Enhancing Zn2+ Storage Performance by Constructing the Interfaces Between VO2 and Co-N-C Layers.

Vanadium oxides have aroused attention as cathode materials in aqueous zinc-ion batteries (AZIBs) due to their low cost and high safety. However, low ion diffusion and vanadium dissolution often lead to capacity decay and deteriorating stability during cycling. Herein, vanadium dioxides (VO2) nanobelts are coated with a single-atom cobalt dispersed N-doped carbon (Co-N-C) layer via a facile calcination strategy to form Co-N-C layer coated VO2 nanobelts (VO2@Co-N-C NBs) for cathodes in AZIBs. Various in-/ex situ characterizations demonstrate the interfaces between VO2 layers and Co-N-C layers can protect the VO2 NBs from collapsing, increase ion diffusion, and enhance the Zn2+ storage performance. Additional density functional theory (DFT) simulations demonstrate that Co─O─V bonds between VO2 and Co-N-C layers can enhance interfacial Zn2+ storage. Moreover, the VO2@Co-N-C NBs provided an ultrahigh capacity (418.7 mAh g-1 at 1 A g-1), outstanding long-term stability (over 8000 cycles at 20 A g-1), and superior rate performance.

B-N Co-Doped Graphene: Stability and Catalytic Activity in Oxygen Reduction Reaction - A Theoretical Insight.

We systematically investigated the stable configurations and catalytic activity in the Oxygen Reduction Reaction (ORR) of graphene co-doped with boron and nitrogen (B-N) using first-principles methods. Compared to single B/N doping, co-doping with BN is energetically favored. We found that intermediate species of ORR process adsorb on boron atoms, which act as catalytic sites. The presence of neighboring nitrogen atoms around boron plays a crucial role in modulating the catalytic activity of boron. For the same adsorption configuration, the adsorption energy of the adsorbate increases with the number of neighboring nitrogen atoms around boron and generally correlates positively with the number of electrons gained by the adsorbate. Regarding the catalytic activity of ORR, excessively strong adsorption of adsorbates impedes their hydrogenation. The best substrates for ORR catalytic activity are B-N-graphene and N-B2-graphene, with the rate-determining step being the hydrogenation of *OO and overpotentials of 0.49 V and 0.54 V, respectively.

Strong Protein Adhesives through Lanthanide-enhanced Structure Folding and Stack Density.

Generating strong adhesion by engineered proteins has the potential for high technical applications. Current studies of adhesive proteins are primarily limited to marine organisms, e.g., mussel adhesive proteins. Here, we present a modular engineering strategy to generate a type of exotic protein adhesives with super strong adhesion behaviors. In the protein complexes, the lanmodulin (LanM) underwent α-helical conformational transition induced by lanthanides, thereby enhancing the stacking density and molecular interactions of adhesive protein. The resulting adhesives exhibited outstanding lap-shear strength of ≈31.7 MPa, surpassing many supramolecular and polymer adhesives. The extreme temperature (-196 to 200 °C) resistance capacity and underwater adhesion performance can significantly broaden their practical application scenarios. Ex vivo and in vivo experiments further demonstrated the persistent adhesion performance for surgical sealing and healing applications.

Raman Fiber Photometry for Understanding Mitochondrial Superoxide Burst and Extracellular Calcium Ion Influx upon Acute Hypoxia in the Brain of Freely Moving Animals.

Developing a novel tool capable of real-time monitoring and simultaneous quantitation of multiple molecules in mitochondria across the whole brain of freely moving animals is the key bottleneck for understanding the physiological and pathological roles that mitochondria play in the brain events. Here we built a Raman fiber photometry, and created a highly selective non-metallic Raman probe based on the triple-recognition strategies of chemical reaction, charge transfer, and characteristic fingerprint peaks, for tracking and simultaneous quantitation of mitochondrial O2.- , Ca2+ and pH at the same location in six brain regions of free-moving animal upon hypoxia. It was found that mitochondrial O2.- , Ca2+ and pH changed from superficial to deep brain regions upon hypoxia. It was discovered that hypoxia-induced mitochondrial O2.- burst was regulated by ASIC1a, leading to mitochondrial Ca2+ overload and acidification. Furthermore, we found the overload of mitochondrial Ca2+ was mostly attributed to the influx of extracellular Ca2+ .

