Observation of interband Berry phase in laser-driven crystals.

Ever since its discovery1, the notion of the Berry phase has permeated all branches of physics and plays an important part in a variety of quantum phenomena2. However, so far all its realizations have been based on a continuous evolution of the quantum state, following a cyclic path. Here we introduce and demonstrate a conceptually new manifestation of the Berry phase in light-driven crystals, in which the electronic wavefunction accumulates a geometric phase during a discrete evolution between different bands, while preserving the coherence of the process. We experimentally reveal this phase by using a strong laser field to engineer an internal interferometer, induced during less than one cycle of the driving field, which maps the phase onto the emission of higher-order harmonics. Our work provides an opportunity for the study of geometric phases, leading to a variety of observations in light-driven topological phenomena and attosecond solid-state physics.

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.

Boosting oxygen vacancies by modulating the morphology of Au decorated In2O3 with enhanced CO2 hydrogenation activity to CH3OH.

CO2 hydrogenation to methanol has become one of the most promising ways for CO2 utilization, however, the CO2 conversion rate and methanol selectivity of this reaction still need to be improved for industrial application. Here we investigated the structure-activity relationship for CO2 conversion to methanol of In2O3-based catalysts by modulating morphology and decorating Au. Three different Au/In2O3 catalysts were prepared, their activity follow the sequence of Au/In2O3-nanosphere (Au/In2O3-NS) > Au/In2O3-nanoplate (Au/In2O3-NP) > Au/In2O3-hollow microsphere (Au/In2O3-HM). Au/In2O3-NS exhibited the best performance with good CO2 conversion of 12.7%, high methanol selectivity of 59.8%, and large space time yield of 0.32 gCH3OH/(hr·gcat) at 300°C. The high performance of Au/In2O3-NS was considered as the presence of Au. It contributes to the creation of more surface oxygen vacancies, which further promoted the CO2 adsorption and facilitated CO2 activation to form the formate intermediates towards methanol. This work clearly suggests that the activity of In2O3 catalyst can be effective enhanced by structure engineering and Au decorating.

Design of Bifunctional Cu-SSZ-13@Mn2Cu1Al1Ox Core-Shell Catalyst with Superior Activity for the Simultaneous Removal of VOCs and NOx.

Synchronous control of volatile organic compounds (VOCs) and nitrogen oxides (NOx) is of great importance for ozone and PM2.5 pollution control. Balancing VOC oxidation and the NH3-SCR reaction is the key to achieving the simultaneous removal of these two pollutants. In this work, a vertically oriented Mn2Cu1Al1Ox nanosheet is grown in situ on the surface of Cu-SSZ-13 to synthesize a core-shell bifunctional catalyst (Cu-SSZ-13@Mn2Cu1Al1Ox) with multiple active sites. The optimized Cu-SSZ-13@Mn2Cu1Al1Ox catalyst delivered excellent performance for the simultaneous removal of VOCs and NOx with both 100% conversion at 300 °C in the presence of 5% water vapor. Physicochemical characterization and density functional theory (DFT) calculations revealed that Cu-SSZ-13@Mn2Cu1Al1Ox possesses more surface acidity and oxygen vacancies. The charge transfer between the core and shell is the intrinsic reason for the improved activity for both VOC and NOx removal. The molecular orbital theory is used to explain the different adsorption energies due to the different bonding modes between the core-shell and mixed individual catalysts. This work provides a novel strategy for designing efficient catalysts for the simultaneous removal of VOCs and NOx or other multiple pollutants.

Mechanistic Insight into the Promotion of the Low-Temperature NH3-SCR Activity over NiMnFeOx LDO Catalysts: A Combined Experimental and DFT Study.

