TiO2 Electron Transport Layer with p-n Homojunctions for Efficient and Stable Perovskite Solar Cells.

Low-temperature processed electron transport layer (ETL) of TiO2 that is widely used in planar perovskite solar cells (PSCs) has inherent low carrier mobility, resulting in insufficient photogenerated electron transport and thus recombination loss at buried interface. Herein, we demonstrate an effective strategy of laser embedding of p-n homojunctions in the TiO2 ETL to accelerate electron transport in PSCs, through localized build-in electric fields that enables boosted electron mobility by two orders of magnitude. Such embedding is found significantly helpful for not only the enhanced crystallization quality of TiO2 ETL, but the fabrication of perovskite films with larger-grain and the less-trap-states. The embedded p-n homojunction enables also the modulation of interfacial energy level between perovskite layers and ETLs, favoring for the reduced voltage deficit of PSCs. Benefiting from these merits, the formamidinium lead iodide (FAPbI3) PSCs employing such ETLs deliver a champion efficiency of 25.50%, along with much-improved device stability under harsh conditions, i.e., maintain over 95% of their initial efficiency after operation at maximum power point under continuous heat and illumination for 500 h, as well as mixed-cation PSCs with a champion efficiency of 22.02% and over 3000 h of ambient storage under humidity stability of 40%. Present study offers new possibilities of regulating charge transport layers via p-n homojunction embedding for high performance optoelectronics.

Temperature-Induced Interface Hybridization of WC Boosts NiCu Activity for Alkaline Hydrogen Oxidation Reaction.

The development of non-precious hydrogen oxidation reaction (HOR) catalysts is a major challenge for the commercialization of Pt-free fuel cells. Herein, a temperature-induced phase hybridization method is reported that greatly improves the catalytic performance of NiCu alloy for the HOR. The migration of W atoms hybridizes the interface of tungsten oxide (WOx) and tungsten carbide (WC) at the onset reduction temperature of WOx, leading to a greatly weakened H binding energy and an optimized OH binding energy, which endows NiCuW/WOx-WC@WC with favorable stability and CO resistance during HOR. The hybridization catalysts deliver a high mass activity of 29.37 mA mg-1 Ni and reach a peak power of 298 mW.cm-2 in H2-O2 anion exchange membrane fuel cells (AEMFCs).

Two new sesterterpenoids from Atractylodes japonica Koidz. ex Kitam.

Two new sesterterpenoids, atractylodes japonica terpenoid acid I (1) and atractylodes japonica terpenoid aldehyde I (2), were isolated from the rhizomes of Atractylodes japonica Koidz. ex Kitam together with ten known compounds (3-12). Their structures were elucidated on the basis of comprehensive spectroscopic analysis (1D/2D NMR, HRESIMS and IR). In addition, all of these isolated compounds were evaluated for their cytotoxic activities against human gastric cancer cell MGC-803 and human hepatocellular cancer cell HepG-2. Most of them exhibited moderate to weak inhibitory effects with IC50 values in the range of 25.15-88.85 µM except for 9-12.

The causal association between artificial sweeteners and the risk of cancer: a Mendelian randomization study.

Artificial sweeteners (ASs) have been widely added to food and beverages because of their properties of low calories and sweet taste. However, whether the consumption of ASs is causally associated with cancer risk is not clear. Here, we utilized the two-sample Mendelian randomization (MR) method to study the potential causal association. Genetic variants like single-nucleotide polymorphisms (SNPs) associated with exposure (AS consumption) were extracted from a genome-wide association study (GWAS) database including 64 949 Europeans and the influence of confounding was removed. The outcome was from 98 GWAS data and included several types of cancers like lung cancer, colorectal cancer, stomach cancer, breast cancer, and so on. The exposure-outcome SNPs were harmonized and then MR analysis was performed. The inverse-variance weighted (IVW) with random effects was used as the main analytical method accompanied by four complementary methods: MR Egger, weighted median, simple mode, and weighted mode. Sensitivity analyses consisted of heterogeneity, pleiotropy, and leave-one-out analysis. Our results demonstrated that ASs added to coffee had a positive association with high-grade and low-grade serous ovarian cancer; ASs added to tea had a positive association with oral cavity and pharyngeal cancers, but a negative association with malignant neoplasm of the bronchus and lungs. No other cancers had a genetic causal association with AS consumption. Our MR study revealed that AS consumption had no genetic causal association with major cancers. Larger MR studies or RCTs are needed to investigate small effects and support this conclusion.

