ABSTRACT
As a prototypical photocatalyst, TiO[Formula: see text] has been extensively studied. An interesting yet puzzling experimental fact was that P25-a mixture of anatase and rutile TiO[Formula: see text]-outperforms the individual phases; the origin of this mysterious fact, however, remains elusive. Employing rigorous first-principles calculations, here we uncover a metastable intermediate structure (MIS), which is formed due to confinement at the anatase/rutile interface. The MIS has a high conduction-band minimum level and thus substantially enhances the overpotential of the hydrogen evolution reaction. Also, the corresponding band alignment at the interface leads to efficient separation of electrons and holes. The interfacial confinement additionally creates a wide distribution of the band gap in the vicinity of the interface, which in turn improves optical absorption. These factors all contribute to the enhanced photocatalytic efficiency in P25. Our insights provide a rationale to the puzzling superior photocatalytic performance of P25 and enable a strategy to achieve highly efficient photocatalysis via interface engineering.
ABSTRACT
Covalent bonding interactions determine the energy-momentum (E-k) dispersion (band structure) of solid-state materials. Here, we show that noncovalent interactions can modulate the E-k dispersion near the Fermi level of a low-dimensional nanoscale conductor. We demonstrate that low energy band gaps may be opened in metallic carbon nanotubes through polymer wrapping of the nanotube surface at fixed helical periodicity. Electronic spectral, chiro-optic, potentiometric, electronic device, and work function data corroborate that the magnitude of band gap opening depends on the nature of the polymer electronic structure. Polymer dewrapping reverses the conducting-to-semiconducting phase transition, restoring the native metallic carbon nanotube electronic structure. These results address a long-standing challenge to develop carbon nanotube electronic structures that are not realized through disruption of π conjugation, and establish a roadmap for designing and tuning specialized semiconductors that feature band gaps on the order of a few hundred meV.
ABSTRACT
The advancement of atomically precise dinuclear heterogeneous catalysts holds great potential in achieving efficient catalytic ozonation performance and contributes to the understanding of synergy mechanisms during reaction conditions. Herein, we demonstrate a "ship-in-a-bottle and pyrolysis" strategy that utilizes Fe2(CO)9 dinuclear-cluster to precisely construct Fe2 site, consisting of two Fe1-N3 units connected by Fe-Fe bonds and firmly bonded to N-doped carbon. Systematic characterizations and theoretical modeling reveal that the Fe-Fe coordination motif markedly reduced the devotion of the antibonding state in the Fe-O bond because of the strong orbital coupling interaction of dual Fe d-d orbitals. This facilitates O-O covalent bond cleavage of O3 and enhances binding strength with reaction intermediates (atomic oxygen species; *O and *OO), thus boosting catalytic ozonation performance. As a result, Fe dinuclear site catalyst exhibits 100% ozonation efficiency for CH3SH elimination, outperforming commercial MnO2 catalysts by 1,200-fold. This research provides insights into the atomic-level structure-activity relationship of ozonation catalysts and extends the use of dinuclear catalysts in catalytic ozonation and beyond.
ABSTRACT
Sr2IrO4 has attracted considerable attention due to its structural and electronic similarities to La2CuO4, the parent compound of high-Tc superconducting cuprates. It was proposed as a strong spin-orbit-coupled Jeff = 1/2 Mott insulator, but the Mott nature of its insulating ground state has not been conclusively established. Here, we use ultrafast laser pulses to realize an insulator-metal transition in Sr2IrO4 and probe the resulting dynamics using time- and angle-resolved photoemission spectroscopy. We observe a gap closure and the formation of weakly renormalized electronic bands in the gap region. Comparing these observations to the expected temperature and doping evolution of Mott gaps and Hubbard bands provides clear evidence that the insulating state does not originate from Mott correlations. We instead propose a correlated band insulator picture, where antiferromagnetic correlations play a key role in the gap opening. More broadly, our results demonstrate that energy-momentum-resolved nonequilibrium dynamics can be used to clarify the nature of equilibrium states in correlated materials.
