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Photocatalytic hydrogen production is one of the most valuable technologies in the future energy system. Here, we designed a metal-covalent organic frameworks (MCOFs) with both small-sized metal clusters and nitrogen-rich ligands, named COF-Cu3TG. Based on our design, small-sized metal clusters were selected to increase the density of active sites and shorten the distance of electron transport to active sites. While another building block containing nitrogen-rich organic ligands acted as a node that could in situ anchor metal atoms during photocatalysis and form interlayer single-atom electron bridges (SAEB) to accelerate electron transport. Together, they promoted photocatalytic performance. This represented the further utilization of Ru atoms and was an additional application of the photosensitizer. N2-Ru-N2 electron bridge (Ru-SAEB) was created in situ between the layers, resulting in a considerable enhancement in the hydrogen production rate of the photocatalyst to 10.47 mmol g-1 h-1. Through theoretical calculation and EXAFS, the existence position and action mechanism of Ru-SAEB were reasonably inferred, further confirming the rationality of the Ru-SAEB configuration. A sufficiently proximity between the small-sized Cu3 cluster and the Ru-SAEB was found to expedite electron transfer. This work demonstrated the synergistic impact of small molecular clusters with Ru-SAEB for efficient photocatalytic hydrogen production.
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Carbon dioxide (CO2) coupled with epoxide to generate cyclic carbonate stands out in carbon neutrality due to its 100% atom utilization. In this work, the mechanism of CO2 cycloaddition with propylene oxide (PO) cocatalyzed by windmill-shaped polyoxovanadate, [(C2N2H8)4(CH3O)4VIV4VV4O16]·4CH3OH (V8-1), and n-Bu4NX (X = Br, I) was thoroughly investigated using density functional theory (DFT) calculations. The ring-opening, CO2-insertion, and ring-closing steps of the process were extensively studied. Our work emphasizes the synergistic effect between V8-1 and n-Bu4NX (X = Br, I). Through the analysis of an independent gradient model based on Hirshfeld partition (IGMH), it was found that the attack of n-Bu4NX (X = Br, I) on Cß of PO triggers a distinct attractive interaction between the active fragment and the surrounding framework, serving as the primary driving force for the ring opening of PO. Furthermore, the effect of different cocatalysts was explored, with n-Bu4NI being more favorable than n-Bu4NBr. Moreover, the role of V8-1 in the CO2 cycloaddition reaction was clarified as not only acting as Lewis acid active sites but also serving as "electron sponges". This work is expected to advance the development of novel catalysts for organic carbonate formation.
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Covalent-organic frameworks (COFs) with photoinduced donor-acceptor (D-A) radical pairs show enhanced photocatalytic activity in principle. However, achieving long-lived charge separation in COFs proves challenging due to the rapid charge recombination. Here, we develop a novel strategy by combining [6 + 4] nodes to construct zyg-type 3D COFs, first reported in COF chemistry. This structure type exhibits a fused Olympic-rings-like shape, which provides a platform for stabilizing the photoinduced D-A radical pairs. The zyg-type COFs containing catalytically active moieties such as triphenylamine and phenothiazine (PTZ) show superior photocatalytic production rates of hydrogen peroxide (H2O2). Significantly, the photochromic radical states of these COFs show up to 400% enhancement in photocatalytic activity compared to the parent states, achieving a remarkable H2O2 synthesis rate of 3324 µmol g-1 h-1, which makes the PTZ-COF one of the best crystalline porous photocatalysts in H2O2 production. This work will shed light on the synthesis of efficient 3D COF photocatalysts built on topologies that can facilitate photogenerating D-A radical pairs for enhanced photocatalysis.
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Ultra-low temperature resistant adhesive is highly desired yet scarce for material adhesion for the potential usage in Arctic/Antarctic or outer space exploration. Here we develop a solvent-free processed low-temperature tolerant adhesive with excellent adhesion strength and organic solvent stability, wide tolerable temperature range (i.e. -196 to 55 °C), long-lasting adhesion effect ( > 60 days, -196 °C) that exceeds the classic commercial hot melt adhesives. Furthermore, combine experimental results with theoretical calculations, the strong interaction energy between polyoxometalate and polymer is the main factor for the low-temperature tolerant adhesive, possessing enhanced cohesion strength, suppressed polymer crystallization and volumetric contraction. Notably, manufacturing at scale can be easily achieved by the facile scale-up solvent-free processing, showing much potential towards practical application in Arctic/Antarctic or planetary exploration.