Mn-based catalysts have attracted much attention in the field of the low-temperature NH3 selective catalytic reduction (NH3-SCR) of NO. However, their poor SO2 resistance, low N2 selectivity, and narrow operation window limit the industrial application of Mn-based oxide catalysts. In this work, NiMnFeOx catalysts were prepared by the layered double hydroxide (LDH)-derived oxide method, and the optimized Ni0.5Mn0.5Fe0.5Ox catalyst had the best denitration activity, excellent N2 selectivity, a wider active temperature range (100-250 °C), higher thermal stability, and better H2O and/or SO2 resistance. A transient reaction revealed that Ni0.5Mn0.5Fe0.5Ox inhibited the NH3 + O2 + NOx pathway to generate N2O, which may be the main reason for its improved N2 selectivity. Combining experimental measurements and density functional theory (DFT) calculations, we elucidated at the atomic level that sulfated NiMnFeOx (111) induces the adjustment of the acidity/basicity of up and down spins and the ligand field reconfiguration of the Mn sites, which improves the overall reactivity of NiMnFeOx catalysts. This work provides atomic-level insights into the promotion of NH3-SCR activity by NiMnFeOx composite oxides, which are important for the practical design of future low-temperature SCR technologies.

Sulfur Changes the Electrochemical CO2 Reduction Pathway over Cu Electrocatalysts.

Electrochemical CO2 reduction to value-added chemicals or fuels offers a promising approach to reduce carbon emissions and alleviate energy shortage. Cu-based electrocatalysts have been widely reported as capable of reducing CO2 to produce a variety of multicarbon products (e.g., ethylene and ethanol). In this work, we develop sulfur-doped Cu2 O electrocatalysts, which instead can electrochemically reduce CO2 to almost exclusively formate. We show that a dynamic equilibrium of S exists at the Cu2 O-electrolyte interface, and S-doped Cu2 O undergoes in situ surface reconstruction to generate active S-adsorbed metallic Cu sites during the CO2 reduction reaction (CO2 RR). Density functional theory (DFT) calculations together with in situ infrared absorption spectroscopy measurements show that the S-adsorbed metallic Cu surface can not only promote the formation of the *OCHO intermediate but also greatly suppress *H and *COOH adsorption, thus facilitating CO2 -to-formate conversion during the electrochemical CO2 RR.

DEC1 represses cardiomyocyte hypertrophy by recruiting PRP19 as an E3 ligase to promote ubiquitination-proteasome-mediated degradation of GATA4.

Although the pro-hypertrophic role of GATA binding protein 4 (GATA4) during cardiac hypertrophy has been well established, the negative regulatory mechanism to counteract its hyperactivation remains elusive. We hypothesized that the hyperactivation of GATA4 could be a result of loss of interaction between GATA4 with specific suppressors. Using high throughput mass spectrometry technology, we carried out a proteomic screen for endogenous suppressor of GATA4, which disassociated with GATA4 during the hypertrophic response in a cultured cardiac myoblast cell line (H9C2 cells). We identified differentiated embryo chondrocyte 1 (DEC1) negatively regulated the function of GATA4 through physical interaction and negatively regulated cardiac hypertrophy both in vivo and in vitro. Particularly, DEC1 promoted the ubiquitination and proteasome-mediated degradation of GATA4, but did not function as an E3 ligase. Again, using mass spectrometry technology, we systematically identified pre-mRNA processing factor 19 (PRP19) as a newfound E3 ligase, which promoted the K6-linked ubiquitination of GATA4 at its lysine 256. Functional experiments performed in cultured neonatal rat ventricular myocytes and H9C2 cells demonstrated that both DEC1 and PRP19 negatively regulated agonist-induced cardiomyocyte hypertrophic responses. Furthermore, rescue experiments performed in these cells revealed that DEC1 and PRP19 suppressed cardiomyocyte hypertrophy by inhibiting the function of GATA4. Our study thus defined the novel DEC1-PRP19-GATA4 axis to be a previously unknown mechanism in regulating cardiomyocyte hypertrophy. Although GATA4 is indispensable for normal cardiac function, harnessing DEC1- or PRP19-mediated negative regulation to counteract the hyperactivation of GATA4 might serve as a novel therapeutic strategy for pathological cardiac hypertrophy.

Chirality-driven topological electronic structure of DNA-like materials.