ABSTRACT
Division plane positioning is crucial for proper growth and development in many organisms. In plants, the division plane is established before mitosis, by accumulation of a cytoskeletal structure called the preprophase band (PPB). The PPB is thought to be essential for recruitment of division site-localized proteins, which remain at the division site after the PPB disassembles. Here, we show that the division site-localized protein TANGLED1 (TAN1) is recruited independently of the PPB to the cell cortex by the plant cytokinetic machinery, the phragmoplast, from experiments using both the PPB-defective mutant discordia1 (dcd1) and chemical treatments that disrupt the phragmoplast in maize. TAN1 recruitment to de novo sites on the cortex is partially dependent on intact actin filaments and the myosin XI motor protein OPAQUE1 (O1). These data imply a yet unknown role for TAN1 and possibly other division site-localized proteins during the last stages of cell division when the phragmoplast touches the cell cortex to complete cytokinesis.
Subject(s)
Cytokinesis , Plant Proteins , Zea mays , Zea mays/metabolism , Zea mays/genetics , Plant Proteins/metabolism , Plant Proteins/genetics , Actin Cytoskeleton/metabolismABSTRACT
Predator detection is key to animal's survival. Superior colliculus (SC) orchestrates the animal's innate defensive responses to visually detected threats, but how threat information is transmitted from the retina to SC is unknown. We discovered that narrow-field neurons in SC were key in this pathway. Using in vivo calcium imaging and optogenetics-assisted interrogation of circuit and synaptic connections, we found that the visual responses of narrow-field neurons were correlated with the animal's defensive behaviors toward visual stimuli. Activation of these neurons triggered defensive behaviors, and ablation of them impaired the animals' defensive responses to looming stimuli. They receive monosynaptic inputs from looming-sensitive OFF-transient alpha retinal ganglion cells, and the synaptic transmission has a unique band-pass feature that helps to shape their stimulus selectivity. Our results describe a cell-type specific retinotectal connection for visual threat detection, and a coding mechanism based on synaptic filtering.
Subject(s)
Retinal Ganglion Cells , Superior Colliculi , Mice , Animals , Superior Colliculi/physiology , Visual PathwaysABSTRACT
Electronic structure calculations indicate that the Sr2FeSbO6 double perovskite has a flat-band set just above the Fermi level that includes contributions from ordinary subbands with weak kinetic electron hopping plus a flat subband that can be attributed to the lattice geometry and orbital interference. To place the Fermi energy in that flat band, electron-doped samples with formulas Sr2-xLaxFeSbO6 (0 ≤ x ≤ 0.3) were synthesized, and their magnetism and ambient temperature crystal structures were determined by high-resolution synchrotron X-ray powder diffraction. All materials appear to display an antiferromagnetic-like maximum in the magnetic susceptibility, but the dominant spin coupling evolves from antiferromagnetic to ferromagnetic on electron doping. Which of the three subbands or combinations is responsible for the behavior has not been determined.
ABSTRACT
There are empirical strategies for tuning the degree of strain localization in disordered solids, but they are system-specific and no theoretical framework explains their effectiveness or limitations. Here, we study three model disordered solids: a simulated atomic glass, an experimental granular packing, and a simulated polymer glass. We tune each system using a different strategy to exhibit two different degrees of strain localization. In tandem, we construct structuro-elastoplastic (StEP) models, which reduce descriptions of the systems to a few microscopic features that control strain localization, using a machine learning-based descriptor, softness, to represent the stability of the disordered local structure. The models are based on calculated correlations of softness and rearrangements. Without additional parameters, the models exhibit semiquantitative agreement with observed stress-strain curves and softness statistics for all systems studied. Moreover, the StEP models reveal that initial structure, the near-field effect of rearrangements on local structure, and rearrangement size, respectively, are responsible for the changes in ductility observed in the three systems. Thus, StEP models provide microscopic understanding of how strain localization depends on the interplay of structure, plasticity, and elasticity.