Unravelling the role of charge transfer state during ultrafast intersystem crossing in compact organic chromophores.

When organic electron donor (D) and acceptor (A) chromophores are linked together, an electron transfer (ET) state can take place. When a short bridge such as one Sigma bond is used to link the donor and the acceptor, complete charge separation is difficult to access and one usually observes an intramolecular charge transfer (CT) state instead. Due to the inevitable coupling between the donor and the acceptor in compact organic chromophores, the most common decay pathway for the CT state is charge recombination, which may lead to a distinct longer wavelength fluorescence emission or non-radiative dissipation of the excited state energy. However, recent studies have shown that unique excited state dynamics can be observed when the CT state is involved during both forward and backward intersystem crossing (ISC) from singlet excited states to triplet excited states in organic chromophores. Analysis of the mechanism for ISC involving the CT state has received much attention over the last decade. In this perspective, we present a collection of molecular design rationales, spectroscopy and theoretical investigations that provide insights into the mechanism of the ISC involving the CT state in compact organic chromophores. We hope that this perspective will prove beneficial for researchers to design novel compact organic chromophores with a predictable ISC property for future biochemical and optoelectronic applications.

Characterization of the promoter of the nitrate transporter-encoding gene nrtA in Aspergillus nidulans.

Aspergillus nidulans nrtA encodes a nitrate transporter that plays an important role in the [Formula: see text] assimilatory process. Many studies have focused on protein functions rather than gene regulation. The knowledge of nrtA[Formula: see text] uptake process, particularly in the regulation mechanism of transcription factors AreA and NirA on nrtA transcription, is very limited. Herein, we investigated the transcriptional regulation of nrtA in response to various N-sources in detail and characterized the promoter activity of nrtA. We confirmed that nrtA was induced by [Formula: see text] and repressed by preferred N-sources. Additionally, for the first time, we found that the transcription of nrtA increased under N-starvation conditions. AreA mediates nrtA transcription under both [Formula: see text] and N-starvation conditions, while NirA is effective only under [Formula: see text] conditions. All of the proposed AreA and NirA binding sites in the promoter region were capable of binding to their corresponding transcription factors in vitro. In vivo, all of the NirA binding sites showed regulation activities, but to AreA, only several of the initiation-codon-proximal binding sites participated in nrtA transcription. Moreover, the active binding sites contributed in different degrees of regulation strength to nrtA transcription, which is unrelated to the distance between the binding sites and initiation codon. These results provided an extensive map of nrtA promoter, defining the functional regulatory elements of A. nidulans nrtA.

Ultrafast spectroscopy of biliverdin dimethyl ester in solution: pathways of excited-state depopulation.

Biliverdin is a bile pigment that has a very low fluorescence quantum yield in solution, but serves as a chromophore in far-red fluorescent proteins being developed for bio-imaging. In this work, excited-state dynamics of biliverdin dimethyl ether (BVE) in solvents were investigated using femtosecond (fs) and picosecond (ps) time-resolved absorption and fluorescence spectroscopy. This study is the first fs timescale investigation of BVE in solvents, and therefore revealed numerous dynamics that were not resolved in previous, 200 ps time resolution measurements. Viscosity- and isotope-dependent experiments were performed to identify the contributions of isomerization and proton transfer to the excited-state dynamics. In aprotic solvents, a ∼2 ps non-radiative decay accounts for 95% of the excited-state population loss. In addition, a minor ∼30 ps emissive decay pathway is likely associated with an incomplete isomerization process around the C15[double bond, length as m-dash]C16 double bond that results in a flip of the D-ring. In protic solvents, the dynamics are more complex due to hydrogen bond interactions between solute and solvent. In this case, the ∼2 ps decay pathway is a minor channel (15%), whereas ∼70% of the excited-state population decays through an 800 fs emissive pathway. The ∼30 ps timescale associated with isomerization is also observed in protic solvents. The most significant difference in protic solvents is the presence of a >300 ps timescale in which BVE can decay through an emissive state, in parallel with excited-state proton transfer to the solvent. Interestingly, a small fraction of a luminous species, which we designate lumin-BVE (LBVE), is present in protic solvents.