Topological aspects of the geometry of DNA and similar chiral molecules have received a lot of attention, but the topology of their electronic structure is less explored. Previous experiments revealed that DNA can efficiently filter spin-polarized electrons between metal contacts, a process called chiral-induced spin selectivity. However, the underlying correlation between chiral structure and electronic spin remains elusive. In this work, we reveal an orbital texture in the band structure, a topological characteristic induced by the chirality. We found that this orbital texture enables the chiral molecule to polarize the quantum orbital. This orbital polarization effect (OPE) induces spin polarization assisted by the spin-orbit interaction of a metal contact and leads to magnetoresistance and chiral separation. The orbital angular momentum of photoelectrons also plays an essential role in related photoemission experiments. Beyond chiral-induced spin selectivity, we predict that the orbital polarization effect could induce spin-selective phenomena even in achiral but inversion-breaking materials.

Elaboration of Aggregated Polysulfide Phases: From Molecules to Large Clusters and Solid Phases.

With the increasing strategies aimed at repressing shuttle problems in the lithium-sulfur battery, dissolved contents of polysulfides are significantly reduced. Except for solid-state Li2S2 and Li2S, aggregated phases of polysulfides remain unexplored, especially in well confined cathode material systems. Here, we report a series of nanosize polysulfide clusters and solid phases from an atomic perspective. The calculated phase diagram and formation energy evolution process demonstrate their stabilities and cohesive tendency. It is interesting to find that Li2S6 can stay in the solid state and contains short S3 chains, further leading to the unique stability and dense structure. Simulated electronic properties indicate reduced band gaps when polysulfides are aggregated, especially for solid phase Li2S6 with a band gap as low as 0.47 eV. Their dissolution behavior and conversion process are also investigated, which provides a more realistic model and gives further suggestions on the future design of the lithium-sulfur battery.

Enhanced Multiple Anchoring and Catalytic Conversion of Polysulfides by Amorphous MoS3 Nanoboxes for High-Performance Li-S Batteries.

The practical implementation of lithium-sulfur batteries is obstructed by poor conductivity, sluggish redox kinetics, the shuttle effect, large volume variation, and low areal loading of sulfur electrodes. Now, amorphous N-doped carbon/MoS3 (NC/MoS3 ) nanoboxes with hollow porous architectures have been meticulously designed as an advanced sulfur host. Benefiting from the enhanced conductivity by the N-doped carbon, reduced shuttle effect by the strong chemical interaction between unsaturated Mo and lithium polysulfides, improved redox reaction kinetics by the catalytic effect of MoS3 , great tolerance of volume variation and high sulfur loading arising from flexible amorphous materials with hollow-porous structures, the amorphous NC/MoS3 nanoboxes enabled sulfur electrodes to deliver a high areal capacity with superior rate capacity and decent cycling stability. The synthetic strategy can be generalized to fabricate other amorphous metal sulfide nanoboxes.

De Haas-van Alphen spectroscopy and magnetic breakdown in moiré graphene.

Quantum oscillations originating from the quantization of electron cyclotron orbits provide sensitive diagnostics of electron bands and interactions. We report on nanoscale imaging of the thermodynamic magnetization oscillations caused by the de Haas-van Alphen effect in moiré graphene. Scanning by means of superconducting quantum interference device (SQUID)-on-tip in Bernal bilayer graphene crystal axis-aligned to hexagonal boron nitride reveals large magnetization oscillations with amplitudes reaching 500 Bohr magneton per electron in weak magnetic fields, unexpectedly low frequencies, and high sensitivity to superlattice filling fraction. The oscillations allow us to reconstruct the complex band structure, revealing narrow moiré bands with multiple overlapping Fermi surfaces separated by unusually small momentum gaps. We identified sets of oscillations that violate the textbook Onsager Fermi surface sum rule, signaling formation of broad-band particle-hole superposition states induced by coherent magnetic breakdown.

[Efficient biosynthesis of γ-aminobutyric acid by rationally engineering the catalytic pH range of a glutamate decarboxylase from Lactobacillus plantarum].