ABSTRACT
Perception is a probabilistic process dependent on external stimulus properties and one's internal state. However, which internal states influence perception and via what mechanisms remain debated. We studied how spontaneous alpha-band activity (8-13â Hz) and pupil fluctuations impact visual detection and confidence across stimulus contrast levels (i.e., the contrast response function, CRF). In human subjects of both sexes, we found that low prestimulus alpha power induced an "additive" shift in the CRF, whereby stimuli were reported present more frequently at all contrast levels, including contrast of zero (i.e., false alarms). Conversely, prestimulus pupil size had a "multiplicative" effect on detection such that stimuli occurring during large pupil states (putatively corresponding to higher arousal) were perceived more frequently as contrast increased. Signal detection modeling reveals that alpha power changes detection criteria equally across the CRF but not detection sensitivity (d'), whereas pupil-linked arousal modulated sensitivity, particularly for higher contrasts. Interestingly, pupil size and alpha power were positively correlated, meaning that some of the effect of alpha on detection may be mediated by pupil fluctuations. However, pupil-independent alpha still induced an additive shift in the CRF corresponding to a criterion effect. Our data imply that low alpha boosts detection and confidence by an additive factor, rather than by a multiplicative scaling of contrast responses, a profile which captures the effect of pupil-linked arousal. We suggest that alpha power and arousal fluctuations have dissociable effects on behavior. Alpha reflects the baseline level of visual excitability, which can vary independent of arousal.
Subject(s)
Alpha Rhythm , Arousal , Pupil , Humans , Female , Male , Pupil/physiology , Arousal/physiology , Adult , Alpha Rhythm/physiology , Young Adult , Photic Stimulation/methods , Visual Perception/physiology , Contrast Sensitivity/physiologyABSTRACT
Blood platelets are small non-nucleated cellular fragments that prevent and stop hemorrhages. They are produced in the bone marrow by megakaryocytes through megakaryopoiesis. This intricate process involves profound microtubule rearrangements culminating in the formation of a unique circular sub-membranous microtubule array, the marginal band, which supports the typical disc-shaped morphology of platelets. Mechanistically, these processes are thought to be controlled by a specific tubulin code. In this review, we summarize the current knowledge on the key isotypes, notably ß1-, α4A- and α8-tubulin, and putative post-translational modifications, involved in platelet and marginal band formation. Additionally, we provide a provisional list of microtubule-associated proteins (MAPs) involved in these processes and a survey of tubulin variants identified in patients presenting defective platelet production. A comprehensive characterization of the platelet tubulin code and the identification of essential MAPs may be expected in the near future to shed new light on a very specialized microtubule assembly process with applications in platelet diseases and transfusion.
Subject(s)
Megakaryocytes , Tubulin , Humans , Tubulin/genetics , Tubulin/metabolism , Megakaryocytes/metabolism , Microtubules/metabolism , Blood Platelets/metabolism , Protein Processing, Post-TranslationalABSTRACT
The parasite Plasmodium vivax preferentially invades human reticulocytes. Its merozoite surface protein 1 paralog (PvMSP1P), particularly the 19-kDa C-terminal region (PvMSP1P-19), has been shown to bind to reticulocytes, and this binding can be inhibited by antisera obtained by PvMSP1P-19 immunization. The molecular mechanism of interactions between PvMSP1P-19 and reticulocytes during P. vivax invasion, however, remains unclear. In this study, we analyzed the ability of MSP1P-19 to bind to different concentrations of reticulocytes and confirmed its reticulocyte preference. LC-MS analysis was used to identify two potential reticulocyte receptors, band3 and CD71, that interact with MSP1P-19. Both PvMSP1P-19 and its sister taxon Plasmodium cynomolgi MSP1P-19 were found to bind to the extracellular loop (loop 5) of band3, where the interaction of MSP1P-19 with band3 was chymotrypsin sensitive. Antibodies against band3-P5, CD71, and MSP1P-19 reduced the binding activity of PvMSP1P-19 and Plasmodium cynomolgi MSP1P-19 to reticulocytes, while MSP1P-19 proteins inhibited Plasmodium falciparum invasion in vitro in a concentration-dependent manner. To sum up, identification and characterization of the reticulocyte receptor is important for understanding the binding of reticulocytes by MSP1P-19.
