De-Pinning Fermi Level and Accelerating Surface Kinetics with an ALD Finish Boost the Fill Factor of BiVO4 Photoanodes to 44.

With the rapid development of performance and long-term stability, bismuth vanadate (BiVO4 ) has emerged as the preferred photoanode in photoelectrochemical tandem devices. Although state-of-the-art BiVO4 photoanodes realize a saturated photocurrent density approaching the theoretical maximum, the fill factor (FF) is still inferior, pulling down the half-cell applied bias photon-to-current efficiency (HC-ABPE). Among the major fundamental limitations are the Fermi level pinning and sluggish surface kinetics at the low applied potentials. This work demonstrates that the plasma-assisted atomic layer deposition technique is capable of addressing these issues by seamlessly installing an angstrom-scale FeNi-layer between BiVO4 and electrolyte. Not only this ultrathin FeNi layer serves as an efficient OER cocatalyst, more importantly, it also effectively passivates the surface states of BiVO4 , de-pins the surface Fermi level, and enlarges the built-in voltage, allowing the photoanode to make optimal use of the photogenerated holes for achieving high FF up to 44% and HC-ABPE to 2.2%. This study offers a new approach for enhancing the FF of photoanodes and provides guidelines for designing efficient unassisted solar fuel devices.

Bidirectional causality between the levels of blood lipids and endometriosis: a two-sample mendelian randomization study.

BACKGROUND: Observational studies have found a correlation between the levels of blood lipids and the development and progression of endometriosis (EM). However, the causality and direction of this correlation is unclear. This study aimed to examine the bidirectional connection between lipid profiles and the risk of EM using publicly available genome-wide association study (GWAS) summary statistics. METHODS: Eligible exposure variables such as levels of triglycerides (TG), total cholesterol (TC), low-density lipoprotein (LDL), and high-density lipoprotein (HDL) were selected using a two-sample Mendelian randomization (MR) analysis method following a series of quality control procedures. Data on EM were obtained from the publicly available Finnish database of European patients. Inverse variance weighted (IVW), MR Egger, weighted median, and weighted mode methods were used to analyze the causal relationship between lipid exposure and EM, exclude confounders, perform sensitivity analyses, and assess the stability of the results. Reverse MR analyses were performed with EM as exposure and lipid results as study outcomes. RESULTS: IVW analysis results identified HDL as a protective factor for EM, while TG was shown to be a risk factor for EM. Subgroup analyses based on the site of the EM lesion identified HDL as a protective factor for EM of the uterus, while TG was identified a risk factor for the EM of the fallopian tube, ovary, and pelvic peritoneum. Reverse analysis did not reveal any effect of EM on the levels of lipids. CONCLUSION: Blood lipids, such as HDL and TG, may play an important role in the development and progression of EM. However, EM does not lead to dyslipidemia.

Prompt Hole Extraction Suppresses V5+ Dissolution and Sustains Large-Area BiVO4 Photoanodes for Over 2100 h Water Oxidation.

Nanostructured bismuth vanadate (BiVO4) is at the forefront of emerging photoanodes in photoelectrochemical tandem devices for solar water splitting owing to the suitable band edge position and efficient charge separation capability. However, the (photo)chemical corrosion involving V5+ dissolution limits the long-term stability of BiVO4. Herein, guided by DFT calculations, we introduce an ALD-derived NiOx catalyst layer on BiVO4 to stabilize the surface Bi-O bonds, facilitate hole extraction, and thus suppress the V5+ dissolution. At the same time, the ALD NiOx catalyst layer could efficiently suppress the surface recombination and accelerate the surface OER kinetics, boosting the half-cell applied bias photon-to-current efficiency of BiVO4 to 2.05%, as well as a fill factor of 47.1%. By adding trace NaVO3 to the electrolyte, the NiOx/BiVO4 photoanode with an illumination area of 10.5 cm2 shows a record operational stability of more than 2100 h.

Organelle Imaging with Terahertz Scattering-Type Scanning Near-Field Microscope.