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Magnetic materials offer a fertile playground for fundamental physics discovery, with not only electronic but also magnonic topological states intensively explored. However, one natural material with both electronic and magnonic nontrivial topologies is still unknown. Here, we demonstrate the coexistence of first-order topological magnon insulators (TMIs) and electronic second-order topological insulators (SOTIs) in 2D honeycomb ferromagnets, giving rise to the nontrivial corner states being connected by the charge-free magnonic edge states. We show that, with C3 symmetry, the phase factor ± Ï caused by the next nearest-neighbor Dzyaloshinskii-Moriya interaction breaks the pseudo-spin time-reversal symmetry T, which leads to the split of magnon bands, i.e., the emergence of TMIs with a nonzero Chern number of C=-1, in experimentally feasible candidates of MoI3, CrSiTe3, and CrGeTe3 monolayers. Moreover, protected by the C3 symmetry, the electronic SOTIs characterized by nontrivial corner states are obtained, bridging the topological aspect of fermions and bosons with a high possibility of innovative applications in spintronics devices.
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We show that circularly polarized light is a versatile way to manipulate both the orbital Hall effect and band topology in two-dimensional ferromagnets. Employing the hexagonal lattice, we proposed that interactions between light and matter allow for the modulation of the valley polarization effect, and then band inversions, accompanied by the band gap closing and reopening processes, can be achieved subsequently at two valleys. Remarkably, the distribution of orbital angular momentum can be controlled by the band inversions, leading to the Floquet engineering of the orbital Hall effect, as well as the topological phase transition from a second-order topological insulator to a Chern insulator with in-plane magnetization, and then to a normal insulator. Furthermore, first-principles calculations validate the feasibility with the 2H-ScI2 monolayer as a candidate material, paving a technological avenue to bridge the orbitronics and nontrivial topology using Floquet engineering.
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The human face is a valuable biomarker of aging, but the collection and use of its image raise significant privacy concerns. Here we present an approach for facial data masking that preserves age-related features using coordinate-wise monotonic transformations. We first develop a deep learning model that estimates age directly from non-registered face point clouds with high accuracy and generalizability. We show that the model learns a highly indistinguishable mapping using faces treated with coordinate-wise monotonic transformations, indicating that the relative positioning of facial information is a low-level biomarker of facial aging. Through visual perception tests and computational 3D face verification experiments, we demonstrate that transformed faces are significantly more difficult to perceive for human but not for machines, except when only the face shape information is accessible. Our study leads to a facial data protection guideline that has the potential to broaden public access to face datasets with minimized privacy risks.
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Envelhecimento , Face , Imageamento Tridimensional , Privacidade , Humanos , Imageamento Tridimensional/métodos , Envelhecimento/fisiologia , Aprendizado Profundo , Feminino , Masculino , Adulto , Adulto Jovem , Idoso , Pessoa de Meia-Idade , Percepção Visual/fisiologiaRESUMO
Recent advances in the manipulation of the orbital angular momentum (OAM) within the paradigm of orbitronics presents a promising avenue for the design of future electronic devices. In this context, the recently observed orbital Hall effect (OHE) occupies a special place. Here, focusing on both the second-order topological and quantum anomalous Hall insulators in two-dimensional ferromagnets, we demonstrate that topological phase transitions present an efficient and straightforward way to engineer the OHE, where the OAM distribution can be controlled by the nature of the band inversion. Using first-principles calculations, we identify Janus RuBrCl and three septuple layers of MnBi2Te4 as experimentally feasible examples of the proposed mechanism of OHE engineering by topology. With our work, we open up new possibilities for innovative applications in topological spintronics and orbitronics.