Subject(s)
Antigens, CD , Plasmodium vivax , Protozoan Proteins , Receptors, Transferrin , Reticulocytes , Plasmodium vivax/metabolism , Plasmodium vivax/genetics , Reticulocytes/metabolism , Reticulocytes/parasitology , Humans , Protozoan Proteins/metabolism , Protozoan Proteins/genetics , Antigens, CD/metabolism , Antigens, CD/genetics , Receptors, Transferrin/metabolism , Receptors, Transferrin/genetics , Anion Exchange Protein 1, Erythrocyte/metabolism , Anion Exchange Protein 1, Erythrocyte/genetics , Protein Binding , Merozoite Surface Protein 1/metabolism , Merozoite Surface Protein 1/genetics , Malaria, Vivax/parasitology , Malaria, Vivax/metabolism , AnimalsABSTRACT
The involvement of the human amygdala in facial mimicry remains a matter of debate. We investigated neural activity in the human amygdala during a task in which an imitation task was separated in time from an observation task involving facial expressions. Neural activity in the amygdala was measured using functional magnetic resonance imaging in 18 healthy individuals and using intracranial electroencephalogram in six medically refractory patients with epilepsy. The results of functional magnetic resonance imaging experiment showed that mimicry of negative and positive expressions activated the amygdala more than mimicry of non-emotional facial movements. In intracranial electroencephalogram experiment and time-frequency analysis, emotion-related activity of the amygdala during mimicry was observed as a significant neural oscillation in the high gamma band range. Furthermore, spectral event analysis of individual trial intracranial electroencephalogram data revealed that sustained oscillation of gamma band activity originated from an increased number and longer duration of neural events in the amygdala. Based on these findings, we conclude that during facial mimicry, visual information of expressions and feedback from facial movements are combined in the amygdalar nuclei. Considering the time difference of information approaching the amygdala, responses to facial movements are likely to modulate rather than initiate affective processing in human participants.
Subject(s)
Electrocorticography , Imitative Behavior , Humans , Emotions/physiology , Amygdala/diagnostic imaging , Amygdala/physiology , Magnetic Resonance Imaging/methods , Hemodynamics , Facial Expression , Brain Mapping/methodsABSTRACT
Previous working memory research has demonstrated robust stimulus representations during memory maintenance in both voltage and alpha-band activity in electroencephalography. However, the exact functions of these 2 neural signatures have remained controversial. Here we systematically investigated their respective contributions to memory manipulation. Human participants either maintained a previously seen spatial location, or manipulated the location following a mental rotation cue over a delay. Using multivariate decoding, we observed robust location representations in low-frequency voltage and alpha-band oscillatory activity with distinct spatiotemporal dynamics: location representations were most evident in posterior channels in alpha-band activity, but were most prominent in the more anterior, central channels in voltage signals. Moreover, the temporal emergence of manipulated representation in central voltage preceded that in posterior alpha-band activity, suggesting that voltage might carry stimulus-specific source signals originated internally from anterior cortex, whereas alpha-band activity might reflect feedback signals in posterior cortex received from higher-order cortex. Lastly, while location representations in both signals were coded in a low-dimensional neural subspace, location representation in central voltage was higher-dimensional and underwent a representational transformation that exclusively predicted memory behavior. Together, these results highlight the crucial role of central voltage in working memory, and support functional distinctions between voltage and alpha-band activity.
Subject(s)
Cerebral Cortex , Memory, Short-Term , Humans , ElectroencephalographyABSTRACT
Understanding the nature and formation of band gaps associated with the propagation of electromagnetic, electronic, or elastic waves in disordered materials as a function of system size presents fundamental and technological challenges. In particular, a basic question is whether band gaps in disordered systems exist in the thermodynamic limit. To explore this issue, we use a two-stage ensemble approach to study the formation of complete photonic band gaps (PBGs) for a sequence of increasingly large systems spanning a broad range of two-dimensional photonic network solids with varying degrees of local and global order, including hyperuniform and nonhyperuniform types. We discover that the gap in the density of states exhibits exponential tails and the apparent PBGs rapidly close as the system size increases for nearly all disordered networks considered. The only exceptions are sufficiently stealthy hyperuniform cases for which the band gaps remain open and the band tails exhibit a desirable power-law scaling reminiscent of the PBG behavior of photonic crystals in the thermodynamic limit.
