Pre-twisting for improved genome modification and miRNA targeting.

Two reports by Dhuri et al. and Oyaghire et al., respectively, show that, through installing chiral centers at the backbone of the artificial nucleic acid, peptide nucleic acid (PNA), enhanced miRNA targeting and genome modification can be achieved, with important implications in fighting cancers and ß-thalassemia.

Direct-write 3D printing of plasmonic nanohelicoids by circularly polarized light.

Chiral plasmonic surfaces with 3D "forests" from nanohelicoids should provide strong optical rotation due to alignment of helical axis with propagation vector of photons. However, such three-dimensional nanostructures also demand multi-step nanofabrication, which is incompatible with many substrates. Large-scale photonic patterns on polymeric and flexible substrates remain unattainable. Here, we demonstrate the substrate-tolerant direct-write printing and patterning of silver nanohelicoids with out-of-plane 3D orientation using circularly polarized light. Centimeter-scale chiral plasmonic surfaces can be produced within minutes using inexpensive medium-power lasers. The growth of nanohelicoids is driven by the symmetry-broken site-selective deposition and self-assembly of the silver nanoparticles (NPs). The ellipticity and wavelength of the incident photons control the local handedness and size of the printed nanohelicoids, which enables on-the-fly modulation of nanohelicoid chirality during direct writing and simple pathways to complex multifunctional metasurfaces. Processing simplicity, high polarization rotation, and fine spatial resolution of the light-driven printing of stand-up helicoids provide a rapid pathway to chiral plasmonic surfaces, accelerating the development of chiral photonics for health and information technologies.

Optical conductivity of the Majorana mode at the s- and d-wave topological superconductor edge.

The Majorana fermion offers fascinating possibilities such as non-Abelian statistics and nonlocal robust qubits, and hunting it is one of the most important topics in current condensed matter physics. Most of the efforts have been focused on the Majorana bound state at zero energy in terms of scanning tunneling spectroscopy searching for the quantized conductance. On the other hand, a chiral Majorana edge channel appears at the surface of a three-dimensional topological insulator when engineering an interface between proximity-induced superconductivity and ferromagnetism. Recent advances in microwave spectroscopy of topological edge states open a new avenue for observing signatures of such Majorana edge states through the local optical conductivity. As a guide to future experiments, we show how the local optical conductivity and density of states present distinct qualitative features depending on the symmetry of the superconductivity, that can be tuned via the magnetization and temperature. In particular, the presence of the Majorana edge state leads to a characteristic nonmonotonic temperature dependence achieved by tuning the magnetization.

Prebiotic access to enantioenriched amino acids via peptide-mediated transamination reactions.

The kinetic resolution of racemic amino acids mediated by dipeptides and pyridoxal provides a prebiotically plausible route to enantioenriched proteinogenic amino acids. The enzymatic transamination cycles that are key to modern biochemical formation of enantiopure amino acids may have evolved from this half of the reversible reaction couple. Kinetic resolution of racemic precursors emerges as a general route to enantioenrichment under prebiotic conditions.

Tapered chiral nanoparticles as broad-spectrum thermally stable antivirals for SARS-CoV-2 variants.

The incessant mutations of viruses, variable immune responses, and likely emergence of new viral threats necessitate multiple approaches to novel antiviral therapeutics. Furthermore, the new antiviral agents should have broad-spectrum activity and be environmentally stable. Here, we show that biocompatible tapered CuS nanoparticles (NPs) efficiently agglutinate coronaviruses with binding affinity dependent on the chirality of surface ligands and particle shape. L-penicillamine-stabilized NPs with left-handed curved apexes display half-maximal inhibitory concentrations (IC50) as low as 0.66 pM (1.4 ng/mL) and 0.57 pM (1.2 ng/mL) for pseudo-type SARS-CoV-2 viruses and wild-type Wuhan-1 SARS-CoV-2 viruses, respectively, which are about 1,100 times lower than those for antibodies (0.73 nM). Benefiting from strong NPs-protein interactions, the same particles are also effective against other strains of coronaviruses, such as HCoV-HKU1, HCoV-OC43, HCoV-NL63, and SARS-CoV-2 Omicron variants with IC50 values below 10 pM (21.8 ng/mL). Considering rapid response to outbreaks, exposure to elevated temperatures causes no change in the antiviral activity of NPs while antibodies are completely deactivated. Testing in mice indicates that the chirality-optimized NPs can serve as thermally stable analogs of antiviral biologics complementing the current spectrum of treatments.

