our results to have an impact on multiple applications in drug discovery, analytical and chiral chemistry, including determination of absolute configuration, as well as in influencing the understanding of artificial and natural molecular systems where rotational motion of the molecules is involved.
Project description:Chiral molecules play an important role in biological and chemical processes, but physical effects due to their symmetry-breaking are generally weak. Several physical chiral separation schemes which could potentially be useful, including the propeller effect, have therefore not yet been demonstrated at the molecular scale. However, it has been proposed that complex nonspherical colloidal particles could act as "colloidal molecules" in mesoscopic model systems to permit the visualization of molecular phenomena that are otherwise difficult to observe. Unfortunately, it is difficult to synthesize such colloids because surface minimization generally favors the growth of symmetric particles. Here we demonstrate the production of large numbers of complex colloids with glancing angle physical vapor deposition. We use chiral colloids to demonstrate the Baranova and Zel'dovich (Baranova, N. B.; and Zel'dovich, B. Y. Chem. Phys. Lett. 1978, 57, 435) propeller effect: the separation of a racemic mixture by application of a rotating field that couples to the dipole moment of the enantiomers and screw propels them in opposite directions. The handedness of the colloidal suspensions is monitored with circular differential light scattering. An exact solution for the colloid's propulsion is derived, and comparisons between the colloidal system and the corresponding effect at the molecular scale are made.
Project description:Synthetic molecular machines designed to operate on materials surfaces can convert energy into motion and they may be useful to incorporate into solid state devices. Here, we develop and characterize a multi-component molecular propeller that enables unidirectional rotations on a material surface when energized. Our propeller is composed of a rotator with three molecular blades linked via a ruthenium atom to a ratchet-shaped molecular gear. Upon adsorption on a gold crystal surface, the two dimensional nature of the surface breaks the symmetry and left or right tilting of the molecular gear-teeth induces chirality. The molecular gear dictates the rotational direction of the propellers and step-wise rotations can be induced by applying an electric field or using inelastic tunneling electrons from a scanning tunneling microscope tip. By means of scanning tunneling microscope manipulation and imaging, the rotation steps of individual molecular propellers are directly visualized, which confirms the unidirectional rotations of both left and right handed molecular propellers into clockwise and anticlockwise directions respectively.
Project description:Stabilization of chiral propeller conformations in triaryl compounds is challenging due to generally low racemization barriers. Nonetheless, it was recently found that chiral conformational preferences can be induced to triaryl boranes by incorporating point-chiral alkylether chains to the aryl blades and subsequently locking the structure with ammonia. A four-point interaction, meaning that the cooperative effects of Lewis-adduct formation and three hydrogen bonds, was proposed as stabilizing mechanism. Herein, it was shown that three such strong interactions suffice to introduce a preferential propeller handedness. Although DFT calculations predict no noteworthy preferences for either P- or M-chiral propellers for some of the investigated triarylborane-amine adducts that were prepared with chiral primary amines, vibrational circular dichroism (VCD) spectroscopic characterizations revealed that there is indeed a measurable excess of one propeller handedness. Furthermore, the steric demand of the amine was found to play a key role in the induction process and especially in preventing blade rotations.
Project description:Efficient charge separation is essential in various optoelectronic systems, yet it continues to pose substantial challenges. Building upon the recent evidence that chiral biomolecules can function as electron spin filters, this study aims to extend the application of chirality-driven charge separation from the molecular level to the mesoscale and supramolecular scale. Utilizing cellulose nanocrystals (CNCs) derived from cellulose, the most abundant biomaterial on Earth, this research leverages their self-assembly into chiral nematic structures and their dielectric properties. A device is introduced featuring a chiral nematic hybrid film composed of CNCs and quantum dots (QDs), decorated with iron oxide nanoparticles. Using the quantum-confined Stark effect (QCSE) to probe charge separation, we reveal significant sensitivity to the circular polarization of light and the chiral nematic structure of the film. This approach achieves effective, long-lasting charge separation, both locally and across length scales exceeding 1 μm, enabling potential applications such as self-assembled devices that combine photovoltaic cells with electric capacitance as well as optical electric-field hybrid biosensors.
