Efficient hydrogen production from formic acid dehydrogenation over ultrasmall PdIr nanoparticles on amine-functionalized yolk-shell mesoporous silica.

Developing heterogeneous catalysts with exceptional catalytic activity over formic acid (HCOOH, FA) dehydrogenation is imperative to employ FA as an effective hydrogen (H2) carrier. In this work, ultrasmall (1.4 nm) and well-dispersed PdIr nanoparticles (NPs) immobilized on amine-functionalized yolk-shell mesoporous silica nanospheres (YSMSNs) with radially oriented mesoporous channels have been synthesized by a co-reduction strategy. The optimized catalyst Pd4Ir1/YSMSNs-NH2 (Pd/Ir molar ratio = 4:1) exhibited a remarkable turnover frequency (TOF) of 5818 h-1 and remarkable stability at 50 °C with the addition of sodium formate (SF), resulting in complete FA conversion and H2 selectivity, exceeding most of the solid heterogeneous catalysts in previous reports under similar circumstances. Kinetic isotope effect (KIE) exploration indicates the cleavage of the CH bond is regarded as the rate-determining step (RDS) during the FA dehydrogenation process. Such excellent catalytic properties arise from the ultrafine and well-dispersed PdIr NPs supported on the nanosphere support YSMSNs-NH2, the electronic synergistic effect of PdIr alloy NPs, and the strong metal-support interaction (MSI) effect between the introduced PdIr NPs and YSMSNs-NH2 support. This work offers a new paradigm for exploiting the highly effective silica-supported Pd-based heterogeneous catalysts over the dehydrogenation of FA.

LTBP2 down-regulated FGF2 to repress vascular smooth muscle cell proliferation and vascular remodeling in a rat model of intracranial aneurysm.

This work probed into the role of latent transforming growth factor beta binding protein 2 (LTBP2) in intracranial aneurysm (IA). The rats underwent IA modeling and then stereotactic injection of short hairpin RNA against LTBP2 (shLTBP2). Hematoxylin-eosin (HE) staining was employed to assess IA model and vascular remodeling. Rat vascular smooth muscle cells (VSMCs) were transfected with shLTBP2, LTBP2 overexpression plasmid and fibroblast growth factor 2 (FGF2) overexpression plasmid. The mRNA and protein expressions of LTBP2, FGF2 and mitochondrial apoptosis-related factors (Caspase-3, Cyt-c, Mcl-1) were tested through qRT-PCR and Western blot. Cell viability, proliferation and apoptosis were examined by cell counting kit-8, EdU assay and flow cytometry. The up-regulated LTBP2 and down-regulated FGF2 were detected in IA rats. LTBP2 knockdown promoted vascular remodeling and Mcl-1 level, and restrained cell apoptosis and expressions of Caspase-3 and Cyt-c in IA model rats. Moreover, LTBP2 knockdown potentiated cell viability, proliferation and FGF2 level, and repressed apoptosis in rat VSMCs, while overexpressed LTBP2 exerted opposite effects. FGF2 overexpression promoted proliferation and Mcl-1 level, and inhibited apoptosis and expressions of Caspase-3 and Cyt-c in rat VSMCs, which also reversed the effects of overexpressed LTBP2 on these aspects. Collectively, LTBP2 down-regulates FGF2 to repress VSMCs proliferation and vascular remodeling in an IA rat model.

Ultrasmall Pd nanoparticles supported on a metal-organic framework DUT-67-PZDC for enhanced formic acid dehydrogenation.