Ultrafast internal conversion dynamics of bilirubin bound to UnaG and its N57A mutant.

Fluorescent proteins (FPs) have become fundamental tools for live cell imaging. Most FPs currently used are members of the green fluorescent protein super-family, but new fluorophores such as bilin-FPs are being developed and optimized. In particular, the UnaG FP incorporates bilirubin (BR) as a chromophore, enhancing its fluorescence quantum yield by three orders of magnitude relative to that in solution. To investigate the mechanism of this dramatic enhancement and provide a basis for further engineering of UnaG and other tetrapyrrole-based fluorophores, we performed picosecond fluorescence and femtosecond transient absorption measurements of BR bound to UnaG and its N57A site-directed mutant. The dynamics of wt-UnaG, which has a fluorescence QY of 0.51, are largely homogeneous, showing an excited state relaxation of ∼200 ps, and a 2.2 ns excited-state lifetime decay with a kinetic isotope effect (KIE) of 1.1 for D2O vs. H2O buffer. In contrast, for UnaG N57A (fluorescence QY 0.01) the results show a large spectral inhomogeneity with excited state decay timescales of 47 and 200 ps and a KIE of 1.4. The non-radiative deactivation of the excited state is limited by proton transfer. The loss of direct hydrogen bonds to the endo-vinyl dipyrrinone moiety of BR leads to high flexibility and structural heterogeneity of UnaG N57A, as seen in the X-ray crystal structure.

A fraction of NADH in solution is "dark": Implications for metabolic sensing via fluorescence lifetime.

The metabolic cofactor and energy carrier NADH (nicotinamide adenine dinucleotide, reduced) has fluorescence yield and lifetime that depends strongly on conformation, a fact that has enabled metabolic monitoring of cells via FLIM (Fluorescence Lifetime Microscopy). Using femtosecond fluorescence upconversion, we show that this molecule in solution participates in ultrafast self-quenching along with both bulk solvent relaxation and spectral relaxation on 1.4 and 26 ps timescales. This, in effect, means up to a third of NADH is effectively "dark" for FLIM in the 400-500 nm observation window commonly employed. Methods to compensate for, avoid or measure dark species corrections are outlined.

Charged Nanowire-Directed Growth of Amorphous Calcium Carbonate Nanosheets in a Mixed Solvent for Biomimetic Composite Films.

Bio-inspired mineralization is an effective way for fabricating complex inorganic materials, which inspires us to develop new methods to synthesize materials with fascinating properties. In this article, we report that the charged tellurium nanowires (TeNWs) can be used as biomacromolecule analogues to direct the formation of amorphous calcium carbonate (ACC) nanosheets (ACCNs) in a mixed solvent. The effects of surface charges and the concentration of the TeNWs on the formation of ACCNs have been investigated. Particularly, the produced ACCNs can be functionalized by Fe3O4 nanoparticles to produce magnetic ACC/Fe3O4 hybrid nanosheets that can be used to construct ACC/Fe3O4 composite films through a self-evaporation process. Moreover, sodium alginate-ACC nanocomposite films with remarkable toughness and good transmittance can also be fabricated by using such ACCNs as nanoscale building blocks. This mineralization approach in a mixed solvent using charged TeNWs as biomacromolecule analogues provides a new way for the synthesis of ACCNs, which can be used as nanoscale building blocks for the fabrication of biomimetic composite films.

