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10,287 result(s) for "Dichroism"
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Accurate secondary structure prediction and fold recognition for circular dichroism spectroscopy
Circular dichroism (CD) spectroscopy is a widely used technique for the study of protein structure. Numerous algorithms have been developed for the estimation of the secondary structure composition from the CD spectra. These methods often fail to provide acceptable results on α/β-mixed or β-structure–rich proteins. The problem arises from the spectral diversity of β-structures, which has hitherto been considered as an intrinsic limitation of the technique. The predictions are less reliable for proteins of unusual β-structures such as membrane proteins, protein aggregates, and amyloid fibrils. Here, we show that the parallel/antiparallel orientation and the twisting of the β-sheets account for the observed spectral diversity. We have developed a method called β-structure selection (BeStSel) for the secondary structure estimation that takes into account the twist of β-structures. This method can reliably distinguish parallel and antiparallel β-sheets and accurately estimates the secondary structure for a broad range of proteins. Moreover, the secondary structure components applied by the method are characteristic to the protein fold, and thus the fold can be predicted to the level of topology in the CATH classification from a single CD spectrum. By constructing a web server, we offer a general tool for a quick and reliable structure analysis using conventional CD or synchrotron radiation CD (SRCD) spectroscopy for the protein science research community. The method is especially useful when X-ray or NMR techniques fail. Using BeStSel on data collected by SRCD spectroscopy, we investigated the structure of amyloid fibrils of various disease-related proteins and peptides. Significance Circular dichroism (CD) spectroscopy is widely used for protein secondary structure analysis. However, quantitative estimation for β-sheet–containing proteins is problematic due to the huge morphological and spectral diversity of β-structures. We show that parallel/antiparallel orientation and twisting of β-sheets account for the observed spectral diversity. Taking into account the twist of β-structures, our method accurately estimates the secondary structure for a broad range of protein folds, particularly for β-sheet–rich proteins and amyloid fibrils. Moreover, the method can predict the protein fold down to the topology level following the CATH classification. We provide a general tool for a quick and reliable structure analysis using conventional or synchrotron radiation CD spectroscopy, which is especially useful when X-ray or NMR techniques fail.
Polarization spectroscopy methods in the determination of interactions of small molecules with nucleic acids – tutorial
The structural characterization of non-covalent complexes between nucleic acids and small molecules (ligands) is of a paramount significance to bioorganic research. Highly informative methods about nucleic acid/ligand complexes such as single crystal X-ray diffraction or NMR spectroscopy cannot be performed under biologically compatible conditions and are extensively time consuming. Therefore, in search for faster methods which can be applied to conditions that are at least similar to the naturally occurring ones, a set of polarization spectroscopy methods has shown highly promising results. Electronic circular dichroism (ECD) is the most commonly used method for the characterization of the helical structure of DNA and RNA and their complexes with ligands. Less common but complementary to ECD, is flow-oriented linear dichroism (LD). Other methods such as vibrational CD (VCD) and emission-based methods (FDCD, CPL), can also be used for suitable samples. Despite the popularity of polarization spectroscopy in biophysics, aside several highly focused reviews on the application of these methods to DNA/RNA research, there is no systematic tutorial covering all mentioned methods as a tool for the characterization of adducts between nucleic acids and small ligands. This tutorial aims to help researchers entering the research field to organize experiments accurately and to interpret the obtained data reliably.
Observation of intrinsic chiral bound states in the continuum
Photons with spin angular momentum possess intrinsic chirality, which underpins many phenomena including nonlinear optics 1 , quantum optics 2 , topological photonics 3 and chiroptics 4 . Intrinsic chirality is weak in natural materials, and recent theoretical proposals 5 – 7 aimed to enlarge circular dichroism by resonant metasurfaces supporting bound states in the continuum that enhance substantially chiral light–matter interactions. Those insightful works resort to three-dimensional sophisticated geometries, which are too challenging to be realized for optical frequencies 8 . Therefore, most of the experimental attempts 9 – 11 showing strong circular dichroism rely on false/extrinsic chirality by using either oblique incidence 9 , 10 or structural anisotropy 11 . Here we report on the experimental realization of true/intrinsic chiral response with resonant metasurfaces in which the engineered slant geometry breaks both in-plane and out-of-plane symmetries. Our result marks, to our knowledge, the first observation of intrinsic chiral bound states in the continuum with near-unity circular dichroism of 0.93 and a high quality factor exceeding 2,663 for visible frequencies. Our chiral metasurfaces may lead to a plethora of applications in chiral light sources and detectors, chiral sensing, valleytronics and asymmetric photocatalysis. Chiral metasurfaces have been produced, with experimental observation of intrinsic chiral bound states in the continuum, which may lead to applications in chiral light sources and detectors, chiral sensing, valleytronics and asymmetric photocatalysis.
