Chiral Switch Research Articles

Solvent-Induced Chirality Switching in the Enantioseparation of Halogen-Substituted Mandelic Acids: Structural Effects on Molecular Packing

The solvent effect on the enantioseparation of halogen-substituted mandelic acid derivatives via diastereomeric salt formation has been investigated. The diastereomeric salts of para-halogen-substi...

The Tripeptide RER Mimics Secreted Amyloid Precursor Protein-Alpha in Upregulating LTP.

Secreted amyloid precursor protein-alpha (sAPPα), generated by enzymatic processing of the APP, possesses a range of neurotrophic and neuroprotective properties and plays a critical role in the molecular mechanisms of memory and learning. One of the key active regions of sAPPα is the central APP domain (E2) that contains within it the tripeptide sequence, RER. This sequence is exposed on the surface of a coiled coil substructure of E2. RER has by itself displayed memory-enhancing properties, and can protect newly formed engrams from interference in a manner similar to that displayed by sAPPα itself. In order to determine whether RER mimics other properties of sAPPα, we investigated the electrophysiological effects of the N-terminal protected acetylated RER (Ac-RER) and an isoform containing a chiral switch in the first amino acid from an l- to a d-orientation (Ac-rER), on synaptic plasticity. We found that, like sAPPα, exogenous perfusion with nanomolar concentrations of Ac-RER or Ac-rER enhanced the induction and stability of long-term potentiation (LTP) in area CA1 of rat and mouse hippocampal slices, in a protein synthesis- and trafficking-dependent manner. This effect did not occur with a control Ac-AAA or Ac-IFR tripeptide, nor with a full-length sAPPα protein where RER was substituted with AAA. Ac-rER also protected LTP against amyloid-beta (Aβ25–35)-induced LTP impairment. Our findings provide further evidence that the RER-containing region of sAPPα is functionally significant and by itself can produce effects similar to those displayed by full length sAPPα, suggesting that this tripeptide, like sAPPα, may have therapeutic potential.

In situ control of radial vortex polarity at room temperature utilizing perpendicular magnetic field pulse

In this paper, the in situ control of radial vortex polarity and chirality at room temperature mediated by perpendicular magnetic field pulse has been reported via micromagnetic simulations. The correlative results show that the polarity and chirality are switched simultaneously without resulting in a large core movement, the simulation built-in magnetic force microscopy provides a deeply insight into the evolution of magnetic configuration during the reversal process. The reversal mechanism reported in this work differs from the reported vortex-antivortex pair creation and annihilation mechanisms, which is useful for bit reading and probing in magnetic data storage devices. Meanwhile, the thermal perturbations at nonzero temperatures will weaken the effect of magnetic field, so the threshold field strength need increase with the elevated temperature to guarantee chirality and polarity reversed completely. This approach presents an alternative efficient means to achieve an ultrafast radial vortex chirality and polarity switching, which paves the way for the practical application of magnetoresistive memory based on radial vortex.

1,2-Dithienyldicyanoethene-Based, Visible-Light-Driven, Chiral Fluorescent Molecular Switch: Rewritable Multimodal Photonic Devices.

Reported here is the first example of a 1,2-dithienyldicyanoethene-based visible-light-driven chiral fluorescent molecular switch that exhibits reversible trans to cis photoisomerization. The trans form in solution almost completely transforms into the cis form, accompanied by a 10-fold decrease in its fluorescence intensity within 60 seconds when exposed to green light (520 nm). The reverse isomerization proceeds upon irradiation with blue light (405 nm). When doped into commercially available achiral liquid crystal hosts, this molecular switch efficiently induces luminescent helical superstructures, that is, a cholesteric phase. The intensity of the circularly polarized fluorescence as well as the selective reflection wavelength of the induced cholesteric phases can be reversibly tuned using visible light of two different wavelengths. Optically rewritable photonic devices using cholesteric films containing this molecular switch are described.

1,2‐Dithienyldicyanoethene‐Based, Visible‐Light‐Driven, Chiral Fluorescent Molecular Switch: Rewritable Multimodal Photonic Devices

AbstractReported here is the first example of a 1,2‐dithienyldicyanoethene‐based visible‐light‐driven chiral fluorescent molecular switch that exhibits reversible trans to cis photoisomerization. The trans form in solution almost completely transforms into the cis form, accompanied by a 10‐fold decrease in its fluorescence intensity within 60 seconds when exposed to green light (520 nm). The reverse isomerization proceeds upon irradiation with blue light (405 nm). When doped into commercially available achiral liquid crystal hosts, this molecular switch efficiently induces luminescent helical superstructures, that is, a cholesteric phase. The intensity of the circularly polarized fluorescence as well as the selective reflection wavelength of the induced cholesteric phases can be reversibly tuned using visible light of two different wavelengths. Optically rewritable photonic devices using cholesteric films containing this molecular switch are described.