Quantitative evaluation on internal seeing induced by heat-stop of solar telescope.

heat-stop is one of the essential thermal control devices of solar telescope. The internal seeing induced by its temperature rise will degrade the imaging quality significantly. For quantitative evaluation on internal seeing, an integrated analysis method based on computational fluid dynamics and geometric optics is proposed in this paper. Firstly, the temperature field of the heat-affected zone induced by heat-stop temperature rise is obtained by the method of computational fluid dynamics calculation. Secondly, the temperature field is transformed to refractive index field by corresponding equations. Thirdly, the wavefront aberration induced by internal seeing is calculated by geometric optics based on optical integration in the refractive index field. This integrated method is applied in the heat-stop of the Chinese Large Solar Telescope to quantitatively evaluate its internal seeing. The analytical results show that the maximum acceptable temperature rise of heat-stop is up to 5 Kelvins above the ambient air at any telescope pointing directions under the condition that the root-mean-square of wavefront aberration induced by internal seeing is less than 25nm. Furthermore, it is found that the magnitude of wavefront aberration gradually increases with the increase of heat-stop temperature rise for a certain telescope pointing direction. Meanwhile, with the variation of telescope pointing varying from the horizontal to the vertical direction, the magnitude of wavefront aberration decreases at first and then increases for the same heat-stop temperature rise.

Heat-stop structure design with high cooling efficiency for large ground-based solar telescope.

A heat-stop is one of the most important thermal control devices for a large ground-based solar telescope. For controlling the internal seeing effect, the temperature difference between the heat-stop and the ambient environment needs to be reduced, and a heat-stop with high cooling efficiency is required. In this paper, a novel design concept for the heat-stop, in which a multichannel loop cooling system is utilized to obtain higher cooling efficiency, is proposed. To validate the design, we analyze and compare the cooling efficiency for the multichannel and existing single-channel loop cooling system under the same conditions. Comparative results show that the new design obviously enhances the cooling efficiency of the heat-stop, and the novel design based on the multichannel loop cooling system is obviously better than the existing design by increasing the thermal transfer coefficient.

Tuning the Electronic Property of Reconstructed Atomic Ni-CuO Cluster Supported on N/O-C for Electrocatalytic Oxygen Evolution.

Electrochemical activation usually accompanies in situ atom rearrangement forming new catalytic sites with higher activity due to reconstructed atomic clusters or amorphous phases with abundant dangling bonds, vacancies, and defects. By harnessing the pre-catalytic process of reconstruction, a multilevel structure of CuNi alloy nanoparticles encapsulated in N-doped carbon (CuNi nanoalloy@N/C) transforms into a highly active compound of Ni-doped CuO nanocluster supported on (N/O-C) co-doped C. Both the exposure of accessible active sites and the activity of individual active sites are greatly improved after the pre-catalytic reconstruction. Manipulating the Cu/Ni ratios of CuNi nanoalloy@N/C can tailor the electronic property and d-band center of the high-active compound, which greatly optimizes the energetics of oxygen evolution reaction (OER) intermediates. This interplay among Cu, Ni, C, N, and O modifies the interface, triggers the active sites, and regulates the work functions, thereby realizing a synergistic boost in OER.

Phase division and recognition of crystal HRTEM images based on machine learning and deep learning.

The High Resolution Transmission Electron Microscope (HRTEM) images provide valuable insights into the atomic microstructure, dislocation patterns, defects, and phase characteristics of materials. However, the current analysis and research of HRTEM images of crystal materials heavily rely on manual expertise, which is labor-intensive and susceptible to subjective errors. This study proposes a combined machine learning and deep learning approach to automatically partition the same phase regions in crystal HRTEM images. The entire image is traversed by a sliding window to compute the amplitude spectrum of the Fast Fourier Transform (FFT) in each window. The generated data is transformed into a 4-dimensional (4D) format. Principal component analysis (PCA) on this 4D data estimates the number of feature regions. Non-negative matrix factorization (NMF) then decomposes the data into a coefficient matrix representing feature region distribution, and a feature matrix corresponding to the FFT magnitude spectra. Phase recognition based on deep learning enables identifying the phase of each feature region, thereby achieving automatic segmentation and recognition of phase regions in HRTEM images of crystals. Experiments on zirconium and oxide nanoparticle HRTEM images demonstrate the proposed method achieve the consistency of manual analysis. Code and supplementary material are available at https://github.com/rememberBr/HRTEM2.