Signatures of fractional quantum anomalous Hall states in twisted MoTe2
The interplay between spontaneous symmetry breaking and topology can result in exotic quantum states of matter. A celebrated example is the quantum anomalous Hall (QAH) state, which exhibits an integer quantum Hall effect at zero magnetic field owing to intrinsic ferromagnetism 1 – 3 . In the presence of strong electron–electron interactions, fractional QAH (FQAH) states at zero magnetic field can emerge 4 – 8 . These states could host fractional excitations, including non-Abelian anyons—crucial building blocks for topological quantum computation 9 . Here we report experimental signatures of FQAH states in a twisted molybdenum ditelluride (MoTe 2 ) bilayer. Magnetic circular dichroism measurements reveal robust ferromagnetic states at fractionally hole-filled moiré minibands. Using trion photoluminescence as a sensor 10 , we obtain a Landau fan diagram showing linear shifts in carrier densities corresponding to filling factor v  = −2/3 and v  = −3/5 ferromagnetic states with applied magnetic field. These shifts match the Streda formula dispersion of FQAH states with fractionally quantized Hall conductance of σ x y = − 2 3 e 2 h and σ x y = − 3 5 e 2 h , respectively. Moreover, the v  = −1 state exhibits a dispersion corresponding to Chern number −1, consistent with the predicted QAH state 11 – 14 . In comparison, several non-ferromagnetic states on the electron-doping side do not disperse, that is, they are trivial correlated insulators. The observed topological states can be electrically driven into topologically trivial states. Our findings provide evidence of the long-sought FQAH states, demonstrating MoTe 2 moiré superlattices as a platform for exploring fractional excitations. Signatures of fractional quantum anomalous Hall states at zero magnetic field are observed in a fractionally filled moiré superlattice in a molybdenum ditelluride twisted bilayer.
Planar chiral metasurfaces with maximal and tunable chiroptical response driven by bound states in the continuum
Optical metasurfaces with high quality factors (Q-factors) of chiral resonances can boost substantially light-matter interaction for various applications of chiral response in ultrathin, active, and nonlinear metadevices. However, current approaches lack the flexibility to enhance and tune the chirality and Q-factor simultaneously. Here, we suggest a design of chiral metasurface supporting bound state in the continuum (BIC) and demonstrate experimentally chiroptical responses with ultra-high Q-factors and near-perfect circular dichroism (CD = 0.93) at optical frequencies. We employ the symmetry-reduced meta-atoms with high birefringence supporting winding elliptical eigenstate polarizations with opposite helicity. It provides a convenient way for achieving the maximal planar chirality tuned by either breaking in-plane structure symmetry or changing illumination angle. Beyond linear CD, we also achieved strong near-field enhancement CD and near-unitary nonlinear CD in the same planar chiral metasurface design with circular eigen-polarization. Sharply resonant chirality realized in planar metasurfaces promises various practical applications including chiral lasers and chiral nonlinear filters. Here, the authors employ the physics of chiral bound states in the continuum and suggest planar chiral metasurfaces with simultaneous ultrahigh quality factor and near-perfect circular dichroism in both linear regime and nonlinear regime.
Nano-achiral complex composites for extreme polarization optics
Composites from 2D nanomaterials show uniquely high electrical, thermal and mechanical properties 1 , 2 . Pairing their robustness with polarization rotation is needed for hyperspectral optics in extreme conditions 3 , 4 . However, the rigid nanoplatelets have randomized achiral shapes, which scramble the circular polarization of photons with comparable wavelengths. Here we show that multilayer nanocomposites from 2D nanomaterials with complex textured surfaces strongly and controllably rotate light polarization, despite being nano-achiral and partially disordered. The intense circular dichroism (CD) in nanocomposite films originates from the diagonal patterns of wrinkles, grooves or ridges, leading to an angular offset between axes of linear birefringence (LB) and linear dichroism (LD). Stratification of the layer-by-layer (LBL) assembled nanocomposites affords precise engineering of the polarization-active materials from imprecise nanoplatelets with an optical asymmetry g -factor of 1.0, exceeding those of typical nanomaterials by about 500 times. High thermal resilience of the composite optics enables operating temperature as high as 250 °C and imaging of hot emitters in the near-infrared (NIR) part of the spectrum. Combining LBL engineered nanocomposites with achiral dyes results in anisotropic factors for circularly polarized emission approaching the theoretical limit. The generality of the observed phenomena is demonstrated by nanocomposite polarizers from molybdenum sulfide (MoS 2 ), MXene and graphene oxide (GO) and by two manufacturing methods. A large family of LBL optical nanocomponents can be computationally designed and additively engineered for ruggedized optics. Multilayer composites of 2D nanomaterials manufactured using a layer-by-layer methodology demonstrates strong polarization rotation, mechanical robustness and operational temperatures as high as 250 °C, despite being nano-achiral and partially disordered.