Nonreciprocity and odd viscosity in chiral active fluids.

Odd viscosity couples stress to strain rate in a dissipationless way. It has been studied in plasmas under magnetic fields, superfluid [Formula: see text], quantum-Hall fluids, and recently in the context of chiral active matter. In most of these studies, odd terms in the viscosity obey Onsager reciprocal relations. Although this is expected in equilibrium systems, it is not obvious that Onsager relations hold in active materials. By directly coarse-graining the kinetic energy and independently using both the Poisson-bracket formalism and a kinetic theory derivation, we find that the appearance of a nonvanishing angular momentum density, which is a hallmark of chiral active materials, necessarily breaks Onsager reciprocal relations. This leads to a non-Hermitian dynamical matrix for the total hydrodynamic momentum and to the appearance of odd viscosity and other nondissipative contributions to the viscosity. Furthermore, by accounting for both the angular momentum density and interactions that lead to odd viscosity, we find regions in the parameter space in which 3D odd mechanical waves propagate and regions in which they are mechanically unstable. The lines separating these regions are continuous lines of exceptional points, suggesting a possible nonreciprocal phase transition.

Monopole-like orbital-momentum locking and the induced orbital transport in topological chiral semimetals.

The interplay between chirality and topology nurtures many exotic electronic properties. For instance, topological chiral semimetals display multifold chiral fermions that manifest nontrivial topological charge and spin texture. They are an ideal playground for exploring chirality-driven exotic physical phenomena. In this work, we reveal a monopole-like orbital-momentum locking texture on the three-dimensional Fermi surfaces of topological chiral semimetals with B20 structures (e.g., RhSi and PdGa). This orbital texture enables a large orbital Hall effect (OHE) and a giant orbital magnetoelectric (OME) effect in the presence of current flow. Different enantiomers exhibit the same OHE which can be converted to the spin Hall effect by spin-orbit coupling in materials. In contrast, the OME effect is chirality-dependent and much larger than its spin counterpart. Our work reveals the crucial role of orbital texture for understanding OHE and OME effects in topological chiral semimetals and paves the path for applications in orbitronics, spintronics, and enantiomer recognition.

3D printing of responsive chiral photonic nanostructures.

Finely controlled flow forces in extrusion-based additive manufacturing can be exploited to program the self-assembly of malleable nanostructures in soft materials by integrating bottom-up design into a top-down processing approach. Here, we leverage the processing parameters offered by direct ink-writing (DIW) to reconfigure the photonic chiral nematic liquid crystalline phase in hydroxypropyl cellulose (HPC) solutions prior to deposition on the writing substrate to direct structural evolution from a particular initial condition. Moreover, we incorporate polyethylene glycol (PEG) into iridescent HPC inks to form a physically cross-linked network capable of inducing kinetic arrest of the cholesteric/chiral pitch at length scales that selectively reflect light throughout the visible spectrum. Based on thorough rheological measurements, we have found that printing the chiral inks at a shear rate where HPC molecules adopt pseudonematic state results in uniform chiral recovery following flow cessation and enhanced optical properties in the solid state. Printing chiral inks at high shear rates, on the other hand, shifts the monochromatic appearance of the extruded filaments to a highly angle-dependent state, suggesting a preferred orientation of the chiral domains. The optical response of these filaments when exposed to mechanical deformation can be used in the development of optical sensors.

Fusing 2D and 3D molecular graphs as unambiguous molecular descriptors for conformational and chiral stereoisomers.