Robotic Actuation-Mediated Quantitative Mechanogenetics for Noninvasive and On-Demand Cancer Therapy.

Cell mechanotransduction signals are important targets for physical therapy. However, current physiotherapy heavily relies on ultrasound, which is generated by high-power equipment or amplified by auxiliary drugs, potentially causing undesired side effects. To address current limitations, a robotic actuation-mediated therapy is developed that utilizes gentle mechanical loads to activate mechanosensitive ion channels. The resulting calcium influx precisely regulated the expression of recombinant tumor suppressor protein and death-associated protein kinase, leading to programmed apoptosis of cancer cell line through caspase-dependent pathway. In stark contrast to traditional gene therapy, the complete elimination of early- and middle-stage tumors (volume ≤ 100 mm3) and significant growth inhibition of late-stage tumor (500 mm3) are realized in tumor-bearing mice by transfecting mechanogenetic circuits and treating daily with quantitative robotic actuation in a form of 5 min treatment over the course of 14 days. Thus, this massage-derived therapy represents a quantitative strategy for cancer treatment.

FFT pattern recognition of crystal HRTEM image with deep learning.

Rapid analysis and processing of large quantities of data obtained from in-situ transmission electron microscope (TEM) experiments can save researchers from the burdensome manual analysis work. The method mentioned in this paper combines deep learning and computer vision technology to realize the rapid automatic processing of end-to-end crystal high-resolution transmission electron microscope (HRTEM) images, which has great potential in assisting TEM image analysis. For the fine-grained result, the HRTEM image is divided into multiple patches by sliding window, and 2D fast Fourier transform (FFT) is performed, and then all FFT images are inputted into the designed LCA-Unet to extract bright spots. LCA-Unet combines local contrast and attention mechanism on the basis of U-net. Even if the bright spots in FFT images are weak, the proposed neural network can extract bright spots effectively. Using computer vision and the information of bright spots above mentioned, the automatic FFT pattern recognition is completed by three steps. First step is to calculate the precise coordinates of the bright spots, the lattice spacings and the inter-plane angles in each patch. Second step is to match the lattice spacing and the angles with the powder diffraction file (PDF) to determine the material phase of each patch. Third step is to merge the patches with same phase. Taking the HRTEM image of zirconium and its oxide nanoparticles as an example, the results obtained by the proposed method are basically consistent with manual identification. Thus the approach could be used to automatically and effectively find the phase region of interest. It takes about 3 s to process a 4 K × 4 K HRTEM image on a modern desktop computer with NVIDIA GPU.

An Analytical Model of Dynamic Power Losses in eGaN HEMT Power Devices.

In this work, we present an analytical model of dynamic power losses for enhancement-mode AlGaN/GaN high-electron-mobility transistor power devices (eGaN HEMTs). To build this new model, the dynamic on-resistance (Rdson) is first accurately extracted via our extraction circuit based on a double-diode isolation (DDI) method using a high operating frequency of up to 1 MHz and a large drain voltage of up to 600 V; thus, the unique problem of an increase in the dynamic Rdson is presented. Then, the impact of the current operation mode on the on/off transition time is evaluated via a dual-pulse-current-mode test (DPCT), including a discontinuous conduction mode (DCM) and a continuous conduction mode (CCM); thus, the transition time is revised for different current modes. Afterward, the discrepancy between the drain current and the real channel current is qualitative investigated using an external shunt capacitance (ESC) method; thus, the losses due to device parasitic capacitance are also taken into account. After these improvements, the dynamic model will be more compatible for eGaN HEMTs. Finally, the dynamic power losses calculated via this model are found to be in good agreement with the experimental results. Based on this model, we propose a superior solution with a quasi-resonant mode (QRM) to achieve lossless switching and accelerated switching speeds.