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The long-lasting humoral immunity induced by viral infections or vaccinations depends on memory B cells with greatly increased affinity to viral antigens, which are evolved from germinal center (GC) responses. However, it is unclear whether antiviral memory B cells represent a distinct subset among the highly heterogeneous memory B cell population. Here, we examined memory B cells induced by a virus-mimicking antigen at both transcriptome and epigenetic levels and found unexpectedly that antiviral memory B cells exhibit an enhanced innate immune response, which appeared to be facilitated by the epigenetic memory that is established through the memory B cell development. In addition, T-bet is associated with the altered chromatin architecture and is required for the formation of the antiviral memory B cells. Thus, antiviral memory B cells are distinct from other GC-derived memory B cells in both physiological functions and epigenetic landmarks.
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Linfócitos B , Células B de Memória , Memória Epigenética , Imunidade Inata , AntiviraisRESUMO
Toll-like receptor 4 (TLR4) is a crucial inflammatory signaling pathway that can serve as a potential treatment target for various disorders. A number of inhibitors have been developed for the TLR4 pathway, and although no inhibitors have been approved for clinical use, most have been screened against the TLR4-MD2 conformation. The venom gland is the organ of venomous snakes that secretes substances that are toxic to other animals. The level of gene transcription in venom glands is different from that in other tissues, includes a large number of biologically active ingredients, and is an important natural resource for the development of new drugs. We constructed a T7 phage display library using the cobra (Naja atra) venom gland from the Guangdong Snake Breeding Plant and performed three rounds of screening with TLR4 as the target, randomly selecting monoclonal phage spots for PCR followed by Sanger sequencing. The obtained sequences were subjected to length analysis, molecular docking, solubility prediction, and stability prediction, and a peptide containing 39 amino acids (NA39) was finally screened out. The BLAST results indicated that NA39 was a sequence in RPL19 (Ribosomal Protein L19). After peptide synthesis, the binding ability of NA39 to TLR4 was verified by the surface plasmon resonance (SPR) technique. In this study, a new peptide that can specifically bind TLR4 was successfully screened from the cobra venom gland cDNA library, further demonstrating the effectiveness of phage display technology in the field of drug discovery.
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Bacteriófagos , Naja naja , Animais , Simulação de Acoplamento Molecular , Receptor 4 Toll-Like , PeptídeosRESUMO
The structural diversity and controllability in two-dimensional (2D) materials offers an intriguing platform for exploring a wide range of topological phenomena. The layer degree of freedom, as a novel technique for material manipulation, requires further investigation regarding its association with topological states. Here, using first-principles calculations and a tight-binding model, we propose a novel mechanism that couples the second-order topological corner states with the layer degree of freedom. By analyzing the edge states, topological indices, and spectra of nanoflakes, we identify ferromagnetic H'-Co2XF2 (X = C, N) as 2D second-order topological insulators with intrinsic ferroelectricity. Moreover, the topological corner states strongly couple with the layer degree of freedom, and, remarkably, ferroelectricity provides a nonvolatile handle to manipulate the layer-polarized corner states. These findings open an avenue for the manipulation of second-order topological states and establish a bridge between ferroelectricity and nontrivial topology.
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In modern industries, the aerobic oxidation of C(sp3)-H bonds to achieve the value-added conversion of hydrocarbons requires high temperatures and pressures, which significantly increases energy consumption and capital investment. The development of a light-driven strategy, even under natural sunlight and ambient air, is therefore of great significance. Here we develop a series of hetero-motif molecular junction photocatalysts containing two bifunctional motifs. With these materials, the reduction of O2 and oxidation of C(sp3)-H bonds can be effectively accomplished, thus realizing efficient aerobic oxidation of C(sp3)-H bonds in e.g., toluene and ethylbenzene. Especially for ethylbenzene oxidation reactions, excellent catalytic capacity (861 mmol g cat-1) is observed. In addition to the direct oxidation of C(sp3)-H bonds, CeBTTD-A can also be applied to other types of aerobic oxidation reactions highlighting their potential for industrial applications.
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Integrating the advantages of homogeneous and heterogeneous catalysis has proved to be an optimal strategy for developing catalytic systems with high efficiency, selectivity, and recoverability. Supramolecular metal-organic cages (MOCs), assembled by the coordination of metal ions with organic linkers into discrete molecules, have performed solvent processability due to their tunable packing modes, endowing them with the potential to act as homogeneous or heterogeneous catalysts in different solvent systems. Here, the design and synthesis of a series of stable {Cu3} cluster-based tetrahedral MOCs with varied packing structures are reported. These MOCs, as homogeneous catalysts, not only show high catalytic activity and selectivity regardless of substrate size during the CO2 cycloaddition reaction, but also can be easily recovered from the reaction media through separating products and co-catalysts by one-step work-up. This is because that these MOCs have varied solubilities in different solvents due to the tunable packing of MOCs in the solid state. Moreover, the entire catalytic reaction system is very clean, and the purity of cyclic carbonates is as high as 97% without further purification. This work provides a unique strategy for developing novel supramolecular catalysts that can be used for homogeneous catalysis and recycled in a heterogeneous manner.