Organelles play core roles in living beings, especially in internal cellular actions, but the hidden information inside the cell is difficult to extract in a label-free manner. In recent years, terahertz (THz) imaging has attracted much attention because of its penetration depth in nonpolar and non-metallic materials and label-free, non-invasive and non-ionizing ability to obtain the interior information of bio-samples. However, the low spatial resolution of traditional far-field THz imaging systems and the weak dielectric contrast of biological samples hinder the application of this technology in the biological field. In this paper, we used an advanced THz scattering near-field imaging method for detecting chloroplasts on gold substrate with nano-flatness combined with an image processing method to remove the background noise and successfully obtained the subcellular-grade internal reticular structure from an Arabidopsis chloroplast THz image. In contrast, little inner information could be observed in the tea chloroplast in similar THz images. Further, transmission electron microscopy (TEM) and mass spectroscopy (MS) were also used to detect structural and chemical differences inside the chloroplasts of Arabidopsis and tea plants. The preliminary results suggested that the interspecific different THz information is related to the internal spatial structures of chloroplasts and metabolite differences among species. Therefore, this method could open a new way to study the structure of individual organelles.

Atomic layer deposited nickel sulfide for bifunctional oxygen evolution/reduction electrocatalysis and zinc-air batteries.

Rechargeable Zn-air batteries are a promising type of metal-air batteries for high-density energy storage. However, their practical use is limited by the use of costly noble-metal electrocatalysts for the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) occurred at the air electrode of the Zn-air batteries. This work reports a new non-precious bifunctional OER/ORR electrocatalyst of NiSx/carbon nanotubes (CNTs), which is made by atomic layer deposition (ALD) of nickel sulfide (NiSx) on CNTs, for the applications for the air electrode of the Zn-air batteries. The NiSx/CNT electrocatalyst on a carbon cloth electrode exhibits a low OER overpotential of 288 mV to reach 10 mA cm-2in current density, and the electrocatalyst on a rotating disk electrode exhibits a half-wave ORR potential of 0.81 V in alkaline electrolyte. With the use of the NiSx/CNT electrocatalyst for the air electrode, the fabricated aqueous rechargeable Zn-air batteries show a fairly good maximum output power density of 110 mW cm-2, which highlights the great promise of the ALD NiSx/CNT electrocatalyst for Zn-air batteries.

Image fusion based on multiscale transform and sparse representation to enhance terahertz images.

High-quality terahertz (THz) images are vital to integrated circuit (IC) manufacturing. Due to the unique sensitivity of THz waves to different materials, the images obtained from the point-spread function (PSF) model have fewer image details and less texture information in some frequency bands. This paper presents an image fusion technique to enhance the resolution of THz IC images. The source images obtained from the PSF model are processed by a fusion method combining a multiscale transform (MST) and sparse representation (SR). The low-pass band is handled by sparse representation, and the high-pass band is fused by the conventional "max-absolute" rule. From both objective and visual perspectives, four popular multiscale transforms-the Laplacian pyramid, the ratio of low-pass pyramids, the dual-tree complex wavelet transform and the curvelet transform-are thoroughly compared at different decomposition levels ranging from one to four. This work demonstrates the feasibility of using image fusion to enhance the resolution of THz IC images.

Convolutional neural network model based on terahertz imaging for integrated circuit defect detections.

Detection of integrated circuit (IC) defects is vital in IC manufacturing. Traditional defect detection methods have relied on scanning electron microscopy and X-ray imaging techniques that are time consuming and destructive. Hence, in this paper we considered terahertz imaging as a label-free and nondestructive alternative. This study aimed to use a convolutional neural network model (CNN) to improve the performance of the terahertz imaging IC detection system. First, we constructed a terahertz imaging IC dataset and analyzed it. Subsequently, a new CNN structure was proposed based on the VGG16 network. Finally, it was optimized based on its structure and dropout rate. The method proposed above can improve IC defects detection accuracy of THz imaging. Most significantly, this work will promote the application of terahertz imaging in practice and provide a foundation to further research in relevant fields.

Dynamics of a nutrient-phytoplankton model with random phytoplankton mortality.