The rapid progress of machine learning (ML) in predicting molecular properties enables high-precision predictions being routinely achieved. However, many ML models, such as conventional molecular graph, cannot differentiate stereoisomers of certain types, particularly conformational and chiral ones that share the same bonding connectivity but differ in spatial arrangement. Here, we designed a hybrid molecular graph network, Chemical Feature Fusion Network (CFFN), to address the issue by integrating planar and stereo information of molecules in an interweaved fashion. The three-dimensional (3D, i.e., stereo) modality guarantees precision and completeness by providing unabridged information, while the two-dimensional (2D, i.e., planar) modality brings in chemical intuitions as prior knowledge for guidance. The zipper-like arrangement of 2D and 3D information processing promotes cooperativity between them, and their synergy is the key to our model's success. Experiments on various molecules or conformational datasets including a special newly created chiral molecule dataset comprised of various configurations and conformations demonstrate the superior performance of CFFN. The advantage of CFFN is even more significant in datasets made of small samples. Ablation experiments confirm that fusing 2D and 3D molecular graphs as unambiguous molecular descriptors can not only effectively distinguish molecules and their conformations, but also achieve more accurate and robust prediction of quantum chemical properties.

Three-dimensional chiral morphodynamics of chemomechanical active shells.

Morphogenesis of active shells such as cells is a fundamental chemomechanical process that often exhibits three-dimensional (3D) large deformations and chemical pattern dynamics simultaneously. Here, we establish a chemomechanical active shell theory accounting for mechanical feedback and biochemical regulation to investigate the symmetry-breaking and 3D chiral morphodynamics emerging in the cell cortex. The active bending and stretching of the elastic shells are regulated by biochemical signals like actomyosin and RhoA, which, in turn, exert mechanical feedback on the biochemical events via deformation-dependent diffusion and inhibition. We show that active deformations can trigger chemomechanical bifurcations, yielding pulse spiral waves and global oscillations, which, with increasing mechanical feedback, give way to traveling or standing waves subsequently. Mechanical feedback is also found to contribute to stabilizing the polarity of emerging patterns, thus ensuring robust morphogenesis. Our results reproduce and unravel the experimentally observed solitary and multiple spiral patterns, which initiate asymmetric cleavage in Xenopus and starfish embryogenesis. This study underscores the crucial roles of mechanical feedback in cell development and also suggests a chemomechanical framework allowing for 3D large deformation and chemical signaling to explore complex morphogenesis in living shell-like structures.

Emergent elastic fields induced by topological phase transitions: Impact of molecular chirality and steric anisotropy.

SignificanceChirality, the property of an object that cannot be superimposed on its mirror image, plays an essential role in condensed matter, such as magnetic, electronic, and liquid crystal systems. Topological phases emerge in such chiral materials, wherein helical and vortex-like structures-called skyrmions-are observed. However, the role of elastic fields in these topological phases remains unexplored. Here, we construct a molecular model of two-dimensional crystals incorporating steric anisotropy and chiral interactions to elucidate this problem. The coupling between the elastic fields and phase transitions between uniform, helical, and half-skyrmion phases can be utilized to switch these topological phases by external forces. Our results provide a fundamental physical principle for designing topological materials using chiral molecular and colloidal crystals.

Odd viscosity-induced Hall-like transport of an active chiral fluid.

Broken time-reversal and parity symmetries in active spinner fluids imply a nondissipative "odd viscosity," engendering phenomena unattainable in traditional passive or active fluids. Here we show that the odd viscosity itself can lead to a Hall-like transport when the active chiral fluid flows through a quenched matrix of obstacles, reminiscent of the anomalous Hall effect. The Hall-like velocity depends significantly on the spinner activity and longitudinal flow due to the interplay between odd viscosity and spinner-obstacle collisions. Our findings underscore the importance of odd viscosity in active chiral matter and elucidate its essential role in the anomalous Hall-like effect.

Control of protein activity by photoinduced spin polarized charge reorganization.