γ-aminobutyric acid can be produced by a one-step enzymatic reaction catalyzed by glutamic acid decarboxylase. The reaction system is simple and environmentally friendly. However, the majority of GAD enzymes catalyze the reaction under acidic pH at a relatively narrow range. Thus, inorganic salts are usually needed to maintain the optimal catalytic environment, which adds additional components to the reaction system. In addition, the pH of solution will gradually rise along with the production of γ-aminobutyric acid, which is not conducive for GAD to function continuously. In this study, we cloned the glutamate decarboxylase LpGAD from a Lactobacillus plantarum capable of efficiently producing γ-aminobutyric acid, and rationally engineered the catalytic pH range of LpGAD based on surface charge. A triple point mutant LpGADS24R/D88R/Y309K was obtained from different combinations of 9 point mutations. The enzyme activity at pH 6.0 was 1.68 times of that of the wild type, suggesting the catalytic pH range of the mutant was widened, and the possible mechanism underpinning this increase was discussed through kinetic simulation. Furthermore, we overexpressed the Lpgad and LpgadS24R/D88R/Y309K genes in Corynebacterium glutamicum E01 and optimized the transformation conditions. An optimized whole cell transformation process was conducted under 40 ℃, cell mass (OD600) 20, 100 g/L l-glutamic acid substrate and 100 µmol/L pyridoxal 5-phosphate. The γ-aminobutyric acid titer of the recombinant strain reached 402.8 g/L in a fed-batch reaction carried out in a 5 L fermenter without adjusting pH, which was 1.63 times higher than that of the control. This study expanded the catalytic pH range of and increased the enzyme activity of LpGAD. The improved production efficiency of γ-aminobutyric acid may facilitate its large-scale production.

Unusual Spin Polarization in the Chirality-Induced Spin Selectivity.

Chirality-induced spin selectivity (CISS) refers to the fact that electrons get spin polarized after passing through chiral molecules in a nanoscale transport device or in photoemission experiments. In CISS, chiral molecules are commonly believed to be a spin filter through which one favored spin transmits and the opposite spin gets reflected; that is, transmitted and reflected electrons exhibit opposite spin polarization. In this work, we point out that such a spin filter scenario contradicts the principle that equilibrium spin current must vanish. Instead, we find that both transmitted and reflected electrons present the same type of spin polarization, which is actually ubiquitous for a two-terminal device. More accurately, chiral molecules play the role of a spin polarizer rather than a spin filter. The direction of spin polarization is determined by the molecule chirality and the electron incident direction. And the magnitude of spin polarization relies on local spin-orbit coupling in the device. Our work brings a deeper understanding on CISS and interprets recent experiments, for example, the CISS-driven anomalous Hall effect.

WBC-AMNet: Automatic classification of WBC images using deep feature fusion network based on focalized attention mechanism.

The recognition and classification of White Blood Cell (WBC) play a remarkable role in blood-related diseases (i.e., leukemia, infections) diagnosis. For the highly similar morphology of different WBC subtypes, it is too confused to classify the WBC effectively and accurately for visual observation of blood cell smears. This paper proposes a Deep Convolutional Neural Network (DCNN) with feature fusion strategies, named WBC-AMNet, for automatically classifying WBC subtypes based on focalized attention mechanism. To obtain more localized attention of CNN, the fusion features of the first and the last convolutional layer are extracted by focalized attention mechanism combining Squeeze-and-Excitation (SE) and Gather-Excite (GE) modules. The new method performs successfully in classifying monocytes, neutrophils, lymphocytes, and eosinophils on the complex background with an overall accuracy of 95.66%, better than that of general CNNs. The multi-classification accuracy of WBC-AMNet with the background segmentation is over 98% in all cases. In addition, Gradient-weighted Class Activation Mapping (Grad-CAM) is employed to visualize the attention heatmaps of different feature maps.

Unravelling the Mechanism of Intermediate-Temperature CO2 Interaction with Molten-NaNO3 -Salt-Promoted MgO.