Daphnetin alleviates silica-induced pulmonary inflammation and fibrosis by regulating the PI3K/AKT1 signaling pathway in mice.

Silicosis is a hazardous occupational disease caused by inhalation of silica, characterized by persistent lung inflammation that leads to fibrosis and subsequent lung dysfunction. Moreover, the complex pathophysiology of silicosis, the challenges associated with early detection, and the unfavorable prognosis contribute to the limited availability of treatment options. Daphnetin (DAP), a natural lactone, has demonstrated various pharmacological properties, including anti-inflammatory, anti-fibrotic, and pulmonary protective effects. However, the effects of DAP on silicosis and its molecular mechanisms remain uncover. This study aimed to evaluate the therapeutic effects of DAP against pulmonary inflammation and fibrosis using a silica-induced silicosis mouse model, and investigate the potential mechanisms and targets through network pharmacology, proteomics, molecular docking, and cellular thermal shift assay (CETSA). Here, we found that DAP significantly alleviated silica-induced lung injury in mice with silicosis. The results of H&E staining, Masson staining, and Sirius red staining indicated that DAP effectively reduced the inflammatory response and collagen deposition over a 28-day period following lung exposure to silica. Furthermore, DAP reduced the number of TUNEL-positive cells, increased the expression levels of Bcl-2, and decreased the expression of Bax and cleaved caspase-3 in the mice with silicosis. More importantly, DAP suppressed the expression levels of NLRP3 signaling pathway-related proteins, including NLRP3, ASC, and cleaved caspase-1, thereby inhibiting silica-induced lung inflammation. Further studies demonstrated that DAP possesses the ability to inhibit the epithelial mesenchymal transition (EMT) induced by silica through the inhibition of the TGF-ß1/Smad2/3 signaling pathway. The experimental results of proteomic analysis found that the PI3K/AKT1 signaling pathway was the key targets of DAP to alleviate lung injury induced by silica. DAP significantly inhibited the activation of the PI3K/AKT1 signaling pathway induced by silica in lung tissues. The conclusion was also verified by the results of molecular and CETSA. To further verify this conclusion, the activity of PI3K/AKT1 signaling pathway was inhibited in A549 cells using LY294002. When the A549 cells were pretreated with LY294002, the protective effect of DAP on silica-induced injury was lost. In conclusion, the results of this study suggest that DAP alleviates pulmonary inflammation and fibrosis induced by silica by modulating the PI3K/AKT1 signaling pathway, and holds promise as a potentially effective treatment for silicosis.

Reconstruction Strategy for Upper Extremity Defects After Bone Tumor Resection Based on 3D Customized Bone Cement Mold.

BACKGROUND: Reconstructing bone defects in the upper extremities and restoring their functions poses a significant challenge. In this study, we describe a novel workflow for designing and manufacturing customized bone cement molds using 3D printing technology to reconstruct upper extremity defects after bone tumor resection. METHODS: Computer tomography data was acquired from the unaffected upper extremities to create a detachable mold, which can be customized to fit the joint precisely by shaping the bone cement accordingly. Fourteen patients who underwent reconstructive surgery following bone tumor resection in the proximal humerus (13 cases) or distal radius (1 case) between January 2014 and December 2022 were retrospectively evaluated. The medical records of this case series were reviewed for the demographic, radiological, and operative data. Metastasis, local recurrence, and complication were also reviewed. Additionally, Musculoskeletal Tumor Society Score (MSTS) and Visual Analogue Scale (VAS) were used to assess clinical outcomes. RESULTS: The mean follow-up period was 49.36 ± 15.18 months (range, 27-82 months). At the end of follow-up, there were no cases of metastasis or recurrence, and patients did not experience complications such as infection, dislocation, or implant loosening. Two cases complicated with subluxation (14.3%), and 1 case underwent revision surgery for prosthetic fracture (7.1%). The average MSTS score was 23.2 ± 1.76 (77.4%, range, 66.7%-86.7%), and the postoperative VAS score was 1.86 ± 1.03 (range, 1-4), which was significantly lower than that before surgery (average preoperative VAS score was 5.21 ± 2.00 (range, 2-8)) (P < .001). CONCLUSION: Customized 3D molds can be utilized to shape bone cement prostheses, which may serve as a potential alternative for reconstructing the proximal humerus and distal radius following en bloc resection of bone tumors. This reconstruction strategy offers apparent advantages, including precise matching of articular surfaces and comparatively reduced costs.