The highly dispersed ultrasmall palladium nanoparticles (Pd NPs) (1.7 nm) were successfully immobilized on a N-containing metal-organic framework (MOF, DUT-67-PZDC) using a co-reduction method, and it is used as an excellent catalyst for formic acid dehydrogenation (FAD). The optimized catalyst Pd/DUT-67-PZDC(10, 10 wt% Pd loading) shows 100% hydrogen (H2) selectivity and formic acid (FA) conversion at 60 °C, and the commendable initial turnover frequency (TOF) values of 2572 h-1 with the sodium formate (SF) as an additive and 1059 h-1 even without SF, which is better than most reported MOF supported Pd monometallic heterogeneous catalysts. The activation energy (Ea) of FAD is 43.2 KJ/mol, which is lower than most heterogeneous catalysts. In addition, the optimized catalyst Pd/DUT-67-PZDC(10) maintained good stability over five consecutive runs, demonstrating only minimal decline in catalytic activity. The outstanding catalytic performance could be ascribed to the synergistic corporations of the unique structure of DUT-67-PZDC carrier with hierarchical pore characteristic, the metal-support interaction (MSI) between the active Pd NPs and DUT-67-PZDC, the highly dispersed Pd NPs with ultrafine size serve as the catalytic active site, as well as the N sites on the support could act as the proton buffers. This work provides a new paradigm for the efficient H2 production of FAD by constructing highly active heterogeneous Pd-based catalysts using MOF supports.

Pyridinic-N Regulated Electron Injection to Modulate *OH Adsorption at Fe-N-C Sites for an Efficient Oxygen Reduction Reaction.

To enhance the efficiency of oxygen reduction reaction (ORR) catalysts, precise control over the adsorption/desorption energy barriers of oxygen intermediates at atomically dispersed Fe-N-C sites is essential yet challenging. Addressing this, we employed a pyrolysis approach using a nitrogen-containing polymer to fabricate Fe single-atom (SA) catalysts embedded in a pyridinic-N enriched carbon matrix. This synthesis strategy yielded Fe SAs that demonstrated a superior electrochemical ORR performance, evidenced by an impressive half-wave potential of 0.941 V and a high limiting current density of 5.72 mA/cm2. Moreover, when applied in homemade Zn-air batteries, this premier catalyst exhibited exceptional specific capacity (720 mAh/gZn), peak power density (253 mW/cm2), and notable long-term stability. Theoretical insights revealed that the increased pyridinic-N content in the catalyst facilitated efficient electron transfer from N atoms to the Fe active sites, thus fine-tuning the d-band center and effectively controlling the adsorption energy barrier of *OH species. These mechanisms synergistically improve the ORR performance. Crucially, this fabrication method shows promise for adaptation to other transition metal-based SAs, including Co, Ni, and Cu, potentially establishing a versatile synthesis route for developing atomically dispersed catalyst systems in future applications.

Electric-field-sensitive hydrogel based on pineapple peel oxidized hydroxyethyl cellulose/gelatin/Hericium erinaceus residues chitosan and its study in curcumin delivery.

This study focused on synthesis of innovative hydrogels with electric field response from modified pineapple peel cellulose and hericium erinaceus chitosan and gelatin based on Schiff base reaction. A series of hydrogels were prepared by oxidized hydroxyethyl cellulose, gelatin and chitosan at different deacetylation degree via mild Schiff base reaction. Subsequently experiments towards the characterization of oxidized hydroxyethyl cellulose/gelatin/chitosan (OHGCS) hydrogel polymers were carried out by FTIR/XRD/XPS, swelling performances and electric response properties. The prepared hydrogels exhibited stable and reversible bending behaviors under repeated on-off switching of electric fields, affected by ionic strength, electric voltage and pH changes. The swelling ratio of OHGCS hydrogels was found reduced as deacetylation degree increasing and reached the maximum ratio âˆ¼ 2250 % for OHGCS-1. In vitro drug releasing study showed the both curcumin loading capacity and release amount of Cur-OHGCS hydrogels arrived about 90 % during 6 h. Antioxidation assessments showed that the curcumin-loaded hydrogels had good antioxidation activities, in which, 10 mg Cur-OHGCS-1 hydrogel could reach to the maximum of about 90 % DPPH scavenging ratio. These results indicate the OHGCS hydrogels have potentials in sensor and drug delivery system.

Bimodal Intelligent Electronic Skin Based on Proximity and Tactile Interaction for Pressure and Configuration Perception.

