Field-Effect Chiral Anomaly Devices with Dirac Semimetal

Charge-based field-effect transistors (FETs) greatly suffer from unavoidable carrier scattering and heat dissipation. Analogous to valley degree of freedom in semiconductors, chiral anomaly current in Weyl/Dirac semimetals is theoretically predicted to be nearly nondissipative over long distances, but still lacks experimental ways to efficiently control its transport. Here, field-effect chirality devices are demonstrated with Dirac semimetal PtSe₂, in which its Fermi level is close to the Dirac point in the conduction band owing to intrinsic defects. The chiral anomaly is further corroborated by the planar Hall effect and nonlocal valley transport measurement, which can also be effectively modulated by external fields, showing robust nonlocal valley transport with micrometer diffusion length. Similar to charge-based FETs, the chiral conductivity in PtSe₂ devices can be modulated by electrostatic gating with an ON/OFF ratio of more than 10³. Basic logic functions in the devices are also demonstrated with electric and magnetic fields as input signals.     

Charge Transportation and Chirality in Liquid Crystalline Helical Network Phases of Achiral BTBT-Derived Polycatenar Molecules

First examples of multichain (polycatenar) compounds, based on the π-conjugated [1]benzothieno[3,2-b]benzothiophene unit are designed, synthesized, and their soft self-assembly and charge carrier mobility are investigated. These compounds, terminated by the new fan-shaped 2-brominated 3,4,5-trialkoxybenzoate moiety, form bicontinuous cubic liquid crystalline (LC) phases with helical network structure over extremely wide temperature ranges (>200 K), including ambient temperature. Compounds with short chains show an achiral cubic phase with the double network, which upon increasing the chain length, is at first replaced by a tetragonal 3D phase and then by a mirror symmetry is broken triple network cubic phase. In the networks, the capability of bypassing defects provides enhanced charge carrier mobility compared to imperfectly aligned columnar phases, and the charge transportation is non-dispersive, as only rarely observed for LC materials. At the transition to a semicrystalline helical network phase, the conductivity is further enhanced by almost one order of magnitude. In addition, a mirror symmetry broken isotropic liquid phase is formed beside the 3D phases, which upon chain elongation is removed and replaced by a hexagonal columnar LC phase.     

Chirality‐Based Biosensors

The fabrication of chiral nanostructures gives rise to characteristic chiroptical activity, which can be used for chirality‐based biosensors. Great progress is made in the use of nanoassemblies for the construction of chiral nanoparticle dimers, pyramids, helices, and twisted structures, and their chiroptical activities correlate with diverse structural geometries and enantiomeric configurations. In DNA‐hybridization‐based chiral nanoassemblies, the assembly parameters, such as the components, gaps, multicomponents, and the aftergrowth of metal, can result in multiple bands and enhanced chiroptical effects. Based on known chiral nanostructures, the existing chiral nanoassembly‐based biosensors together with their targets and signal amplification strategies are reviewed. Chirality involves multiple signals, and multitarget biosensors are introduced with newly developed chiral architectures for the accurate and reliable monitoring of biomarkers in living cells. The interactions between chiral nanoarchitectures and biosystems are also highlighted, which are important not only in the chiral dynamic switching of nano‐objects for biomonitoring, but also in manipulating cell growth, proliferation, and adhesion. The future perspectives on chiral fabrication and its use in biosensors are also comprehensively discussed.     

Understanding the Self-Assembly of Cellulose Nanocrystals—Toward Chiral Photonic Materials

Over millions of years, animals and plants have evolved complex molecules and structures that endow them with vibrant colors. Among the sources of natural coloration, structural color is prominent in insects, bird feathers, snake skin, plants, and other organisms, where the color arises from the interaction of light with nanoscale features rather than absorption from a pigment. Cellulose nanocrystals (CNCs) are a biorenewable resource that spontaneously organize into chiral nematic liquid crystals having a hierarchical structure that resembles the Bouligand structure of arthropod shells. The periodic, chiral nematic organization of CNC films leads them to diffract light, making them appear iridescent. Over the past two decades, there have been many advances to develop the photonic properties of CNCs for applications ranging from cosmetics to sensors. Here, the origin of color in CNCs, the control of photonic properties of CNC films, the development of new composite materials of CNCs that can yield flexible photonic structures, and the future challenges in this field are discussed. In particular, recent efforts to make flexible photonic materials using CNCs are highlighted.     

Supramolecular Chiral Aggregates Exhibiting Nonlinear CD–ee Dependence

Although a linear relationship between the optical activity (normally the CD signal) and the enantiomeric excess (ee) of chiral auxiliaries has been the most commonly observed dependence in dynamic supramolecular helical aggregates, positive nonlinear CD–ee dependence, known as the “majority-rules effect” (MRE), indicative of chiral amplification, has also been well documented and to some extent understood. In sharp contrast, the negative nonlinear CD–ee dependence has been much less reported and is not well understood. Here, the state of the art of both the positive and negative nonlinear CD–ee dependence in noncovalently bound supramolecular helical aggregates is summarized, with the hope that the vast examples of supramolecular aggregates showing positive nonlinear dependence, in terms of the methods of investigations, variations in the structure of the building block (single species or multiple species), and theoretical modeling using the mismatch penalty energy and helix reversal penalty energy, would help to guide the design of building blocks to form aggregates showing negative nonlinear dependence, and thus to understand the mechanisms. The potential applications of those functional supramolecular aggregates are also discussed.     