The value of low-intensity pulsed ultrasound in reducing ovarian injury caused by chemotherapy in mice.

BACKGROUND: Ovarian damage and follicle loss are major side effects of chemotherapy in young female patients with cancer. However, effective strategies to prevent these injuries are still lacking. The purpose of this study was to verify low-intensity pulsed ultrasound (LIPUS) can reduce ovarian injury caused by chemotherapy and to explore its underlying mechanisms in mice model. METHODS: The mice were randomly divided into the Control group, Cisplatin group, and Cisplatin + LIPUS group. The Cisplatin group and Cisplatin + LIPUS group were intraperitoneally injected with cisplatin every other day for a total of 10 injections, and the Control group was injected with saline. On the second day of each injection, the Cisplatin + LIPUS group received irradiation, whereas the other two groups received sham irradiation. We used a variety of biotechnologies to detect the differences in follicle count, granulosa cell apoptosis, fibrosis, transcriptome level, oxidative damage, and inflammation in differently treated mice. RESULT: LIPUS was able to reduce primordial follicle pool depletion induced by cisplatin and inhibit the apoptosis of granulosa cells. Transcriptomic results confirmed that LIPUS can reduce ovarian tissue injury. We demonstrated that LIPUS can relieve ovarian fibrosis by inhibiting TGF-ß1/Smads pathway. Meanwhile, it can reduce the oxidative damage and reduced the mRNA levels of proinflammatory cytokines caused by chemotherapy. CONCLUSION: LIPUS can reduce the toxic effects of chemotherapy drugs on ovaries, inhibit ovarian fibrosis, reduce the inflammatory response, and redcue the oxidative damage, reduce follicle depletion and to maintain the number of follicle pools.

Constructing copper Phthalocyanine/Molybdenum disulfide (CuPc/MoS2) S-scheme heterojunction with S-rich vacancies for enhanced Visible-Light photocatalytic CO2 reduction.

Constructing a heterojunction by combining two semiconductors with similar band structures is a successful approach to obtaining photocatalysts with high efficiency. Herein, a CuPc/DR-MoS2 heterojunction involving copper phthalocyanine (CuPc) and molybdenum disulfide with S-rich vacancies (13.66%) is successfully prepared by the facile hydrothermal method. Experimental results and theoretical calculations firmly demonstrated that photoelectrons exhibit an S-scheme charge transfer mechanism in the CuPc/DR-MoS2 heterojunction. The S-scheme heterojunction system has proven significant advantages in promoting the charge separation and transfer of photogenerated carriers, enhancing visible-light responsiveness, and achieving robust photoredox capability. As a result, the optimized 3CuPc/DR-MoS2 S-scheme heterojunction exhibits photocatalytic yields of CO and CH4 at 200 and 111.6 µmol g-1h-1, respectively. These values are four times and 4.5 times greater than the photocatalytic yields of pure DR-MoS2. This study offers novel perspectives on the advancement of innovative and highly effective heterojunction photocatalysts.

Intragrain impurity annihilation for highly efficient and stable perovskite solar cells.