This study formulates a stochastic nutrient-phytoplankton model which incorporates the effect of white noise on phytoplankton growth. The global existence and uniqueness of a positive solution, stochastic boundedness, and stochastically asymptotic stability are well explored. A stochastic ecological reproductive index R0s is formulated to characterize the global dynamics. The theoretical analysis demonstrates that, if R0s<1, then phytoplankton dies out with probability one; if R0s>1 and some other conditions hold, then there exists an invariant and asymptotically stable density of the system and the approach involves integral Markov semigroups theory. Numerical simulations are presented to illustrate the analytical findings and to investigate the long-time effect of water temperature, light, nutrients, and environmental noise on the dynamic evolution of phytoplankton.

Research Advances of Amorphous Metal Oxides in Electrochemical Energy Storage and Conversion.

Amorphous metal oxides (AMOs) have aroused great enthusiasm across multiple energy areas over recent years due to their unique properties, such as the intrinsic isotropy, versatility in compositions, absence of grain boundaries, defect distribution, flexible nature, etc. Here, the materials engineering of AMOs is systematically reviewed in different electrochemical applications and recent advances in understanding and developing AMO-based high-performance electrodes are highlighted. Attention is focused on the important roles that AMOs play in various energy storage and conversion technologies, such as active materials in metal-ion batteries and supercapacitors as well as active catalysts in water splitting, metal-air batteries, and fuel cells. The improvements of electrochemical performance in metal-ion batteries and supercapacitors are reviewed regarding the enhancement in active sites, mechanical strength, and defect distribution of amorphous structures. Furthermore, the high electrochemical activities boosted by AMOs in various fundamental reactions are elaborated on and they are related to the electrocatalytic behaviors in water splitting, metal-air batteries, and fuel cells. The applications in electrochromism and high-conducting sensors are also briefly discussed. Finally, perspectives on the existing challenges of AMOs for electrochemical applications are proposed, together with several promising future research directions.

Terahertz Spectroscopic Signatures of Microcystin Aptamer Solution Probed with a Microfluidic Chip.

Terahertz signature detection of biological samples in aqueous solution remains a great challenge due to the strong terahertz absorption of water. Here we propose a new preparation process for fabricating a microfluidic chip and use it as an effective sensor to probe the terahertz absorption signatures of microcystin aptamer (a linear single-stranded DNA with 60 nucleotides) dissolved in TE buffer with different concentrations. The microfluidic chip made of silicon includes thousands of 2.4 µm × 2.4 µm square-cross-section channels. One repeatable terahertz absorption signature is detected and recognized around 830 GHz, fitted to a Lorentz oscillator. This signature is theorized to originate from the bending of hydrogen bonds formed between adjacent hydrated DNA bases surrounded by water molecules. Furthermore, the low-lying vibrational modes are also investigated by molecular dynamics simulations which suggest that strong resonant oscillations are highly probable in the 815⁻830 GHz frequency band.

Characterization of Nucleobases in Broadband Terahertz Spectra from 0.5 to 10 THz with the Air-Biased-Coherent-Detection Technique.

Terahertz time-domain spectroscopy (THz-TDS) is an effective coherent detection technique for deeply understanding the structures and functions of biomolecules. However, generally not full information in the whole THz range can be obtained due to the limited detection bandwidth (usually less than 5 THz) of the traditional THz-TDS systems. In this paper, effective THz absorption spectra in 0.5⁻10 THz range of five typical nucleobases of DNA/RNA are characterized with a super broadband THz detection technique, called the air-biased- coherent-detection (THz-ABCD) technique. Few unexpected characteristic absorption peaks appeared in the low-frequency region and meanwhile a series of anticipated characteristic absorption peaks are found in the high-frequency region. The fingerprint spectra of these nucleobases are helpful for further analysis on the vibration and twisting behavior of hydrogen bonds, van der Waals and electrostatic forces etc. between and within DNA/RNA biomolecules.

Epigenetic Changes are Associated with Programmed Cell Death Induced by Heat Stress in Seedling Leaves of Zea mays.