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We put forward that stacked Chern insulators with opposite chiralities offer a strategy to achieve gapless helical edge states in two dimensions. We employ the square lattice as an example and elucidate that the gapless chiral and helical edge states emerge in the monolayer and antiferromagnetically stacked bilayer, characterized by Chern number C=-1 and spin Chern number CS=-1, respectively. Particularly, for a topological phase transition to the normal insulator in the stacked bilayer, a band gap closing and reopening procedure takes place accompanied by helical edge states disappearing, where the Chern insulating phase in the monolayer vanishes at the same time. Moreover, EuO is revealed as a suitable candidate for material realization. This work is not only valuable to the research of the quantum anomalous Hall effect but also offers a favorable platform to realize magnetic topologically insulating materials for spintronics applications.
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Electrocatalytic CO2 reduction (ECR) coupled with organic oxidation is a promising strategy to produce high value-added chemicals and improve energy efficiency. However, achieving the efficient redox coupling reaction is still challenging due to the lack of suitable electrocatalysts. Herein, we designed two bifunctional polyimides-linked covalent organic frameworks (PI-COFs) through assembling phthalocyanine (Pc) and porphyrin (Por) by non-toxic hydrothermal methods in pure water to realize the above catalytic reactions. Due to the high conductivity and well-defined active sites with different chemical environments, NiPc-NiPor COF performs efficient ECR coupled with methanol oxidation reaction (MOR) (Faradaic efficiency of CO (FECO) = 98.12%, partial current densities of CO (jCO) = 6.14 mA cm-2 for ECR, FEHCOOH = 93.75%, jHCOOH = 5.81 mA cm-2 for MOR at low cell voltage (2.1 V) and remarkable long-term stability). Furthermore, experimental evidences and density functional theory (DFT) calculations demonstrate that the ECR process mainly conducts on NiPc unit with the assistance of NiPor, meanwhile, the MOR prefers NiPor conjugating with NiPc. The two units of NiPc-NiPor COF collaboratively promote the coupled oxidation-reduction reaction. For the first time, this work achieves the rational design of bifunctional COFs for coupled heterogeneous catalysis, which opens a new area for crystalline material catalysts.
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While the difference in catalytic reactivity between mono- and multimetallic sites is often attributed to more than just the number of active sites, still few catalyst model systems have been developed to explore more underlying causal factors. In this work, we have elaborately designed and constructed three stable calix[4]arene (C4A)-functionalized titanium-oxo compounds, Ti-C4A, Ti4-C4A, and Ti16-C4A, with well-defined crystal structures, increasing nuclearity, and tunable light absorption capacity and energy levels. Among them, Ti-C4A and Ti16-C4A can be taken as model catalysts to compare the differences in reactivity between mono- and multimetallic sites. Taking CO2 photoreduction as the basic catalytic reaction, both compounds can achieve CO2-to-HCOO- conversion with high selectivity (close to 100%). Moreover, the catalytic activity of multimetallic Ti16-C4A is up to 2265.5 µmol g-1 h-1, which is at least 12 times higher than that of monometallic Ti-C4A (180.0 µmol g-1 h-1), and is the best-performing crystalline cluster-based photocatalyst known to date. Catalytic characterization combined with density functional theory calculations shows that in addition to the advantage of having more metal active sites (for adsorption and activation of more CO2 molecules), Ti16-C4A can effectively reduce the activation energy required for the CO2 reduction reaction by completing the multiple electron-proton transfer process rapidly with synergistic metal-ligand catalysis, thus exhibiting superior catalytic performance to that of monometallic Ti-C4A. This work provides a crystalline catalyst model system to explore the potential factors underlying the difference in catalytic reactivity between mono- and multimetallic sites.