The flexible bimodal e-skin exhibits significant promise for integration into the next iteration of human-computer interactions, owing to the integration of tactile and proximity perception. However, those challenges, such as low tactile sensitivity, complex fabrication processes, and incompatibility with bimodal interactions, have restricted the widespread adoption of bimodal e-skin. Herein, a bimodal capacitive e-skin capable of simultaneous tactile and proximity sensing has been developed. The entire process eliminates intricate fabrication techniques, employing DLP-3D printing for the electrode layers and sacrificial templating for the dielectric layers, conferring high tactile sensitivity (1.672 kPa-1) and rapid response capability (∼30 ms) to the bimodal e-skin. Moreover, exploiting the "fringing electric field" effect inherent in parallel-plate capacitors has facilitated touchless sensing, thereby enabling static distance recognition and dynamic gesture recognition of varying materials. Interestingly, an e-skin sensing array was created to identify the positions and pressure levels of various objects of different masses. Furthermore, with the aid of machine learning techniques, an artificial neural network has been established to possess intelligent object recognition capabilities, facilitating the identification, classification, and training of various object configurations. The advantages of the bimodal e-skin render it highly promising for extensive applications in the field of next-generation human-machine interaction.

Evaluation of the efficacy and safety of CalliSpheres® microsphere-transarterial chemoembolization in large hepatocellular carcinoma.

OBJECTIVE: The prognosis of large hepatocellular carcinoma (HCC) is still unfavorable due to limited and challenging treatment. CalliSpheres® microsphere-transarterial chemoembolization (CSM-TACE) is an effective therapy for general HCC but not frequently applied for large HCC. Hence, this study aimed to investigate the efficacy and safety of CSM-TACE in large HCC patients. MATERIALS AND METHODS: This prospective study analyzed 100 large HCC (tumor size >5 cm) patients receiving CSM-TACE. Treatment response, survival, change in liver function indexes, and adverse events were recorded. RESULT: The best complete response, partial response, stable disease, and progressive disease rates were 2.0%, 31.3%, 65.7%, and 1.0%, respectively, leading to the best objective response rate (ORR) of 33.3% and disease control rate of 99.9%. Multivariate analysis showed that intrahepatic metastasis was independently related to poor ORR (odd ratio = 0.366, P = 0.023). The 1- and 2-year progression-free survival (PFS) rates were 88.9% and 80.6%, with a mean [95% confidence interval (CI)] PFS of 21.6 (20.4-22.9) months. The 1- and 2-year overall survival (OS) rates were 99.0% and 99.0%, with a mean (95% CI) OS of 23.8 (23.3-24.2) months. Total bilirubin (P < 0.001), alanine transaminase (P < 0.001), aspartate transaminase (P < 0.001), and α-fetoprotein (P = 0.045) were abnormal in a short-term period then stably recovered from 1 month ± 15 days after drug-eluting bead-TACE to 24 months ± 15 days. During hospitalization and postdischarge, tolerable abdominal pain and decreased appetite were common adverse events. CONCLUSIONS: CSM-TACE shows favorable treatment response and survival with acceptable tolerance among large HCC patients, indicating that it may promote the management of these patients.

Resection of high-grade glioma involving language areas assisted by multimodal techniques under general anesthesia: a retrospective study.