Intragrain impurities can impart detrimental effects on the efficiency and stability of perovskite solar cells, but they are indiscernible to conventional characterizations and thus remain unexplored. Using in situ scanning transmission electron microscopy, we reveal that intragrain impurity nano-clusters inherited from either the solution synthesis or post-synthesis storage can revert to perovskites upon irradiation stimuli, leading to the counterintuitive amendment of crystalline grains. In conjunction with computational modelling, we atomically resolve crystallographic transformation modes for the annihilation of intragrain impurity nano-clusters and probe their impacts on optoelectronic properties. Such critical fundamental findings are translated for the device advancement. Adopting a scanning laser stimulus proven to heal intragrain impurity nano-clusters, we simultaneously boost the efficiency and stability of formamidinium-cesium perovskite solar cells, by virtual of improved optoelectronic properties and relaxed intra-crystal strain, respectively. This device engineering, inspired and guided by atomic-scale in situ microscopic imaging, presents a new prototype for solar cell advancement.

Phenol as proton shuttle and buffer for lithium-mediated ammonia electrosynthesis.

Ammonia is a crucial component in the production of fertilizers and various nitrogen-based compounds. Now, the lithium-mediated nitrogen reduction reaction (Li-NRR) has emerged as a promising approach for ammonia synthesis at ambient conditions. The proton shuttle plays a critical role in the proton transfer process during Li-NRR. However, the structure-activity relationship and design principles for effective proton shuttles have not yet been established in practical Li-NRR systems. Here, we propose a general procedure for verifying a true proton shuttle and established design principles for effective proton shuttles. We systematically evaluate several classes of proton shuttles in a continuous-flow reactor with hydrogen oxidation at the anode. Among the tested proton shuttles, phenol exhibits the highest Faradaic efficiency of 72 ± 3% towards ammonia, surpassing that of ethanol, which has been commonly used so far. Experimental investigations including operando isotope-labelled mass spectrometry proved the proton-shuttling capability of phenol. Further mass transport modeling sheds light on the mechanism.

Long-term continuous ammonia electrosynthesis.

Ammonia is crucial as a fertilizer and in the chemical industry and is considered to be a carbon-free fuel1. Ammonia electrosynthesis from nitrogen under ambient conditions offers an attractive alternative to the Haber-Bosch process2,3, and lithium-mediated nitrogen reduction represents a promising approach to continuous-flow ammonia electrosynthesis, coupling nitrogen reduction with hydrogen oxidation4. However, tetrahydrofuran, which is commonly used as a solvent, impedes long-term ammonia production owing to polymerization and volatility problems. Here we show that a chain-ether-based electrolyte enables long-term continuous ammonia synthesis. We find that a chain-ether-based solvent exhibits non-polymerization properties and a high boiling point (162 °C) and forms a compact solid-electrolyte interphase layer on the gas diffusion electrode, facilitating ammonia release in the gas phase and ensuring electrolyte stability. We demonstrate 300 h of continuous operation in a flow electrolyser with a 25 cm2 electrode at 1 bar pressure and room temperature, and achieve a current-to-ammonia efficiency of 64 ± 1% with a gas-phase ammonia content of approximately 98%. Our results highlight the crucial role of the solvent in long-term continuous ammonia synthesis.

Sampling rate requirement for accurate calculation of heart rate and its variability based on the electrocardiogram.

Objective. To develop analytical formulas which can serve as quantitative guidelines for the selection of the sampling rate for the electrocardiogram (ECG) required to calculate heart rate (HR) and heart rate variability (HRV) with a desired level of accuracy.Approach. We developed analytical formulas which relate the ECG sampling rate to conservative bounds on HR and HRV errors: (i) one relating HR and sampling rate to a HR error bound and (ii) the others relating sampling rate to HRV error bounds (in terms of root-mean-square of successive differences (RMSSD) and standard deviation of normal sinus beats (SDNN)). We validated the formulas using experimental data collected from 58 young healthy volunteers which encompass a wide HR and HRV ranges through strenuous exercise.Main results. The results strongly supported the validity of the analytical formulas as well as their tightness. The formulas can be used to (i) predict an upper bound of inaccuracy in HR and HRV for a given sampling rate in conjunction with HR and HRV as well as to (ii) determine a sampling rate to achieve a desired accuracy requirement at a given HR or HRV (or its range).Significance. HR and its variability (HRV) derived from the ECG have been widely utilized in a wide range of research in physiology and psychophysiology. However, there is no established guideline for the selection of the sampling rate for the ECG required to calculate HR and HRV with a desired level of accuracy. Hence, the analytical formulas may guide in selecting sampling rates for the ECG tailored to various applications of HR and HRV.