Switching of Skyrmion chirality by local heating

Magnetic Skyrmions are energetically stable entities formed in a ferromagnet with a diameter of typically below 100 nm and are easily displaceable using an electrical current of 102 A/cm2, resulting the Skyrmions to be more advantageous than domain walls for spintronic memory applications. Here, we demonstrated switching of a chirality of magnetic Skyrmions formed in magnetic thin films by introducing a pulsed heat spot using micromagnetic simulation. Skyrmions are found to expand with a pulsed heat spot, which induces the magnetic moments surrounding the Skyrmion to rotate by this expansion, followed by the chirality switching of the Skyrmion. Such simple controllability can be used as a fundamental building block for memory and logic devices using the chirality of Skyrmions as a data bit.

Spin-orbit coupling controlled near-field propagation and focusing of Bloch surface wave.

Bloch surface wave (BSW) can be considered as the dielectric analogue of surface plasmon polariton (SPP) with less loss since it is sustained at the surface of a truncated dielectric multilayer. As dielectric materials show nearly no ohmic loss, BSW can propagates much farther compared to SPP, and thus is beneficial for planar optical devices. In this paper, we study the spin-orbital interaction between incident beam and BSW. We demonstrate that due to the spin-orbital coupling, the near-field properties of generated BSW can be controlled with a meta-antenna structure. The meta-antenna is composed of two gold nano-antennas oriented at 45° and 135° as a near-field coupler. By careful design of the meta-antenna, the generated BSW can be guided and focused depending on the chirality of the incident beam. Three examples of meta-antennas are demonstrated for chiral sensitive focusing, directional switching and asymmetric focusing. The proposed method can be applied as a design method for low-loss on-chip photonic devices.

Precise Manipulation of Temperature-Driven Chirality Switching of Molecular Universal Joints through Solvent Mixing.

Three chiral bicyclic pillar[5]arene derivatives termed as molecular universal joints (MUJs), were synthesized and separated enantiomerically. These MUJs showed temperature-driven chirality switching in certain solvents. Herein, it is demonstrated that temperature-driven chirality switching could also be realized by mixing two miscible organic solvents, in each of which chirality inversion is not accomplishable. Additionally, solvent mixing drastically varied the inversion temperature of the MUJs, for example, from far below zero to room temperature. Moreover, the temperature-driven Sp /Rp to Rp /Sp chirality switching direction could be reversed by the solvent mixing and it was critically controlled by the mixing ratios of the two solvents. These observations allowed precise manipulation of the chirality switching behavior of the MUJs. Such a chirality switching was ascribed to the influences of solvent and temperature on the in-out equilibrium of the side rings, which is delicately controlled by several processes, including the solvation/desolvation and the inclusion/exclusion of the side rings and solvent molecules. Crucially, the solvent mixing introduced new supramolecular processes, in particular the desolvation of solvent molecules from the mixed solvent system and the solvation of the side ring by the mixed solvent, which significantly disturbed the original in-out equilibrium of MUJs and drastically switched the entropy and enthalpy changes of conformational interconversion.

Precise Manipulation of Temperature‐Driven Chirality Switching of Molecular Universal Joints through Solvent Mixing

AbstractInvited for the cover of this issue is Cheng Yang and co‐workers at Sichuan University. The image depicts solvent mixing as a precise, but powerful and pervasive method for manipulating the temperature‐driven chirality switching behavior of molecular universal joints. Read the full text of the article at 10.1002/chem.201902676.

Front Cover: Precise Manipulation of Temperature‐Driven Chirality Switching of Molecular Universal Joints through Solvent Mixing (Chem. Eur. J. 54/2019)

Front Cover: Precise Manipulation of Temperature‐Driven Chirality Switching of Molecular Universal Joints through Solvent Mixing (Chem. Eur. J. 54/2019)

Polyketides and a Dihydroquinolone Alkaloid from a Marine-Derived Strain of the Fungus Metarhizium marquandii.