BACKGROUND: Multimodal techniques-assisted resection of glioma under general anesthesia (GA) has been shown to achieve similar clinical outcomes as awake craniotomy (AC) in some studies. In this study, we aim to validate the use of multimodal techniques can achieve the maximal safe resection of high-grade glioma involving language areas (HGILAs) under GA. METHODS: HGILAs cases were reviewed and collected between January 2009 and December 2020 in our center. Patients were separated into multimodal group (using neuronavigation, intraoperative MRI combined with direct electrical stimulation [DES] and neuromonitoring [IONM]) and conventional group (neuronavigation alone) and clinical outcomes were compared between groups. Studies of HGILAs were reviewed systematically and the meta-analysis results of previous (GA or AC) studies were compared with our results. RESULTS: Finally, there were 263 patients in multimodal group and 137 patients in conventional group. Compared to the conventional group, the multimodal group achieved the higher median EOR (100% versus 94.32%, P < 0.001) and rate of gross total resection (GTR) (73.8% versus 36.5%, P < 0.001) and the lower incidence of permanent language deficit (PLD) (9.5% versus 19.7%, P = 0.004). The multimodal group achieved the longer median PFS (16.8 versus 10.3 months, P < 0.001) and OS (23.7 versus 15.7 months, P < 0.001) than the conventional group. The multimodal group achieved a higher rate of GTR than the cohorts in previous multimodal studies under GA and AC (73.8% versus 55.7% [95%CI 32.0-79.3%] versus 53.4% [35.5-71.2%]). The multimodal group had a lower incidence of PLD than the cohorts in previous multimodal studies under GA (9.5% versus 14.0% [5.8-22.1%]) and our incidence of PLD was a little higher than that of previous multimodal studies under AC (9.5% versus 7.5% [3.7-11.2%]). Our multimodal group also achieved a relative longer survival than previous studies. CONCLUSIONS: Surgery assisted by multimodal techniques can achieve maximal safe resection for HGILAs under GA. Further prospective studies are needed to compare GA with AC for HGILAs.

The difference in the composition of gut microbiota is greater among bats of different phylogenies than among those with different dietary habits.

Bats have a very long evolutionary history and are highly differentiated in their physiological functions. Results of recent studies suggest effects of some host factors (e.g., phylogeny and dietary habit) on their gut microbiota. In this study, we examined the gut microbial compositions of 18 different species of bats. Results showed that Firmicutes, Gammaproteobacteria, and Actinobacteria were dominant in all fecal samples of bats. However, the difference in the diversity of gut microbiota among bats of different phylogenies was notable (p = 0.06). Various species of Firmicutes, Actinobacteria, and Gammaproteobacteria were found to contribute to the majority of variations in gut microbiota of all bats examined, and Aeromonas species were much more abundant in bats that feed on both insects and fish than in those of insectivores. The abundance of various species of Clostridium, Euryarchaeota, and ancient bacterial phyla was found to vary among bats of different phylogenies, and various species of Vibrio varied significantly among bats with different dietary habits. No significant difference in the number of genes involved in various metabolic pathways was detected among bats of different phylogenies, but the abundance of genes involved in 5 metabolic pathways, including transcription; replication, recombination, and repair; amino acid transport and metabolism; and signal transduction mechanisms, was different among bats with different dietary habits. The abundance of genes in 3 metabolic pathways, including those involved in stilbenoid, diarylheptanoid, and gingerol biosynthesis, was found to be different between insectivorous bats and bats that feed on both insects and fish. Results of this study suggest a weak association between dietary habit and gut microbiota in most bats but a notable difference in gut microbiota among bats of different phylogenies.

Endoscopic cadaveric analysis of the origin of the ophthalmic artery.

PURPOSE: The ophthalmic artery is often involved in suprasellar and parasellar surgeries, but the anatomical structure where the ophthalmic artery originates has not been fully clarified from the perspective of an endoscopic endonasal approach (EEA). METHODS: A total of 10 fresh cadaveric heads (20 sides) were dissected through an EEA, and the origin of the bilateral ophthalmic arteries and their adjacent structures were observed from a ventral view. The origin of the ophthalmic artery in 50 healthy people was retrospectively studied on computed tomography angiography imaging. RESULTS: The ophthalmic artery originated from the intradural segment (75%), paraclinoid segment (15%), or parasellar segment (10%) of the internal carotid artery. The cross-sectional view of the internal carotid artery through the EEA showed that the ophthalmic artery originated from the middle 1/3 (75%) or medial 1/3 (25%) of the upper surface of the internal carotid artery. On computed tomography angiography, the ophthalmic artery originated from the middle 1/3 (77%) and medial 1/3 (22%) of the upper surface of the internal carotid artery. All ophthalmic arteries were near the level of the distal dural ring (DDR) of the internal carotid artery, that is, within 3 mm above or below the DDR. CONCLUSIONS: The ophthalmic artery usually originates in the middle 1/3 of the upper surface of the intradural segment of the internal carotid artery within 3 mm of the DDR. The ophthalmic artery can be protected to the utmost extent after its origin is identified through an EEA.