Subject(s)
Electronics , Memory , Photons , Records , ThermodynamicsABSTRACT
The genomes of some purple photosynthetic bacteria contain a multigene puc family encoding a series of α- and ß-polypeptides that together form a heterogeneous antenna of light-harvesting 2 (LH2) complexes. To unravel this complexity, we generated four sets of puc deletion mutants in Rhodopseudomonas palustris, each encoding a single type of pucBA gene pair and enabling the purification of complexes designated as PucA-LH2, PucB-LH2, PucD-LH2, and PucE-LH2. The structures of all four purified LH2 complexes were determined by cryogenic electron microscopy (cryo-EM) at resolutions ranging from 2.7 to 3.6 Å. Uniquely, each of these complexes contains a hitherto unknown polypeptide, γ, that forms an extended undulating ribbon that lies in the plane of the membrane and that encloses six of the nine LH2 αß-subunits. The γ-subunit, which is located near to the cytoplasmic side of the complex, breaks the C9 symmetry of the LH2 complex and binds six extra bacteriochlorophylls (BChls) that enhance the 800-nm absorption of each complex. The structures show that all four complexes have two complete rings of BChls, conferring absorption bands centered at 800 and 850 nm on the PucA-LH2, PucB-LH2, and PucE-LH2 complexes, but, unusually, the PucD-LH2 antenna has only a single strong near-infared (NIR) absorption peak at 803 nm. Comparison of the cryo-EM structures of these LH2 complexes reveals altered patterns of hydrogen bonds between LH2 αß-side chains and the bacteriochlorin rings, further emphasizing the major role that H bonds play in spectral tuning of bacterial antenna complexes.
Subject(s)
Bacteriochlorophylls , Rhodopseudomonas , Bacterial Proteins/metabolism , Bacteriochlorophylls/metabolism , Cryoelectron Microscopy , Light-Harvesting Protein Complexes/metabolism , Peptides/metabolism , Rhodopseudomonas/geneticsABSTRACT
Hyperbolic lattices are a new form of synthetic quantum matter in which particles effectively hop on a discrete tessellation of two-dimensional (2D) hyperbolic space, a non-Euclidean space of uniform negative curvature. To describe the single-particle eigenstates and eigenenergies for hopping on such a lattice, a hyperbolic generalization of band theory was previously constructed, based on ideas from algebraic geometry. In this hyperbolic band theory, eigenstates are automorphic functions, and the Brillouin zone is a higher-dimensional torus, the Jacobian of the compactified unit cell understood as a higher-genus Riemann surface. Three important questions were left unanswered: whether a band theory can be expected to hold for a non-Euclidean lattice, where translations do not generally commute; whether a formal Bloch theorem can be rigorously established; and whether hyperbolic band theory can describe finite lattices realized in an experiment. In the present work, we address all three questions simultaneously. By formulating periodic boundary conditions for finite but arbitrarily large lattices, we show that a generalized Bloch theorem can be rigorously proved but may or may not involve higher-dimensional irreducible representations (irreps) of the nonabelian translation group, depending on the lattice geometry. Higher-dimensional irreps correspond to points in a moduli space of higher-rank stable holomorphic vector bundles, which further generalizes the notion of Brillouin zone beyond the Jacobian. For a large class of finite lattices, only 1D irreps appear, and the hyperbolic band theory previously developed becomes exact.