The optimization of MgO-based adsorbents as advanced CO2 -capture materials is predominantly focused on their molten-salt modification, for which theoretical and experimental contributions provide great insights for their high CO2 -capture performance. The underlying mechanism of the promotion effect of the molten salt on CO2 capture, however, is a topic of controversy. Herein, advanced experimental characterization techniques, including in situ environmental transmission electron microscopy (eTEM) and CO2 chemisorption by diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS), transient 18 O-isotopic exchange, and density functional theory (DFT), are employed to elucidate the mechanism of the CO2 interaction with molten-salt-modified MgO in the 250-400 °C range. Herein, eTEM studies using low (2-3 mbar) and high (700 mbar) CO2 pressures illustrate the dynamic evolution of the molten NaNO3 salt promoted and unpromoted MgO carbonation with high magnification (<50 nm). The formation of 18 O-NaNO3 (use of 18 O2 ) and C16 O18 O following CO2 interaction, verifies the proposed reaction path: conversion of NO3 - (NO3 -  â†’ NO2 +  + O2- ), adsorption of NO2 + on MgO with significant weakening of CO2 adsorption strength, and formation of [Mg2+ … O2- ] ion pairs preventing the development of an impermeable MgCO3 shell, which largely increases the rate of bulk MgO carbonation.

A Novel Serum Biomarker Model to Discriminate Aortic Dissection from Coronary Artery Disease.

Background: The misdiagnosis of aortic dissection (AD) can lead to a catastrophic prognosis. There is currently a lack of stable serological indicators with excellent efficacy for the differential diagnosis of AD and coronary artery disease (CAD). A recent study has shown an association between AD and iron metabolism. Thus, we investigated whether iron metabolism could discriminate AD from CAD. Methods: This retrospective and multicenter cross-sectional study investigated the efficacy of biomarkers of iron metabolism for the differential diagnosis of AD. We collected biomarkers of iron metabolism, liver function, kidney function, and other biochemistry test, and further, logistic regression analysis was applied. Results: Between Oct. 8, 2020, and Mar. 1, 2021, we recruited 521 patients diagnosed with AD, CAD, and other cardiovascular diseases (OCDs) with the main symptoms of chest and back pain and assigned them to discovery set (n = 330) or validation set (n = 191). We found that six serum biomarkers, including serum iron, low-density lipoprotein, uric acid, transferrin, high-density lipoprotein, and estimated glomerular filtration rate, can serve as a novel comprehensive indicator (named FLUTHE) for the differential diagnosis of AD and CAD with a sensitivity of 0.954 and specificity of 0.905 to differentially diagnose AD and CAD more than 72 h past symptom onset. Conclusion: Our findings provide insight into the role of iron metabolism in diagnosing and distinguishing AD, which might in the future be a key component in AD diagnosis. Furthermore, we establish a novel model named "FLUTHE" with higher efficiency, safety, and economy, especially for patients with chest pain for more than 72 h.

Association of Daily Mean Temperature and Temperature Variability With Onset Risks of Acute Aortic Dissection.

Background The association between ambient temperature and cardiovascular diseases has been well established, but evidence of temporal changes in the risk of acute aortic dissection (AAD) onset is lacking. Methods and Results We conducted an 8-year time-series study based on data from 2120 patients diagnosed with AAD at Tongji Hospital (Wuhan, China). Daily meteorological parameters were measured in the study area. Spearman's rank correlation analysis was applied to measure the associations between daily meteorological data and air pollution indicators. A distributed lag nonlinear model following quasi-Poisson regression was used to express the nonlinear exposure-response relationships and lag effects of daily mean temperature and temperature variability on the occurrence of AAD. Considering a 25-day lag effect, lower or higher temperatures with reference to 25°C did not alter the onset risk of AAD. The lag effect of daily mean temperature on the incidence of AAD is statistically significant within 2 days, and the impact of daily mean temperature on the risk is most influential on the day. The exposure-response curve between daily mean temperature and onset risks of AAD at lag 0 showed that the extremely cold temperature (2.5th percentile, 0.5°C) significantly increased the AAD risk for the total (relative risk, 1.733; 95% CI, 1.130-2.658) and type A dissection (relative risk, 3.951; 95% CI, 1.657-9.418). Temperature variability within 1 week did not affect the onset risks of AAD for the total. Conclusions We confirmed that extremely cold temperatures significantly increased the AAD risk, which could contribute to early prevention and timely diagnosis of the disease.

[Effects of 12-week Tai Chi exercise on the microvascular reactivity of the middle-aged and elderly patients with mild hypertension and its mechanism].