A Phase 1/2 Multicenter Randomized Trial of Local Ablation plus Toripalimab versus Toripalimab Alone for Previously Treated Unresectable Hepatocellular Carcinoma.

PURPOSE: To assess the safety and efficacy of local ablation plus PD-1 inhibitor toripalimab in previously treated unresectable hepatocellular carcinoma (HCC). PATIENTS AND METHODS: In the multicenter, two-stage, and randomized phase 1/2 trial, patients were randomly assigned to receive toripalimab alone (240 mg, every 3 weeks), subtotal local ablation followed by toripalimab starting on post-ablation day 3 (Schedule D3), or on post-ablation day 14 (Schedule D14). The first endpoint of stage 1 was to determine which combination schedule could continue and progression-free survival (PFS) as the primary endpoint for stage 1/2. RESULTS: A total of 146 patients were recruited. During stage 1, Schedule D3 achieved numerically higher objective response rate (ORR) than Schedule D14 for non-ablation lesions (37.5% vs. 31.3%), and was chosen for stage 2 evaluation. For the entire cohort of both stages, patients with Schedule D3 had a significantly higher ORR than with toripalimab alone (33.8% vs. 16.9%; P = 0.027). Moreover, patients with Schedule D3 had improved median PFS (7.1 vs. 3.8 months; P < 0.001) and median overall survival (18.4 vs. 13.2 months; P = 0.005), as compared with toripalimab alone. In addition, six (9%) patients with toripalimab, eight (12%) with Schedule D3, and 4 (25%) with Schedule D14 developed grade 3 or 4 adverse events, and one patient (2%) with Schedule D3 manifested grade 5 treatment-related pneumonitis. CONCLUSIONS: In patients with previously treated unresectable HCC, subtotal ablation plus toripalimab improved the clinical efficacy as compared with toripalimab alone, with an acceptable safety profile.

Transjugular Intrahepatic Portosystemic Shunt Benefits for Hepatic Sinusoidal Obstruction Syndrome Associated with Consumption of Gynura Segetum: a Propensity Score-Matched Analysis.

PURPOSE: Pyrrolidine alkaloids-related hepatic sinusoidal obstruction syndrome (PA-HSOS) is associated with a high mortality rate without standardized therapy. The efficacy of transjugular intrahepatic portosystemic shunts (TIPS) remains controversial. The study aimed to explore the risk factors influencing the clinical response in patients with PA-HSOS related to Gynura segetum (GS) to assess the disease prognosis at an early stage and to evaluate the efficacy of TIPS in these patients. METHODS: This study retrospectively enrolled patients diagnosed with PA-HSOS between January 2014 and June 2021 with a clear history of exposure to GS. Univariate and multivariate logistic regression analyses were used to evaluate the risk factors influencing the clinical response in patients with PA-HSOS. Propensity score matched (PSM) was performed to compensate for differences in baseline characteristics between patients with and without TIPS. The primary outcome was the clinical response defined as the disappearance of ascites with normal total bilirubin levels and/or a reduction of elevated transaminase levels < 50% within 2 weeks. RESULTS: A total of 67 patients were identified in our cohort with a clinical response rate of 58.2%. Of these, thirteen patients were assigned to the TIPS group and 54 to the conservative treatment group. Logistic regression analysis revealed that TIPS treatment (P = 0.047), serum globulin levels (P = 0.043), and prothrombin time (P = 0.001) were independent factors influencing clinical response. After PSM, there was a higher long-term survival rate of patients (92.3% vs. 51.3%, P = 0.021) and a shorter hospital stay (P = 0.043), but a high trend in hospital costs (P = 0.070) in the TIPS group. The 6-month survival probability in patients undergoing TIPS therapy was more than ninefold higher than in patients without receiving that treatment [hazard ratio (95% CI) = 9.304 (4.250, 13.262), P < 0.05]. CONCLUSIONS: TIPS therapy may be an effective treatment option for patients with GS-related PA-HSOS.