ABSTRACT
The growing demands for ammonia in agriculture and transportation fuel stimulate researchers to develop sustainable electrochemical methods to synthesize ammonia ambiently, to get past the energy-intensive Haber-Bosch process. However, the conventionally used aqueous electrolytes limit N2 solubility, leading to insufficient reactant molecules in the vicinity of the catalyst during electrochemical nitrogen reduction reaction (NRR). This hampers the yield and production rate of ammonia, irrespective of how efficient the catalyst is. Herein, we introduce an aqueous electrolyte (NaBF4), which not only acts as an N2-carrier in the medium but also works as a full-fledged "co-catalyst" along with our active material MnN4 to deliver a high yield of NH3 (328.59 µg h-1 mgcat-1) at 0.0 V versus reversible hydrogen electrode. BF3-induced charge polarization shifts the metal d-band center of the MnN4 unit close to the Fermi level, inviting N2 adsorption facilely. The Lewis acidity of the free BF3 molecules further propagates their importance in polarizing the N≡N bond of the adsorbed N2 and its first protonation. This push-pull kind of electronic interaction has been confirmed from the change in d-band center values of the MnN4 site as well as charge density distribution over our active model units, which turned out to be effective enough to lower the energy barrier of the potential determining steps of NRR. Consequently, a high production rate of NH3 (2.45 × 10-9 mol s-1 cm-2) was achieved, approaching the industrial scale where the source of NH3 was thoroughly studied and confirmed to be chiefly from the electrochemical reduction of the purged N2 gas.
ABSTRACT
We propose a band engineering scheme on the biphenylene network, a newly synthesized carbon allotrope. We illustrate that the electronic structure of the biphenylene network can be significantly altered by controlling conditions affecting the symmetry and destructive interference of wave functions through periodic fluorination. First, we investigate the mechanism for the appearance of a type-II Dirac fermion in a pristine biphenylene network. We show that the essential ingredients are mirror symmetries and stabilization of the compact localized eigenstates via destructive interference. While the former is used for the band-crossing point along high symmetry lines, the latter induces highly inclined Dirac dispersions. Subsequently, we demonstrate the transformation of the biphenylene network's type-II Dirac semimetal phase into various Dirac phases such as type-I Dirac, gapped type-II Dirac, and nodal line semimetals through the deliberate disruption of mirror symmetry or modulation of destructive interference by varying the concentration of fluorine atoms.
ABSTRACT
Miniaturized photodetectors are becoming increasingly sought-after components for next-generation technologies, such as autonomous vehicles, integrated wearable devices, or gadgets embedded on the Internet of Things. A major challenge, however, lies in shrinking the device footprint while maintaining high efficiency. This conundrum can be solved by realizing a nontrivial relation between the energy and momentum of photons, such as dispersion-free devices, known as flat bands. Here, we leverage flat-band meta-optics to simultaneously achieve critical absorption over a wide range of incidence angles. For a monolithic silicon meta-optical photodiode, we achieved an â¼10-fold enhancement in the photon-to-electron conversion efficiency. Such enhancement over a large angular range of â¼36° allows incoming light to be collected via a large-aperture lens and focused on a compact photodiode, potentially enabling high-speed and low-light operation. Our research unveils new possibilities for creating compact and efficient optoelectronic devices with far-reaching impact on various applications, including augmented reality and light detection and ranging.
ABSTRACT
Two-dimensional (2D) ferroelectrics possessing out-of-plane (OP) polarization are highly desirable for applications and fundamental physics. Here, by first-principles calculations, we reveal that large-angle interlayer twisting can efficiently stabilize an unexpected ordering of sizable electric dipoles, producing OP polarization out of the centrosymmetric ground-state structure of Tl2S, in great contrast to the recently proposed interlayer-sliding ferroelectricity. The ferroelectricity originates from a nonlinear coupling between a polar order dominantly contributed by electrons and an unstable phonon mode associated with a commensurate k point (1/3, 1/3, 0) in the two constituent monolayers, therefore indicating an improper and electronic ferroelectric nature. More interestingly, a flat band and a van Hove singularity occur in its electronic structures just below the Fermi level in the large-angle twisted bilayer Tl2S. The unusual coexistence of improper electronic ferroelectricity, a flat band, and a van Hove singularity in one 2D material offers exceptional opportunities for exploring novel physics and applications.