Considerable electric fields are present within living cells, and the role of bioelectricity has been well established at the organismal level. Yet much remains to be learned about electric-field effects on protein function. Here, we use phototriggered charge injection from a site-specifically attached ruthenium photosensitizer to directly demonstrate the effect of dynamic charge redistribution within a protein. We find that binding of an antibody to phosphoglycerate kinase (PGK) is increased twofold under illumination. Remarkably, illumination is found to suppress the enzymatic activity of PGK by a factor as large as three. These responses are sensitive to the photosensitizer position on the protein. Surprisingly, left (but not right) circularly polarized light elicits these responses, indicating that the electrons involved in the observed dynamics are spin polarized, due to spin filtration by protein chiral structures. Our results directly establish the contribution of electrical polarization as an allosteric signal within proteins. Future experiments with phototriggered charge injection will allow delineation of charge rearrangement pathways within proteins and will further depict their effects on protein function.

Dimensional and Doping Engineering of Chiral Perovskites with Enhanced Spin Selectivity for Green Emissive Spin Light-Emitting Diodes.

Chiral perovskites play a pivotal role in spintronics and optoelectronic systems attributed to their chiral-induced spin selectivity (CISS) effect. Specifically, they allow for spin-polarized charge transport in spin light-emitting diodes (LEDs), yielding circularly polarized electroluminescence at room temperature without external magnetic fields. However, chiral lead bromide-based perovskites have yet to achieve high-performance green emissive spin-LEDs, owing to limited CISS effects and charge transport. Herein, we employ dimensional regulation and Sn2+-doping to optimize chiral bromide-based perovskite architecture for green emissive spin-LEDs. The optimized (PEA)x(S/R-PRDA)2-xSn0.1Pb0.9Br4 chiral perovskite film exhibits an enhanced CISS effect, higher hole mobility, and better energy level alignment with the emissive layer. These improvements allow us to fabricate green emissive spin-LEDs with an external quantum efficiency (EQE) of 5.7% and an asymmetry factor |gCP-EL| of 1.1 × 10-3. This work highlights the importance of tailored perovskite architectures and doping strategies in advancing spintronics for optoelectronic applications.

Unraveling the Origin of Reverse Plasmonic Circular Dichroism from Discrete Bichiral Au Nanoparticles.

Bichiral plasmonic nanoparticles exhibited intriguing geometry-dependent circular dichroism (CD) reversal; however, the crucial factor that dominates the plasmonic CD is still unclear. Combined with CD spectroscopy and theoretical multipole analysis, we demonstrate that plasmonic CD originates from the excitation of electric quadrupolar plasmons. Moreover, a comparative study of two distinct quadrupolar modes reveals the correlation between the sign of the CD and the local geometric handedness at the plasmonic hotspots, thereby establishing a structure-property relationship in bichiral nanoparticles. The reverse CD is attributed to the opposite directions of the wavelength shift of the two plasmon modes upon changing the particle geometry. By finely tuning the size of bichiral nanoparticles, we can further reveal that the dependence of plasmonic CD on the electric quadrupolar plasmons. Our work sheds light on the physical origin of plasmonic CD and provides important guidelines for the design of chiral plasmonic nanoparticles toward chirality-dependent applications.

Kink-Controlled Gold Nanoparticles for Electrochemical Glucose Oxidation.

Enzymes in nature efficiently catalyze chiral organic molecules by elaborately tuning the geometrical arrangement of atoms in the active site. However, enantioselective oxidation of organic molecules by heterogeneous electrocatalysts is challenging because of the difficulty in controlling the asymmetric structures of the active sites on the electrodes. Here, we show that the distribution of chiral kink atoms on high-index facets can be precisely manipulated even on single gold nanoparticles; and this enabled stereoselective oxidation of hydroxyl groups on various sugar molecules. We characterized the crystallographic orientation and the density of kink atoms and investigated their specific interactions with the glucose molecule due to the geometrical structure and surface electrostatic potential.