Confirmation of the existence of Himalayan long-eared bats, Plecotushomochrous (Chiroptera, Vespertilionidae), in China.

The existence of Himalayan long-eared bats, Plecotushomochrous (Chiroptera, Vespertilionidae), in China has not been previously confirmed. In this study, four bats captured with harp traps from two sites in the Maoershan National Nature Reserve in Guangxi, China were investigated. These bats have long, wide auricles, each with a prominent tragus. The length of each auricle is about the same as that of a forearm. Hairs on the ventral fur have a dark base with mixed grey and yellowish tips; those on the dorsal fur also have a dark base and are bicolored with brown tips. The thumbs are very short. A concavity is present in the front of the dorsal side of the cranium. Based on morphological characteristics and phylogeny using Cyt b gene sequences, these bats were identified as P.homochrous, thus confirming the existence of Himalayan long-eared bats in China.

Disordered dolomite as an unusual biomineralization product found in the center of a natural Cassis pearl.

Natural pearls are produced without human intervention, mainly due to various irritations from the surrounding environment to their mantle tissues. Pearls usually possess similar mineral compositions to the host shells, which means they are also dominated by aragonite and calcite. In this study, we report a natural pearl from a Cassis species mollusk containing granular central structures. Raman spectroscopy, laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS), energy dispersive X-ray spectroscopy (EDS) coupled with scanning electron microscope (SEM), and X-ray diffraction (XRD) analyses were carried out in order to characterize the mineral composition in the center region of this pearl. Our results showed that this pearl's center was made of mostly disordered dolomite (Ca0.53Mg0.47CO3) mixing with small amount of aragonite and high magnesium-calcite. To the best of our knowledge, this is the first time disordered dolomite was conclusively identified inside of a natural pearl and such information expanded our knowledge on internal growth structures and formation of natural pearls.

Vacancy and doping engineering of Ni-based charge-buffer electrode for highly-efficient membrane-free and decoupled hydrogen/oxygen evolution.

The realization of the membrane-free two-step water electrolysis is particularly important yet challenging for the low-cost and large-scale supply of hydrogen energy. In this effort, Co-doped Ni(OH)2 nanosheets were successfully anchored onto the nickel foam (NF) substrate through the in-situ growth of metal-organic frame material and the subsequent alkali-etching technique. Using the well-regulated Co-doping Ni(OH)2@NF electrodes as a charge mediator, electrochemical hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) were decoupled on time scales, thus affording a membrane-free two-step route for H2 and O2 productions. In this architecture, the first HER process on the cathode could be maintained for 1300 s at a current of 100 mA, while the corresponding Ni(OH)2 charge mediator was simultaneously oxidized to NiOOH, with a decent cell voltage of 1.542 V. The subsequent OER process involved a reduction/regeneration of Ni(OH)2 (from NiOOH to Ni(OH)2) and an anodic O2-production, with an operating voltage of 0.291 V. Moreover, the Ni-Zn battery assembled through the combination of NiOOH and Zn sheet could replace the second step of OER to achieve the coupling of continuous H2-production and battery discharge, thus also providing a new way for hydrogen production without an external power supply. Experiment and theoretical calculations have shown that the cobalt-doping not only improved the conductivity of the charge-buffer electrode, but also shifted its redox potential cathodically and boosted the adsorption affinity of the buffer medium to OH- ions, both contributing to promoted HER and OER activity. Therefore, this decoupled water electrolysis device affords a promising pathway to support the efficient conversion of renewables to hydrogen.

miR-195-5p Targets CDK1 To Regulate New DNA Synthesis and Inhibit the Proliferation of Hepatocellular Carcinoma Cells.