Histone modification plays a crucial role in regulation of chromatin architecture and function, responding to adverse external stimuli. However, little is known about a possible relationship between epigenetic modification and programmed cell death (PCD) in response to environmental stress. Here, we found that heat stress induced PCD in maize seedling leaves which was characterized by chromatin DNA laddering and DNA strand breaks detected by a terminal deoxynucleotidyl transferase-mediated dUTP nick end labeling (TUNEL) test. The activities of the reactive oxygen species (ROS)-related enzymes superoxide dismutase (SOD), peroxidase (POD) and catalase (CAT) were progressively increased over time in the heat-treated seedlings. However, the concentration of H2O2 remained at relatively lower levels, while the concentration of superoxide anion ([Formula: see text]) was increased, accompanied by the occurrence of higher ion leakage rates after heat treatment. The total acetylation levels of histones H3K9, H4K5 and H3 were significantly increased, whereas the di-methylation level of histone H3K4 was unchanged and the di-methylation level of histone H3K9 was decreased in the seedling leaves exposed to heat stress compared with the control seedlings, accompanied by increased nucleolus size indicative of chromatin decondensation. Furthermore, treatment of seedlings with trichostatin A (TSA), which always results in genomic histone hyperacetylation, caused an increase in the [Formula: see text] level within the cells. The results suggested that heat stress persistently induced [Formula: see text], leading to PCD in association with histone modification changes in the maize leaves.

Histone acetylation associated up-regulation of the cell wall related genes is involved in salt stress induced maize root swelling.

BACKGROUND: Salt stress usually causes crop growth inhibition and yield decrease. Epigenetic regulation is involved in plant responses to environmental stimuli. The epigenetic regulation of the cell wall related genes associated with the salt-induced cellular response is still little known. This study aimed to analyze cell morphological alterations in maize roots as a consequence of excess salinity in relation to the transcriptional and epigenetic regulation of the cell wall related protein genes. RESULTS: In this study, maize seedling roots got shorter and displayed swelling after exposure to 200 mM NaCl for 48 h and 96 h. Cytological observation showed that the growth inhibition of maize roots was due to the reduction in meristematic zone cell division activity and elongation zone cell production. The enlargement of the stele tissue and cortex cells contributed to root swelling in the elongation zone. The cell wall is thought to be the major control point for cell enlargement. Cell wall related proteins include xyloglucan endotransglucosylase (XET), expansins (EXP), and the plasma membrane proton pump (MHA). RT-PCR results displayed an up-regulation of cell wall related ZmEXPA1, ZmEXPA3, ZmEXPA5, ZmEXPB1, ZmEXPB2 and ZmXET1 genes and the down-regulation of cell wall related ZmEXPB4 and ZmMHA genes as the duration of exposure was increased. Histone acetylation is regulated by HATs, which are often correlated with gene activation. The expression of histone acetyltransferase genes ZmHATB and ZmGCN5 was increased after 200 mM NaCl treatment, accompanied by an increase in the global acetylation levels of histones H3K9 and H4K5. ChIP experiment showed that the up-regulation of the ZmEXPB2 and ZmXET1 genes was associated with the elevated H3K9 acetylation levels on the promoter regions and coding regions of these two genes. CONCLUSIONS: These data suggested that the up-regulation of some cell wall related genes mediated cell enlargement to possibly mitigate the salinity-induced ionic toxicity, and different genes had specific function in response to salt stress. Histone modification as a mediator may contribute to rapid regulation of cell wall related gene expression, which reduces the damage of excess salinity to plants.

Comparison of chromatin epigenetic modification patterns among root meristem, elongation and maturation zones in maize (Zea mays L.).

Plant roots mainly consist of division, elongation and maturation regions. Histone modifications of chromatin play a vital role in plant cell growth and differentiation. However, there has been no systematic attempt to investigate the distribution patterns of histone modifications in the different plant root zones. In this study, histone H3 acetylation (H3K9ac), histone H4 acetylation (H4K5ac), and histone H3 methylation (H3K4me2, H3K4me3, H3K9me1, H3K9me2, and H3K27me2) levels and distribution patterns were examined in the root meristem, elongation and maturation zones of maize primary roots. Overall, the cells of the maturation zone displayed the highest level of multiple histone modifications. The lowest level of histone modification was detected in the root meristem. H3K9ac was enriched in the euchromatin and nucleoli of most nuclei from the elongation and maturation zones. The nucleoli of more than 60% of cells from all root regions were labeled by H4K5ac. In only a small proportion of cells (less than 7%), knobs showed H4K5ac signals. H3K4me2 and H3K4me3 were specifically detected in euchromatin. H3K9me1, H3K9me2 and H3K27me2 labeled heterochromatin and euchromatin in all the root tissues analyzed. Over 30% of elongation and maturation cells exhibited H3K9me1 signals around knobs, approximately 5% of maturation cells showed signals of H3K9me2 around knobs, and H3K27me2 was stained weakly in approximately 95% of maturation cells in knobs. Analysis of the genomic patterns of histone modifications across functionally distinct regions of maize roots reveals a root zone-specific chromatin distribution.