Embedding Atomically Dispersed Iron Sites in Nitrogen-Doped Carbon Frameworks-Wrapped Silicon Suboxide for Superior Lithium Storage.

Silicon suboxide (SiOx ) has attracted widespread interest as Li-ion battery (LIB) anodes. However, its undesirable electronic conductivity and apparent volume effect during cycling impede its practical applications. Herein, sustainable rice husks (RHs)-derived SiO2 are chosen as a feedstock to design SiOx /iron-nitrogen co-doped carbon (Fe-N-C) materials. Using a facile electrospray-carbonization strategy, SiOx nanoparticles (NPs) are encapsulated in the nitrogen-doped carbon (N-C) frameworks decorating atomically dispersed iron sites. Systematic characterizations including high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure (XAFS) verify the existence of Fe single atoms and typical coordination environment. Benefiting from its structural and compositional merits, the SiOx /Fe-N-C anode delivers significantly improved discharge capacity of 799.1 mAh g-1 , rate capability, and exceptional durability, compared with pure SiO2 and SiOx /N-C, which has been revealed by the density functional theory (DFT) calculations. Additionally, the electrochemical tests and in situ X-ray diffraction (XRD) analysis reveal the oxidation of Lix Si phase and the storage mechanism. The synthetic strategy is universal for the design and synthesis of metal single atoms/clusters dispersed N-C frameworks encapsulated SiOx NPs. Meanwhile, this work provides impressive insights into developing various LIB anode materials suffering from inferior conductivity and huge volume fluctuations.

Does financial inclusion help alleviate household poverty and vulnerability in China?

This paper investigates the impact of financial Inclusion on household poverty and vulnerability by constructing a household financial inclusion index using the China Household Finance Survey 2015. It is found that financial Inclusion significantly reduces the probability of poverty and vulnerability of households and has a more significant impact on vulnerable groups such as rural and urban low-income people. Further, financial Inclusion has a more significant effect on poor families that do not receive government support for poverty alleviation and can complement co-insurance mechanisms to help families better cope with vulnerabilities caused by synergistic community shocks. Finally, promoting entrepreneurship and improving risk management capabilities are the main channels of financial Inclusion.

Renal adverse reactions of tyrosine kinase inhibitors in the treatment of tumours: A Bayesian network meta-analysis.

Objectives: Tumours remain a serious threat to human life. Following rapid progress in oncology research, tyrosine kinase inhibitors have been used to treat multiple tumour types. Given the great influence of kidneys on pharmacokinetics, renal toxicities associated with TKIs have attracted attention. However, the TKIs with the lowest risks of renal impairment are unclear. In this study, we conducted a Bayesian network meta-analysis to compare the incidence of renal impairment among different TKIs in patients with tumours. Methods and analysis: Six databases (PubMed, EMBASE, The Cochrane Library, Chinese National Knowledge Infrastructure, Wanfang Data, and China Biomedical Literature Database) were electronically searched from inception to 1 November 2021 to identify randomized controlled trials on the incidence of renal impairment for different TKIs in patients with tumours. Two reviewers independently screened the literature, extracted data, and assessed the risk of bias of the included studies. Then, a pairwise meta-analysis was conducted using Stata version 13, and network meta-analysis within the Bayesian framework was conducted using R software version 3.5.3 with the package "gemtc 0.8-2" recalling JAGS (version 4.3.0). Results: Overall, 34 randomized controlled trials were included in this study. Although renal toxicity was common among patients receiving TKIs, the incidence and severity greatly differed among the drugs and studies. Elevated creatinine and protein levels were the most common nephrotoxic events, whereas haematuria was relatively rare. Among TKIs, nintedanib and ripretinib carried the lowest risks of renal impairment. Conclusion: TKIs displayed different profiles of renal toxicity because of their different targets and underlying mechanisms. Clinicians should be aware of the risks of renal impairment to select the optimal treatment and improve patient adherence to treatment. Systematic Review Registration: [www.crd.york.ac.uk/prospero/], identifier [CRD42022295853].