Five new sesquiterpenoids isolated from Dictamnus dasycarpus Turcz.

Five new sesquiterpenoids, dictamtrinorguaianols E and F (1-2), and dictameudesmnosides F, G, and H (3-5), along with seven known sesquiterpenoids (6-12) were isolated from Dictamnus dasycarpus Turcz. The structures of all new compounds were characterized by spectroscopic methods, including UV, IR, HR-ESI-MS, and 1D and 2D NMR. The In-vitro anti-proliferative activities of all the compounds against two human cancer cell lines (SW982 and A549) were evaluated by CCK-8 assay. Compounds 1 and 4 showed medium anti-proliferative activity against SW982 cells, with IC50 values of 3.49 ± 0.10 and 6.42 ± 1.23 µM, respectively. Additionally, compounds 2, 7, and 8 exhibited medium anti-proliferative activity against A549 cells, with IC50 values ranging from 0.80 ± 0.05 to 6.60 ± 0.46 µM.

CRDet: A circle representation detector for lung granulomas based on multi-scale attention features with center point calibration.

Lung granuloma is a very common lung disease, and its specific diagnosis is important for determining the exact cause of the disease as well as the prognosis of the patient. And, an effective lung granuloma detection model based on computer-aided diagnostics (CAD) can help pathologists to localize granulomas, thereby improving the efficiency of the specific diagnosis. However, for lung granuloma detection models based on CAD, the significant size differences between granulomas and how to better utilize the morphological features of granulomas are both critical challenges to be addressed. In this paper, we propose an automatic method CRDet to localize granulomas in histopathological images and deal with these challenges. We first introduce the multi-scale feature extraction network with self-attention to extract features at different scales at the same time. Then, the features will be converted to circle representations of granulomas by circle representation detection heads to achieve the alignment of features and ground truth. In this way, we can also more effectively use the circular morphological features of granulomas. Finally, we propose a center point calibration method at the inference stage to further optimize the circle representation. For model evaluation, we built a lung granuloma circle representation dataset named LGCR, including 288 images from 50 subjects. Our method yielded 0.316 mAP and 0.571 mAR, outperforming the state-of-the-art object detection methods on our proposed LGCR.

Genome-wide analysis of bZIP gene family members in Pleurotus ostreatus, and potential roles of PobZIP3 in development and the heat stress response.

The basic leucine zipper (bZIP) transcription factor (TF) is widespread among eukaryotes and serves different roles in fungal processes including nutrient utilization, growth, stress responses and development. The oyster mushroom (Pleurotus ostreatus) is an important and widely cultivated edible mushroom worldwide; nevertheless, reports are lacking on the identification or function of bZIP gene family members in P. ostreatus. Herein, 11 bZIPs on 6 P. ostreatus chromosomes were systematically identified, which were classified into 3 types according to their protein sequences. Phylogenetic analysis of PobZIPs with other fungal bZIPs indicated that PobZIPs may have differentiated late. Cis-regulatory element analysis revealed that at least one type of stress-response-related element was present on each bZIP promoter. RNA-seq and RT-qPCR analyses revealed that bZIP expression patterns were altered under heat stress and different developmental stages. We combined results from GST-Pull-down, EMSA and yeast two-hybrid assays to screen a key heat stress-responsive candidate gene PobZIP3. PobZIP3 overexpression in P. ostreatus enhanced tolerance to high temperature and cultivation assays revealed that PobZIP3 positively regulates the development of P. ostreatus. RNA-seq analysis showed that PobZIP3 plays a role in glucose metabolism pathways, antioxidant enzyme activity and sexual reproduction. These results may support future functional studies of oyster mushroom bZIP TFs.

Potential added value of computed tomography radiomics to multimodal prediction models for benign and malignant breast tumors.