Promoter-associated histone acetylation is involved in the osmotic stress-induced transcriptional regulation of the maize ZmDREB2A gene.

Epigenetic modifications play a key role in the transcriptional regulation of stress-induced gene expression in plants. In this study, we showed that the overall acetylation levels of histone H3 lysine 9 (H3K9) and H4 lysine 5 (H4K5) in the genome were increased in maize seedlings after mannitol treatment (to mimic osmotic stress). Mannitol treatment significantly induced the upregulation of the maize osmotic stress responsive gene Zea mays dehydration-responsive element binding protein 2A (ZmDREB2A), whereas abscisic acid (ABA) did not result in the induction of this gene. The application of exogenous ABA under osmotic stress conditions strongly repressed the induction of the ZmDREB2A gene. Chromatin immunoprecipitation and chromatin accessibility by real-time PCR experiments revealed that the promoter region of the ZmDREB2A gene was quickly hyperacetylated and decondensed after the mannitol treatment, suggesting that the promoter region is poised for histone acetylation to allow for fast induction of the ZmDREB2A gene. However, under osmotic stress conditions, the ABA treatment decreased the acetylation status and chromatin accessibility to micrococcal nuclease. These results suggest that osmotic stress activates the transcription of the ZmDREB2A gene by increasing the levels of acetylated histones H3K9 and H4K5 associated with the ZmDREB2A promoter region.

Yeast ß-glucan promotes antiviral type I interferon response via dectin-1.

Pseudorabies virus (PRV), an alphaherpesvirus, is a neglected zoonotic pathogen. Dectin-1 sensing of ß-glucan (BG) induces trained immunity, which can possibly form a new strategy for the prevention of viral infection. However, alphaherpesvirus including PRV have received little to no investigation in the context of trained immunity. Here, we found that BG pretreatment improved the survival rate, weight loss outcomes, alleviated histological injury and decreased PRV copy number of tissues in PRV-infected mice. Type I interferons (IFNs) including IFN-α/ß levels in serum were significantly increased by BG. However, these effects were abrogated in the presence of Dectin-1 antagonist. Dectin-1-mediated effect of BG was also confirmed in porcine and murine macrophages. These results suggested that BG have effects on type I IFNs with antiviral property involved in Dectin-1. In piglets, oral or injected immunization with BG and PRV vaccine could significantly elevated the level of PRV-specific IgG and type I IFNs. And it also increased the antibody levels of porcine reproductive and respiratory syndrome virus vaccine and classical swine fever vaccine that were later immunized, indicating a broad-spectrum effect on improving vaccine immunity. On the premise that the cost was greatly reducing, the immunological effect of oral was better than injection administration. Our findings highlighted that BG induced type I IFNs related antiviral effect against PRV involved in Dectin-1 and potential application value as a feed additive to help control the spread of PRV and future emerging viruses.

Near-Field Terahertz Morphological Reconstruction Nanoscopy for Subsurface Imaging of Protein Layers.