Three new natural products (1-3), including two butenolide derivatives (1 and 2) and one dihydroquinolone derivative (3), together with nine known natural products were isolated from a marine-derived strain of the fungus Metarhizium marquandii. The structures of the new compounds were unambiguously deduced by spectroscopic means including HRESIMS and 1D/2D NMR spectroscopy, ECD, VCD, OR measurements, and calculations. The absolute configuration of marqualide (1) was determined by a combination of modified Mosher's method with TDDFT-ECD calculations at different levels, which revealed the importance of intramolecular hydrogen bonding in determining the ECD features. The (3R,4R) absolute configuration of aflaquinolone I (3), determined by OR, ECD, and VCD calculations, was found to be opposite of the (3S,4S) absolute configuration of the related aflaquinolones A-G, suggesting that the fungus M. marquandii produces aflaquinolone I with a different configuration (chiral switching). The absolute configuration of the known natural product terrestric acid hydrate (4) was likewise determined for the first time in this study. TDDFT-ECD calculations allowed determination of the absolute configuration of its chirality center remote from the stereogenic unsaturated γ-lactone chromophore. ECD calculations aided by solvent models revealed the importance of intramolecular hydrogen bond networks in stabilizing conformers and determining relationships between ECD transitions and absolute configurations.

Visible-Light-Induced Self-Organized Helical Superstructure in Orientationally Ordered Fluids.

Light-induced phenomena occurring in nature and in synthetic materials are fascinating and have been exploited for technological applications. Here visible-light-induced formation of a helical superstructure is reported, i.e., a cholesteric liquid crystal phase, in orientationally ordered fluids, i.e., nematic liquid crystals, enabled by a visible-light-driven chiral molecular switch. The cyclic-azobenzene-based chiral molecular switch exhibits reversible photoisomerization in response to visible light of different wavelengths due to the band separation of n-π* transitions of its trans- and cis-isomers. Green light (530 nm) drives the trans-to-cis photoisomerization whereas the cis-to-trans isomerization process of the chiral molecular switch can be caused by blue light (440 nm). It is observed that the helical twisting power of this chiral molecular switch increases upon irradiation with green light, which enables reversible induction of helical superstructure in nematic liquid crystals containing a very small quantity of the molecular switch. The occurrence of the light-induced helical superstructure enables the formation of diffraction gratings in cholesteric films.

A Primer of Deuterium in Drug Design

A Primer of Deuterium in Drug Design

Steric Dependence of Chirality Effect in Surface-Mediated Peptide Assemblies Identified with Scanning Tunneling Microscopy

Amino acid chirality has been recognized as an important driving force in constructing peptide architectures, via interactions such as chirality-induced stereochemical effect. The introduction of site-specific chiral conversion of l- and d-amino acids in peptide sequences could enable the pursuit of the chirality effects in peptide assembly. In this work, we characterized the assemblies of heptapeptides with various side chain moieties and their chiral variants using STM. Specifically, two pairs of amino acids, Gln (Q) and Asn (N), Glu (E) and Asp (D), having one methylene difference in their side chains, are selected to elucidate the steric dependence of amino acid chiral effects on surface-bound peptide assemblies. The observed heptapeptide assembly structures reveal that chirality switching of a single amino acid is able to destabilize the surface-mediated peptide assemblies, and this disturbance effect can be positively correlated with the steric hindrance of amino acid side chains. Furthermore, the strength of the impact due to chiral conversion on heptapeptide assembly structure is noticeably dependent on the mutation sites, indicative of structural heterogeneity of chiral effects. These results could contribute to the molecular insights of chirality-induced stereochemical interactions in peptide assembly.

Magnesium for Dynamic Nanoplasmonics.

ConspectusThe key component of nanoplasmonics is metals. For a long time, gold and silver have been the metals of choice for constructing plasmonic nanodevices because of their excellent optical properties. However, these metals possess a common characteristic, i.e., their optical responses are static. The past decade has been witnessed tremendous interest in dynamic control of the optical properties of plasmonic nanostructures. To enable dynamic functionality, several approaches have been proposed and implemented. For instance, plasmonic nanostructures can be fabricated on stretchable substrates or on programmable templates so that the interactions between the constituent metal nanoparticles and therefore the optical responses of the plasmonic systems can be dynamically changed. Also, plasmonic nanostructures can be embedded in tunable dielectric materials, taking advantage of the sensitive dependence of the localized surface plasmon resonances on the neighboring environment. Another approach, which is probably the most intriguing one, is to directly regulate the carrier densities and dielectric functions of the metals themselves.In this Account, we discuss a relatively new metal in nanoplasmonics, magnesium, and its important role in the development of dynamic plasmonic nanodevices at visible frequencies. We first elucidate the basic optical properties of Mg and compare it with conventional plasmonic materials such as Au, Ag, and others. Then we describe a unique characteristic of Mg, i.e., its reversible phase transitions between the metallic state and a dielectric state, magnesium hydride, through hydrogenation and dehydrogenation. This sets the basis for Mg in dynamic nanoplasmonics. In particular, the structural properties and dielectric functions of the two distinct states are discussed in detail. Subsequently, we highlight the experimental investigations of the physical mechanisms and nanoscale understanding of Mg nanoparticles during hydrogenation and dehydrogenation. We then introduce a plethora of newly developed Mg-based dynamic optical nanodevices for applications in plasmonic chirality switching, dynamic color displays with Mg nanoparticles and films, and dynamic metasurfaces for ultrathin and flat optical elements. We also outline strategies to enhance the stability, reversibility, and durability of Mg-based nanodevices. Finally, we end this Account by outlining the remaining challenges, possible solutions, and promising applications in the field of Mg-based dynamic nanoplasmonics. We envision that Mg-based dynamic nanoplasmonics will not only provide insights into understanding the catalytic processes of hydrogen diffusion in metals by optical means but also will open an avenue toward functional plasmonic nanodevices with tailored optical properties for real-world applications.