Background: Early diagnosis is crucial to the treatment of breast cancer, but conventional imaging detection is challenging. Radiomics has the potential to improve early diagnostic efficacy in a noninvasive manner. This study examined whether integrating computed tomography (CT) radiomics information based on ultrasound (US) models can improve the efficacy of breast cancer prediction. Methods: We retrospectively analyzed 420 patients with pathologically confirmed benign or malignant breast tumors. Clinical data and examination images were collected, and the population was divided into training (n=294) and validation (n=126) groups at a ratio of 7:3. The region of interest (ROI) was manually segmented along the tumor boundary using MaZda software, and the features of each ROI was extracted. After dimension reduction and screening, the best features were retained. Subsequently, random forest (RF), support vector machines, and K-nearest neighbor classifiers were used to establish prediction models in an US and combined-methods group. Results: Finally, 8 of the 379 features were retained in the US group. Random forest was found to be the best model, and the area under the curve (AUC) of the training and validation groups was 0.90 [95% confidence interval (CI): 0.852-0.942] and 0.85 (95% CI: 0.775-0.930), respectively. Meanwhile, 12 of the 750 features were retained in the combined group. In this regard, random forest proved to be the best model, and the AUC of the training and validation group was 0.95 (95% CI: 0.918-0.981) and 0.92 (95% CI: 0.866-0.969), respectively. The calibration curve showed a good fit of the model. The decision curve showed that the clinical net benefit of the combined group was far greater than that of any single examination, and the prediction model of the combined group exhibited a degree of practical clinical value. Conclusions: The combined model based on US and CT images has potential application value in the prognostic prediction of benign and malignant breast diseases.

Multifunctional gelatin nanoparticle stabilized-Pickering emulsion hydrogel based on dextran and amikacin with controlled drug release and enhanced antibacterial capability for promoting infected wound healing.

Plant essential oils possess broad-spectral antimicrobial property, but the applications are impeded by their insolubility in water, extreme volatility, and strong irritation. Nanoparticle-stabilized emulsion (Pickering emulsion) gels are colloidal systems with ability to accommodate two immiscible phases in one system. The thick adsorption nanoparticle layers and the cross-linked networks in continuous phase could provide protective barriers for antibacterial oil and achieve on-demand controlled release. An emulsion hydrogel templated from gelatin nanoparticle-stabilized emulsion is one-pot constructed by conducting a tunable cross-linking process between oxidized dextran (Odex) and amikacin in the continuous phase and concomitantly trapping tea tree essential oil (TO) droplets in the three-dimensional network. The resulted emulsion hydrogel presents tunable gelation time, adequate mechanical strength, fascinating injectability, and self-healing capability. It is pH-responsiveness and presents controlled release of amikacin and TO, exhibiting a long-term bacteriostasis of 144 h. The emulsion hydrogel facilitates the outstanding wound healing efficiency in 14 days (95.2 ± 0.8 % of wound closure), accompanied with enhanced collagen deposition and angiogenic activities. The incorporation of TO into emulsion hydrogel system reduced its irritation and improved its biosafety, showing potential application in bacteria inhibition even as implants in vivo.

Causal effect of age first had sexual intercourse and lifetime number of sexual partners on cervical cancer.

Objective: In this study, we aimed to investigate whether age first had sexual intercourse (AFSI) and lifetime number of sexual partners (LNSP) have a direct causal effect on cervical cancer by Mendelian randomization (MR) analysis. Methods: Four approaches were used for MR Analysis, including MR-Egger, weighted method, weighted median, and inverse variance weighted (IVW). MR Pleiotropy RESidual Sum and Outlier (MR-PRESSO) as well as MR-Egger regression analysis were conducted to detect whether there was pleiotropy between IVs and outcome, and the outlier SNPs can be detected by MR-PRESSO. The presence or absence of heterogeneity among IVs was suggested according to Cochran's Q statistic. Leave-one-out sensitivity analysis was performed to identify and remove SNPs which could independently change the results. We corrected the results using Bonferroni correction. Results: From the results of IVW, AFSI had a negative effect on cervical cancer (OR = 0.996, 95 % CI: 0.995, 0.998 P = 1.70E-07), which still persisted after Bonferroni correction. However, no causal effect of LNSP on cervical cancer was found according to the IVW results (OR = 1.003, 95 % CI: 1.000, 1.007, P = 0.071). From the results of MR-PRESSO and MR-Egger, no SNP with horizontal pleiotropy between cervical cancer was detected and no SNP was identified as an outlier SNP. Cochran's Q statistic suggested that no heterogeneity existed among IVs of AFSI and LNSP. According to Leave-one-out analysis, the results of MR did not change after excluding any single IV. Conclusion: This MR study reveals that early AFSI has a causal effect on cervical cancer.