Project description:Two commercialized polysaccharide-based chiral stationary phases, Lux cellulose-2 and Lux amylose-2, were examined for their chiral recognition ability on a set of 18 biologically active racemic 4,5-dihydro-1H-pyrazole derivatives by applying normal and polar organic elution modes. The results showed that all compounds were baseline-resolved with at least one of the used elution modes. The cellulose-based column was superior using polar organic mobile-phase compositions with analysis times close to 5 min and resolutions up to 18, while the enantiomer-resolving ability of amylose-based columns was greater using the normal elution mode with analysis times close to 30 min and resolutions up to 30. The competition between the analytes and the mobile phase constituents on H-bond interactions with the stationary phase has been discussed, and the impact of this competition on chiral recognition has been investigated. It was found that the polar organic mode is very beneficial for short run times and sharp peaks. The developed enantioselective high-performance liquid chromatography (HPLC) methods will be applied to monitor the stereoselective synthesis of compounds 1-18 or to develop preparative HPLC techniques for compounds 1-18, followed by stereospecific pharmacological studies for each enantiomer separately. Greenness profile assessment of the different elution solvents was carried out using the AGREE metric approach.
Project description:An unprecedentedly high degree of chiral amplification of supramolecular helices in a sergeants and soldiers system was realized using a propeller-shaped molecule, triphenylamine (TPA), as the monomer. One sergeant controlled the handedness of 500 soldiers in supramolecular helices. We further demonstrated that a TPA derivative could switch its role from sergeant to soldier and vice versa depending on its partners. These achievements could be realized using the dynamic propeller conformation of TPA and provide new insights into supramolecular assemblies and the supramolecular chiral amplification of helices.
Project description:Separation of the enantiomers of new chiral alkynes in strategic syntheses and bioorthogonal studies is always problematic. The chiral column high-performance liquid chromatography (HPLC) method in general could not be directly used to resolve such substrates, since the differentiation of the alkyne segment with the other alkane/alkene segment is not significant in the stationary phase, and the alkyne group is not a good UV chromophore. Usually, a pre-column derivatization reaction with a tedious workup procedure is needed. Making use of easily-prepared stable alkyne-cobalt-complexes, we developed a simple and general method by analyzing the in situ generated cobalt-complex of chiral alkynes using chiral column HPLC. This new method is especially suitable for the alkynes without chromophores and other derivable groups.
Project description:Chiral separations of five β-adrenergic antagonists (propranolol, esmolol, atenolol, metoprolol, and bisoprolol) were studied by capillary electrophoresis using six cyclodextrins (CDs) as the chiral selectors. Carboxymethylated-β-cyclodextrin (CM-β-CD) exhibited a higher enantioselectivity power compared to the other tested CDs. The influences of the concentration of CM-β-CD, buffer pH, buffer concentration, temperature, and applied voltage were investigated. The good chiral separation of five β-adrenergic antagonists was achieved using 50 mM Tris buffer at pH 4.0 containing 8 mM CM-β-CD with an applied voltage of 24 kV at 20 °C. In order to understand possible chiral recognition mechanisms of these racemates with CM-β-CD, host-guest binding procedures of CM-β-CD and these racemates were studied using the molecular docking software Autodock. The binding free energy was calculated using the Autodock semi-empirical binding free energy function. The results showed that the phenyl or naphthyl ring inserted in the hydrophobic cavity of CM-β-CD and the side chain was found to point out of the cyclodextrin rim. Hydrogen bonding between CM-β-CD and these racemates played an important role in the process of enantionseparation and a model of the hydrogen bonding interaction positions was constructed. The difference in hydrogen bonding formed with the -OH next to the chiral center of the analytes may help to increase chiral discrimination and gave rise to a bigger separation factor. In addition, the longer side chain in the hydrophobic phenyl ring of the enantiomer was not beneficial for enantioseparation and the chiral selectivity factor was found to correspond to the difference in binding free energy.