Protein layers formed on solid surfaces have important applications in various fields. High-resolution characterization of the morphological structures of protein forms in the process of developing protein layers has significant implications for the control of the layer's quality as well as for the evaluation of the layer's performance. However, it remains challenging to precisely characterize all possible morphological structures of protein in various forms, including individuals, networks, and layers involved in the formation of protein layers with currently available methods. Here, we report a terahertz (THz) morphological reconstruction nanoscopy (THz-MRN), which can reveal the nanoscale three-dimensional structural information on a protein sample from its THz near-field image by exploiting an extended finite dipole model for a thin sample. THz-MRN allows for both surface imaging and subsurface imaging with a vertical resolution of ∼0.5 nm, enabling the characterization of various forms of proteins at the single-molecule level. We demonstrate the imaging and morphological reconstruction of single immunoglobulin G (IgG) molecules, their networks, a monolayer, and a heterogeneous double layer comprising an IgG monolayer and a horseradish peroxidase-conjugated anti-IgG layer. The established THz-MRN presents a useful approach for the label-free and nondestructive study of the formation of protein layers.

Terahertz spectra of proteinuria and non-proteinuria.

In clinical practice, proteinuria detection is of great significance in the diagnosis of kidney diseases. Dipstick analysis is used in most outpatient settings to semi-quantitatively measure the urine protein concentration. However, this method has limitations for protein detection, and alkaline urine or hematuria will cause false positive results. Recently, terahertz time-domain spectroscopy (THz-TDS) with strong hydrogen bonding sensitivity has been proven to be able to distinguish different types of biological solutions, which means that protein molecules in urine may have different THz spectral characteristics. In this study, we performed a preliminary clinical study investigating the terahertz spectra of 20 fresh urine samples (non-proteinuria and proteinuria). The results showed that the concentration of urine protein was positively correlated with the absorption of THz spectra at 0.5-1.2 THz. At 1.0 THz, the pH values (6, 7, 8, and 9) had no significant effect on the THz absorption spectra of urine proteins. The terahertz absorption of proteins with a high molecular weight (albumin) was greater than that of proteins with a low molecular weight (ß2-microglobulin) at the same concentration. Overall, THz-TDS spectroscopy for the qualitative detection of proteinuria is not affected by pH and has the potential to discriminate between albumin and ß2-microglobulin in urine.

Terahertz spectroscopic monitoring and analysis of citrus leaf water status under low temperature stress.

Low temperature stress, in the form of chilling and freezing, is one of the major environmental factors impacting on citrus yield, which changes plant's water state and results in the crops' sub-health or injury. The innovative terahertz (THz) spectroscopy and imaging based sensing technology has been shown to be a suitable tool for plant leaf water status determination, due to THz radiation's innate sensitivity to hydrogen bond vibration in aqueous solutions, which is usually related to plant phenotype change. We demonstrate experimentally that the THz absorption coefficient of leaf could be used for distinguishing plant's physiological stress status, exhibiting clear decreasing or increasing trend under chilling or freezing stress respectively. The underlying rationale might be that membrane damage shows a diverse pattern, changing the intra- or extra-cellular liquid environments, likely being linked to the various THz spectral characteristics. There were different adaptations in leaf morphology, leading to different leaf density, which in turn affects the water volume fraction. Moreover, different patterns of the dynamic equilibrium state of free water and bound water under chilling and freezing treatment were revealed by THz spectroscopy. Here, THz spectroscopic monitoring has shown unique potential for judging citrus's low temperature stress state through bio-water detection and discrimination.

ABA-mediated inhibition of seed germination is associated with ribosomal DNA chromatin condensation, decreased transcription, and ribosomal RNA gene hypoacetylation.

Seed germination is a highly organized biological process accompanied by many cellular and metabolic changes. The ribosomal RNA (rRNA) gene, which forms the nucleolus at interphase and is transcribed for ribosome production and protein synthesis, has an important role during seed germination. In this study, we report that there is a decondensation of ribosomal DNA (rDNA) chromatin during seed germination accompanied with increased rRNA gene expression and overall genomic hyperacetylation. Analysis of the rRNA gene promoter region by using chromatin immunoprecipitation (ChIP) shows that there is an increase in acetylation levels at the rRNA gene promoter region. Application of seed germination inhibitor abscisic acid (ABA) suppresses rDNA chromatin decondensation, the expression of rRNA genes and global genomic acetylation. The further ChIP experiments show that ABA treatment hinders the elevation of acetylation levels in the promoter region of the rRNA gene. The data together indicate that ABA treatment inhibits seed germination, which is associated with rDNA chromatin condensation, decreased transcription and rRNA gene hypoacetylation.