Light-driven molecular switch for reconfigurable spin filters

Artificial molecular switches and machines that enable the directional movements of molecular components by external stimuli have undergone rapid advances over the past several decades. Particularly, overcrowded alkene-based artificial molecular motors are highly attractive from the viewpoint of chirality switching during rotational steps. However, the integration of these molecular switches into solid-state devices is still challenging. Herein, we present an example of a solid-state spin-filtering device that can switch the spin polarization direction by light irradiation or thermal treatment. This device utilizes the chirality inversion of molecular motors as a light-driven reconfigurable spin filter owing to the chiral-induced spin selectivity effect. Through this device, we found that the flexibility at the molecular scale is essential for the electrodes in solid-state devices using molecular machines. The present results are beneficial to the development of solid-state functionalities emerging from nanosized motions of molecular switches.

Tunable circular dichroism of bilayer b-type chiral nanostructures

Circular dichroism (CD) of chiral molecules are key to medicine detection, optoelectronic devices and chiral biosensors. However, the CD effects of natural chiral molecules are weak that prevents their wide applications. Chiral plasmonic nanostructures have been demonstrated as an effective way to enhance CD effects of natural molecules due to the localized enhanced electromagnetic field and the high contrast in chiroptical response to left- and right-handed circular polarized light. Here we proposed a 3D plasmonic chiral platform consisting of bilayer b-shape nanoelements and investigated their tunable CD effects through rotating the upper layer b-elements. Near-field analysis based on Born–Kuhn model had been proposed to explain the mechanism of the tunable CD effects. Results demonstrated that a maximum CD signal was achieved with the 3D chiral nanostructure supporting bonding and antibonding plasmonic modes under left- and right-handed circular polarized light, respectively. While the smallest CD was for the nanostructure only supporting one mode (antibonding mode) under circular polarized light. The tunable CD effects of the bilayer b-type nanostructures is beneficial for chiral optical switches and high-sensitivity chiral biosensors.

Reversible Circularly Polarized Reflection in a Self-Organized Helical Superstructure Enabled by a Visible-Light-Driven Axially Chiral Molecular Switch.

Development of light-driven functional materials capable of displaying reversible properties is currently a vibrant frontier from both scientific and technological points of view. Here a new visible-light-driven chiral molecular switch is synthesized and characterized. To the best of our knowledge, this is the first example of a chiral molecular switch in which the visible-light-driven azobenzene motif is directly linked to an axially chiral scaffold through a C-C bond. The chiral molecular switch exhibits trans-to- cis photoisomerization upon 530 nm irradiation and cis-to- trans isomerization upon 450 nm irradiation. The switch can thus be photoisomerized in both directions using visible light of different wavelengths, a promising attribute for device applications. It was found that this relatively rigid molecular switch exhibited a high helical twisting power (HTP) in liquid crystal hosts and a large change of HTP value upon photoisomerization. We achieved dynamic reflection tuning across the visible spectrum through incorporation into a self-organized helical superstructure, i.e., a cholesteric liquid crystal. We also demonstrated patterned photodisplays reflecting red, green, and blue circularly polarized light using these cholesteric films. Phototunable color displays were fabricated by selective light irradiation where the information can be reversibly hidden by applying an electric field and restored by applying either a mechanical force or an electric field of higher voltage.

Deterministic Switching of Polarization Vortices in Compositionally Graded Ferroelectrics Using a Mechanical Field

Practical control of polarization vortices in ferroelectric nanostructures could plays an important role in next-generation nanoscale electronic devices. However, switching vortex polarization is quite challenging, never mind via mechanical methods. This study identifies deterministic switching of vortex chirality in a compositionally graded ferroelectric nanoplate under compressive stress, using phase-field simulations and ferroelectric instability analysis. In addition, the underlying mechanism for such vortex control is explored. These results are tantalizing for nonvolatile memory and oxide electronics.

Separated Edge-Soliton-Mediated Dynamic Switching of Vortex Chirality and Polarity

Separated Edge-Soliton-Mediated Dynamic Switching of Vortex Chirality and Polarity