Objective: To study the effects of 12-week Taijiquan exercise on the microvascular reactivity of middle-aged and elderly patients with mild hypertension and to explore the mechanisms of microvascular reactivity. Methods: Thirty patients with mild hypertension were divided into exercise group (53.8±6.3 years old) and control group (52.6±7.5 years old). The number and gender ratio of the two groups were the same. The exercise group performed Tai Chi exercise for 12 weeks, and the control group maintained the original lifestyle and did not do other regular sports. The two groups of subjects were tested for microvascular reactivity, blood pressure, serum nitric oxide content, and nitric oxide synthase activity before exercise intervention, 6th week and 12th week, respectively. Results: There was no significant difference in the basic values of each index between the two groups of subjects before the test (P＞ 0.05). In the 6th week, the microvascular reactivity (blood flow increase rate), systolic blood pressure, diastolic blood pressure, nitric oxide content, nitric oxide synthase activity of the exercise group did not significantly change from the basic value (P＞0.05). At the 12th week, the microvascular reactivity, nitric oxide content, c nitric oxide synthase activity were significantly higher than those of the base values and the control group (P＜0.05), but the systolic blood pressure and diastolic blood pressure were significantly lower than those of the base values and control group (P＜0.05). In the control group, there were no significant changes in the 6th and 12th week values of each index from the basic value (P＞0.05). Conclusion: Twelve weeks of Taijiquan exercise can improve the microvascular reactivity of middle-aged hypertensive patients, reduce blood pressure, and increase the nitric oxide content and c nitric oxide synthase of patients. The increase of endogenous nitric oxide production is one of the biological mechanisms of Tai Chi exercise to improve the microvascular responsiveness of hypertension patients.

Estimation of in-situ biogas upgrading in microbial electrolysis cells via direct electron transfer: Two-stage machine learning modeling based on a NARX-BP hybrid neural network.

With the increasing of data in wastewater treatment, data-driven machine learning models are useful for modeling biological processes and complex reactions. However, few data-driven models have been developed for simulating the microbial electrolysis cells (MECs) and traditional models are too ambiguous to comprehend the mechanisms. In this study, a new general data-driven two-stage model was firstly developed to predict CH4 production from in-situ biogas upgrading in the biocathode MECs via direct electron transfer (DET), named NARX-BP hybrid neural networks. Compared with traditional one-stage model, the model could well predict methane production via DET with excellent performance (all R2 and MES of 0.918 and 6.52 × 10-2, respectively) and reveal the mechanisms of biogas upgrading, for the new systematical modeling approach could improve the versatility and applicability by inputting significant intermediate variables. In addition, the model is generally available to support long-term prediction and optimal operation for anaerobic digestion or complex MEC systems.

Engineering d-p Orbital Hybridization in Single-Atom Metal-Embedded Three-Dimensional Electrodes for Li-S Batteries.

Single-atom metal catalysts (SACs) are used as sulfur cathode additives to promote battery performance, although the material selection and mechanism that govern the catalytic activity remain unclear. It is shown that d-p orbital hybridization between the single-atom metal and the sulfur species can be used as a descriptor for understanding the catalytic activity of SACs in Li-S batteries. Transition metals with a lower atomic number are found, like Ti, to have fewer filled anti-bonding states, which effectively bind lithium polysulfides (LiPSs) and catalyze their electrochemical reaction. A series of single-atom metal catalysts (Me = Mn, Cu, Cr, Ti) embedded in three-dimensional (3D) electrodes are prepared by a controllable nitrogen coordination approach. Among them, the single-atom Ti-embedded electrode has the lowest electrochemical barrier to LiPSs reduction/Li2 S oxidation and the highest catalytic activity, matching well with the theoretical calculations. By virtue of the highly active catalytic center of single-atom Ti on the conductive transport network, high sulfur utilization is achieved with a low catalyst loading (1 wt.%) and a high area-sulfur loading (8 mg cm-2 ). With good mechanical stability for bending, these 3D electrodes are suitable for fabricating bendable/foldable Li-S batteries for wearable electronics.