Label-free comparative proteomic analysis of Pleurotus eryngii grown on sawdust, bagasse, and peanut shell substrates.

The white rot fungi Pleurotus eryngii are environmental microorganisms that can effectively break down lignocellulosic biomass. However, understanding of the mechanisms by which P. eryngii is effective in degrading lignocellulose is still limited. This work aimed to examine the extracellular secretory proteins implicated in the breakdown of lignocellulose in P. eryngii and identify degradation tactics across various cultivation substrates. Thus, a comparative analysis of the secretory proteins based on Nanoliquid chromatography combined with tandem mass spectrometry was conducted among P. eryngii cultivated on sawdusts, bagasse, peanut shells, and glucose. In total, 647, 616, 604, and 511 proteins were identified from the four samples, respectively. Gene Ontology and Kyoto Encyclopedia of Genes and Genomes pathway analysis of protein expression differences identified pathways (hydrolytic enzymes, catalytic activity, metabolic processes, cellular processes, and response to stimuli) significantly enriched in proteins associated with lignocellulose degradation in P. eryngii. An integrated analysis of proteome data revealed specifically or differentially expressed genes secreted by P. eryngii in different cultivation substrates. The most prevalent carbohydrate-active enzymes involved in lignocellulose degradation in the secretome of the four samples were laccase (Lac), manganese peroxidase (MnP), aryl alcohol oxidase (AaO), and copper radical oxidase (CRO). Among them, Lac 2 mainly involved in the lignin degradation of sawdust peanut shells, and bagasse by P. eryngii, and Mnp 3 was mainly involved in the degradation of peanut shells. AaO and Lac 4 were mainly involved in glucose substrate defense and oxidative stress. It was found that exogenous addition of sawdust and peanut shells significantly increased lignolytic enzyme abundance. These findings provide insight and guidance for improving agricultural waste resource recovery. In this study, the secretomes of P. eryngii grown on four different carbon sources were compared. The findings revealed the extracellular enzymes implicated in the degradation of lignocellulose, offering avenues for further investigation into the biotransformation mechanisms of P. eryngii biomass and the potential utilization of agricultural wastes. SIGNIFICANCE: The cost of the substrate for mushroom cultivation has increased as the production of edible fungus has risen year after year. Therefore, the use of these locally available lignocellulosic wastes as substrates offers a cost-cutting option. Further, the overuse of wood for the cultivation of edible mushrooms is also detrimental to the conservation of forest resources or the ecological environment. Consequently, the use of other agricultural wastes as an alternative to sawdust or other woody substrates is a viable approach for cultivating P. eryngii. The distribution of extracellular lignocellulosic degrading enzymes, inferred in the present study could help improve the cultivation efficiency of P. eryngii vis-à-vis managing agricultural waste.

Calcium-mediated nitrogen reduction for electrochemical ammonia synthesis.

Ammonia (NH3) is a key commodity chemical for the agricultural, textile and pharmaceutical industries, but its production via the Haber-Bosch process is carbon-intensive and centralized. Alternatively, an electrochemical method could enable decentralized, ambient NH3 production that can be paired with renewable energy. The first verified electrochemical method for NH3 synthesis was a process mediated by lithium (Li) in organic electrolytes. So far, however, elements other than Li remain unexplored in this process for potential benefits in efficiency, reaction rates, device design, abundance and stability. In our demonstration of a Li-free system, we found that calcium can mediate the reduction of nitrogen for NH3 synthesis. We verified the calcium-mediated process using a rigorous protocol and achieved an NH3 Faradaic efficiency of 40 ± 2% using calcium tetrakis(hexafluoroisopropyloxy)borate (Ca[B(hfip)4]2) as the electrolyte. Our results offer the possibility of using abundant materials for the electrochemical production of NH3, a critical chemical precursor and promising energy vector.