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Selective oxidation of alcohols to aldehydes is an industrially significant chemical transformation. Herein, we report a mixed-valence polyoxovanadate-based metal-organic framework (MOF), (H2bix)5{[Cd(bix)2][VIV8VV7O36Cl]2}·3H2O (V-Cd-MOF), for catalyzing the additive-free oxidation of a series of aromatic alcohols with high selectivity and in nearly quantitative yield to the corresponding aldehydes with O2 as the oxidant. Experimental results, corroborated with density functional theory calculations, indicate that it is the synergistic operation of the dual active sites of the VIV-O-VV building units in the polyoxovanadate cluster that is responsible for the excellent catalytic performance observed: on the one hand, the exposed and readily accessible reduced VIV site is believed to activate O2, resulting in a reactive oxygen species for the subsequent activation and breaking of the substrate's Cα-H bond. On the other hand, the VV site coordinates with the alcoholic O atom to facilitate the cleavage of the O-H bond. The catalyst can be recycled by centrifugation and re-used at least five times with uncompromised performance. To our knowledge, V-Cd-MOF represents the first example of a polyoxometalate-based MOF catalyst for additive-free selective oxidation of alcohol to aldehyde with O2 as an oxidant.
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Weyl semimetals (WSMs) have attracted great attentions that provide intriguing platforms for exploring fundamental physical phenomena and future topotronics applications. Despite the fact that numerous WSMs are achieved, WSMs with long-distance distribution of Weyl points (WPs) in given material candidates remain elusive. Here, the emergence of intrinsic ferromagnetic WSMs in BaCrSe2 with the nontrivial nature explicitly confirmed by the Chern number and Fermi arc surface states analysis is theoretically demonstrated. Remarkably, unlike previous WSMs for which opposite chirality WPs are located very close to each other, the WPs of BaCrSe2 host a long-distance distribution, as much as half of the reciprocal space vector, suggesting that the WPs are highly robust and difficult to be annihilated by perturbations. The presented results not only advance the general understanding of magnetic WSMs but also put forward potential applications in topotronics.
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The photoredox-mediated iridium(III)/nickel(II)/3-acetoxyquinuclidine triple-synergistic catalysis was comprehensively investigated by taking a C(sp3 )-C(sp2 ) bond cross-coupling as a reaction model using density functional theory (DFT) calculations. The synergistic mechanism of the triple catalytic system includes a reductive quenching cycle (IrIII -*IrIII -IrII -IrIII ), an organocatalytic cycle, and a nickel catalytic cycle (NiII -NiI -NiIII -[NiIII ]â -NiII ). Electronic process analysis shows that 3-acetoxyquinuclidine acts as a hydrogen atom transfer (HAT) catalyst to regioselectively provide α-carbon centered radical. Due to more favorable oxidative addition of C-Br to Ni(I) than HAT to avoid the formation of stable Ni(II) species, the generated α-carbon centered radical prefers to be captured by oxidative addition product Ni(III) to form an unusual [NiIII ]â Câ species when 3-acetoxyquinuclidine was employed. These theoretical insights not only provide deep electronic process understanding of the photoredox-mediated iridium(III)/nickel(II) synergistic catalysis, but also clarify the electron-withdrawing group effect of quinuclidine, which has a potential guiding role for further development of new cross-coupling reactions.
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The understanding and manipulate of the second-order corner states are central to both fundamental physics and future topotronics applications. Despite the fact that numerous second-order topological insulators (SOTIs) are achieved, the efficient engineering in a given material remains elusive. Here, the emergence of 2D multiferroics SOTIs in SbAs and BP5 monolayers is theoretically demonstrated, and an efficient and straightforward way for engineering the nontrivial corner states by ferroelasticity and ferroelectricity is remarkably proposed. With ferroelectric polarization of SbAs and BP5 monolayers, the nontrivial corner states emerge in the mirror symmetric corners and are perpendicular to orientations of the in-plane spontaneous polarization. And remarkably the spatial distribution of the corner states can be effectively tuned by a ferroelastic switching. At the intermediate states of both ferroelectric and ferroelastic switchings, the corner states disappear. These finding not only combines exotic SOTIs with multiferroics but also pave the way for experimental discovery of 2D tunable SOTIs.