Universal Chiral-Plasmon-Induced Upward and Downward Transfer of Circular Dichroism to Achiral Molecules.

Electromagnetic chirality transfer represents an effective means of the nanoscale manipulation of optical chirality. While most of the previous reports have exclusively focused on the circular dichroism (CD) transfer from UV-responsive chiral molecules toward visible-resonant achiral colloidal nanoparticles, here we demonstrate a reverse process in which plasmonic chirality can be transferred to achiral molecules, either upward from visible to UV or downward from visible to near infrared (NIR). By hybridizing achiral UV- or NIR-responsive dye molecules with chiral metal nanoparticles in solution, we observe a chiral-plasmon-induced CD (CPICD) signal at the intrinsically achiral molecular absorption bands. Full-wave electromagnetic modeling reveals that both near-field Coulomb interaction and far-field radiative coupling contribute to the observed CPICD, indicating that the mechanism considered here is universal for different material systems and types of optical resonances. Our study provides a set of design guidelines for broadband nanophotonic chiral sensing from the UV to NIR spectral regime.

Polychromatic Dual-Mode Imaging with Structured Chiral Photonic Crystals.

Optical spatial differentiation is a typical operation of optical analog computing and can single out the edge to accelerate the subsequent image processing, but in some cases, overall information about the object needs to be presented synchronously. Here, we propose a multifunctional optical device based on structured chiral photonic crystals for the simultaneous realization of real-time dual-mode imaging. This optical differentiator is realized by self-organized large-birefringence cholesteric liquid crystals, which are photopatterned to encode with a special integrated geometric phase. Two highly spin-selective modes of second-order spatial differentiation and bright-field imaging are exhibited in the reflected and transmitted directions, respectively. Two-dimensional edges of both amplitude and phase objects have been efficiently enhanced in high contrast and the broadband spectrum. This work extends the ingenious building of hierarchical chiral nanostructures, enriches their applications in the emerging frontiers of optical computing, and boasts considerable potential in machine vision and microscopy.

Uncovering Maximum Chirality in Resonant Nanostructures.

Chiral nanostructures allow engineering of chiroptical responses; however, their design usually relies on empirical approaches and extensive numerical simulations. It remains unclear if a general strategy exists to enhance and maximize the intrinsic chirality of subwavelength photonic structures. Here, we suggest a microscopic theory and uncover the origin of strong chiral responses of resonant nanostructures. We reveal that the reactive helicity density is critically important for achieving maximum chirality at resonances. We demonstrate our general concept on the examples of planar photonic crystal slabs and metasurfaces, where out-of-plane mirror symmetry is broken by a bilayer design. Our findings provide a general recipe for designing photonic structures with maximum chirality, paving the way toward many applications, including chiral sensing, chiral emitters and detectors, and chiral quantum optics.

Chiral Separation of Copper Sulfide [S-Cu36] Nanocluster Using a Chiral Adaptive Counterion.

This work presents a new strategy to achieve the growth of copper sulfide nanoclusters with high nuclearity. Through a phosphine-assisted C-S reductive cleavage approach, an intrinsically chiral [Cu4] cluster passes through a [S-Cu9] cluster and transforms into a higher-nuclearity [S-Cu36] cluster, which features a core-shell structure with a [Cu4]4+ core encapsulated by a chiral [Cu20S12] shell. Interestingly, the spiral arrangement of the bidental ligands on the surface of the [S-Cu36] cluster leads to the L-/R-enantiomeric configurations. Moreover, by utilization of [Na(THF)6]+ as a chiral adaptive counterion, [S-Cu36] can be interlocked separately, thus enabling the isolation of homochiral clusters. Theoretical calculation suggests that the configuration transition between two enantiomeric [Na(THF)6]+ species is favorable at room temperature, thereby promoting the cocrystallization of resulting chiral products. This study introduces a novel perspective on the synthesis of chiral copper sulfide nanoclusters and presents an innovative approach to achieving the chiral separation of nanoclusters.