Theoretical Prediction of Chiral 3D Hybrid Organic–Inorganic Perovskites

Hybrid organic–inorganic perovskites (HOIPs), in particular 3D HOIPs, have demonstrated remarkable properties, including ultralong charge‐carrier diffusion lengths, high dielectric constants, low trap densities, tunable absorption and emission wavelengths, strong spin–orbit coupling, and large Rashba splitting. These superior properties have generated intensive research interest in HOIPs for high‐performance optoelectronics and spintronics. Here, 3D hybrid organic–inorganic perovskites that implant chirality through introducing the chiral methylammonium cation are demonstrated. Based on structural optimization, phonon spectra, formation energy, and ab initio molecular dynamics simulations, it is found that the chirality of the chiral cations can be successfully transferred to the framework of 3D HOIPs, and the resulting 3D chiral HOIPs are both kinetically and thermodynamically stable. Combining chirality with the impressive optical, electrical, and spintronic properties of 3D perovskites, 3D chiral perovskites is of great interest in the fields of piezoelectricity, pyroelectricity, ferroelectricity, topological quantum engineering, circularly polarized optoelectronics, and spintronics.     

Diporphyrin tweezer for multichannel spectroscopic analysis of enantiomeric excess

Chiral 1,1’-binaphthyl-linked diporphyrin ‘tweezers’ (R)-1/(S)-1 and the corresponding zinc(II) complexes (R)-2/(S)-2 were prepared as chiral host molecules, and their utility for chiral analyses (especially enantiomeric excess (ee) determinations) were evaluated. Tris(1-n-dodecyl)porphyrins were used for the first time as the interacting units. Host capabilities of the diporphyrin tweezers were investigated by titrations with (R,R)- and (S,S)-cyclohexane-1,2-diamine (CHDA). The host molecules could be used as multichannel probes of ee by using UV-vis, circular dichroism (CD), fluorescence emission and ¹H nuclear magnetic resonance (¹H-NMR) methods. Chiral configurations could also be differentiated using CD or ¹H-NMR spectroscopy. All three optical techniques give good resolution of ee with reasonable sensitivity considering the low concentrations used (ca. 10⁻⁶ mol·L⁻¹). The ee determination of CHDA enantiomers using NMR spectroscopy is also possible because of the reasonably well separated resonances in the case of (R,R)- and (S,S)-CHDA. Non-metallated (R)-1/(S)-1 hosts could not be used to detect chiral information in a strongly acidic chiral guest. This work demonstrates the utility of 1,1’-binapthyl-linked chiral hosts for chiral analysis of ditopically interacting enantiomers.     

Textile‐surface interfacial asymmetric polymerization

This research demonstrated that polymerization of aniline on cellulose produces chiroptically active composites. Polymerization of aniline in the presence of cotton fibers consisting of chiral cellulose are performed to prepare a polyaniline (PANI)/cotton composite. The polymerization is conducted at the cotton interface. The resultant PANI/cotton composite shows chiroptical activity elucidated with diffuse reflectance circular dichroism. In this reaction, textile‐surface interfacial asymmetric polymerization is performed with imprinting of chiral structure from the cotton as a natural chiroptically active polymer to the PANI. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41118.     

Efficient and Scalable Kinetic Resolution of Racemic 4‐Formyl[2.2]paracyclophane via Asymmetric Transfer Hydrogenation

Herein we wish to report a new non‐enzymatic kinetic resolution of racemic 4‐formyl[2.2]paracyclophane based on Noyori asymmetric transfer hydrogenations (KR‐ATH). Our approach, which provides an efficient access to enantiopure (R_p)‐ and (S_p)‐4‐formyl[2.2]paracyclophane (>99% ee, 39% and 41% isolated yields, respectively), is operationally simple and can be run on the gram‐scale thus confirming the practical applicability of this method.

     

Planar‐Chiral Cyclopentadienyl‐Ruthenium‐Catalyzed Regio‐ and Enantioselective Asymmetric Allylic Alkylation of Silyl Enolates under Unusually Mild Conditions

We report the asymmetric allylic alkylation of allylic chlorides with silyl enolates as a carbon nucleophile using a planar‐chiral cyclopentadienyl‐ruthenium (Cp′Ru) catalyst. The reaction proceeds under unusually mild conditions to give the desired branched products with complete regioselectivity and high enantioselectivity, and reactive functional groups, such as aldehyde, can be tolerated. In this reaction system, Cp′Ru plays an important role in activating both silyl enolate and allylic chloride.