Giant tunneling magnetoresistance in spin-filter van der Waals heterostructures
An electrical current running through two stacked magnetic layers is larger if their magnetizations point in the same direction than if they point in opposite directions. These so-called magnetic tunnel junctions, used in electronics, must be carefully engineered. Two groups now show that high magnetoresistance intrinsically occurs in samples of the layered material CrI 3 sandwiched between graphite contacts. By varying the number of layers in the samples, Klein et al. and Song et al. found that the electrical current running perpendicular to the layers was largest in high magnetic fields and smallest near zero field. This observation is consistent with adjacent layers naturally having opposite magnetizations, which align parallel to each other in high magnetic fields. Science , this issue p. 1218 , p. 1214 The atomic layers of the material CrI 3 act as spin filters in graphite/CrI 3 /graphite junctions. Magnetic multilayer devices that exploit magnetoresistance are the backbone of magnetic sensing and data storage technologies. Here, we report multiple-spin-filter magnetic tunnel junctions (sf-MTJs) based on van der Waals (vdW) heterostructures in which atomically thin chromium triiodide (CrI 3 ) acts as a spin-filter tunnel barrier sandwiched between graphene contacts. We demonstrate tunneling magnetoresistance that is drastically enhanced with increasing CrI 3 layer thickness, reaching a record 19,000% for magnetic multilayer structures using four-layer sf-MTJs at low temperatures. Using magnetic circular dichroism measurements, we attribute these effects to the intrinsic layer-by-layer antiferromagnetic ordering of the atomically thin CrI 3 . Our work reveals the possibility to push magnetic information storage to the atomically thin limit and highlights CrI 3 as a superlative magnetic tunnel barrier for vdW heterostructure spintronic devices.
Chiral atomically thin films
Graphene layers can be placed on top of each other with accurate twisting angles and show a remarkably high circular dichroism. Chiral materials possess left- and right-handed counterparts linked by mirror symmetry. These materials are useful for advanced applications in polarization optics 1 , 2 , stereochemistry 3 , 4 and spintronics 5 , 6 . In particular, the realization of spatially uniform chiral films with atomic-scale control of their handedness could provide a powerful means for developing nanodevices with novel chiral properties. However, previous approaches based on natural or grown films 1 , 2 , 7 , 8 , or arrays of fabricated building blocks 9 , 10 , 11 , could not offer a direct means to program intrinsic chiral properties of the film on the atomic scale. Here, we report a chiral stacking approach, where two-dimensional materials are positioned layer-by-layer with precise control of the interlayer rotation ( θ ) and polarity, resulting in tunable chiral properties of the final stack. Using this method, we produce left- and right-handed bilayer graphene, that is, a two-atom-thick chiral film. The film displays one of the highest intrinsic ellipticity values (6.5 deg μm –1 ) ever reported, and a remarkably strong circular dichroism (CD) with the peak energy and sign tuned by θ and polarity. We show that these chiral properties originate from the large in-plane magnetic moment associated with the interlayer optical transition. Furthermore, we show that we can program the chiral properties of atomically thin films layer-by-layer by producing three-layer graphene films with structurally controlled CD spectra.
Topological molecular nanocarbons
The generation of topologically complex nanocarbons can spur developments in science and technology. However, conventional synthetic routes to interlocked molecules require heteroatoms. We report the synthesis of catenanes and a molecular trefoil knot consisting solely of para-connected benzene rings. Characteristic fluorescence of a heterocatenane associated with fast energy transfer between two rings was observed, and the topological chirality of the all-benzene knot was confirmed by enantiomer separation and circular dichroism spectroscopy. The seemingly rigid all-benzene knot has rapid vortex-like motion in solution even at –95°C, resulting in averaged nuclear magnetic resonance signals for all hydrogen atoms. This interesting dynamic behavior of the knot was theoretically predicted and could stimulate deeper understanding and applications of these previously untapped classes of topological molecular nanocarbons.
Room-temperature intrinsic ferromagnetism in epitaxial CrTe2 ultrathin films
While the discovery of two-dimensional (2D) magnets opens the door for fundamental physics and next-generation spintronics, it is technically challenging to achieve the room-temperature ferromagnetic (FM) order in a way compatible with potential device applications. Here, we report the growth and properties of single- and few-layer CrTe 2 , a van der Waals (vdW) material, on bilayer graphene by molecular beam epitaxy (MBE). Intrinsic ferromagnetism with a Curie temperature ( T C ) up to 300 K, an atomic magnetic moment of ~0.21  μ B /Cr and perpendicular magnetic anisotropy (PMA) constant ( K u ) of 4.89 × 10 5  erg/cm 3 at room temperature in these few-monolayer films have been unambiguously evidenced by superconducting quantum interference device and X-ray magnetic circular dichroism. This intrinsic ferromagnetism has also been identified by the splitting of majority and minority band dispersions with ~0.2 eV at Г point using angle-resolved photoemission spectroscopy. The FM order is preserved with the film thickness down to a monolayer ( T C  ~ 200 K), benefiting from the strong PMA and weak interlayer coupling. The successful MBE growth of 2D FM CrTe 2 films with room-temperature ferromagnetism opens a new avenue for developing large-scale 2D magnet-based spintronics devices. The emergence of two dimensional ferromagnetism suffers from an inherent fragility to thermal fluctuations, which typically restricts the Curie temperature to below room temperature. Here, Zhang et al present CrTe 2 thin films grown via molecular beam epitaxy with a Curie temperature exceeding 300 K.