In cell biological functions and viability, cyclin-dependent kinase 1 (CDK1) takes an essential part. miR-195-5p is pivotal in pathogenesis and development of hepatocellular carcinoma (HCC). But in HCC, whether there is a connection between CDK1 and miR-195-5p remains an unanswered question. In view of this, this study focuses on exploring the mechanism of miR-195-5p/CDK1 in the progression of HCC. The bioinformatics method was applied to predict target mRNA and upstream miRNAs, and further analyzes the signal enrichment pathway of target mRNA. We utilized qRT-PCR and Western blot for detecting expression of genes, as well as their corresponding protein levels. Cell cycle was assayed through flow cytometry. As for the examination of DNA replication, the EDU staining was employed. Cell proliferation was determined via plate colony formation assay. The combined application of bioinformatics analysis and dual-luciferase gene assay assisted in figuring out the binding relationship between miR-195-5p and CDK1. DNA damage was marked by immunofluorescence staining. CDK1 was overexpressed in HCC cells, and enriched in cell cycle and DNA replication pathway. Silencing CDK1 modulated cell cycle of HCC cells and inhibited DNA replication and proliferation. In HCC cells, miR-195-5p targeted and reduced CDK1 expression, inhibited the G1 phase-to-S phase transition, induced DNA damage response, and inhibited DNA replication and proliferation. miR-195-5p targeted CDK1 and repressed synthesis of new DNA in HCC cells, thus restraining HCC cell proliferation.

Metal-organic framework derived Fe3C nanoparticles coupled single-atomic iron for boosting oxygen reduction reaction.

Developing transition metal electrocatalysts, especially single-atom catalysts (SACs), is significant. However, most of the synthesis procedures of SACs involve the formation of nanoparticles (NPs), and the produced NPs always play an influential role during electrocatalytic processing, so exploring the synergistic effects between metallic and isolated metal species is of great interest. Herein, we report a Zn/Fe-metal-organic framework (MOF)-derived Fe3C coupling FeNx catalyst constructed via coordination confinement pyrolysis effect successfully. Compared with the Pt/C catalyst and most precious metal-free catalysts, the optimized catalyst Fe3C-FeNx/NC-7 demonstrates superior oxygen reduction reaction (ORR) activity in 0.1 M KOH. The half-wave potential (E1/2) reaches up to 0.93 V with the limiting current density (jL) of 5.65 mA/cm2 at 5 mV/s scanning rate and 1600 rpm. The excellent performance originates from the synergistic effect of FeNx and Fe3C active units combined with wide-distributed nitrogen atoms. The Fe3C NPs further optimize the electronic structure and adsorption/desorption free energy of the catalyst. The assembled primary Zn-air battery (ZAB) displays a satisfying open-circuit potential of 1.53 V and an excellent specific capacity of 835 mA·h·g-1. The maximum power density achieves 283 mW/cm2, outclassing the commercial Pt/C-based ZAB. This result demonstrates the promising application prospect of the catalyst-cooperated metallic NPs with isolated single metal species.

Aspirin inhibits the biological behavior of gallbladder carcinoma cells by modulating vascular endothelial growth factor.

OBJECTIVE: To elucidate the effect of aspirin (ASP) on the biological behavior of gallbladder carcinoma (GBC) cells and its influence on vascular endothelial growth factor (VEGF) expression. METHODS: Cell Counting Kit-8 (CCK-8) assay was performed to determine the effects of ASP on GBC-SD cell proliferation. In addition, Transwell assay and flow cytometry were carried out to observe the role of ASP in GBC-SD cell migration, invasion and apoptosis, respectively. Tumor necrosis factor-α (TNF-α), nuclear factor kappa-B (NF-κB), and VEGF concentrations in GBC-SD cells were examined by enzyme-linked immunosorbent assays (ELISAs). RESULTS: ASP suppressed GBC-SD cell proliferation in a dose-dependent manner, and a concentration ≥ 2 mmol/L could significantly inhibit the migration and invasion of GBC-SD cells and induce apoptosis. In addition, the anticancer effect of ASP in GBC-SD cells may be linked to its inhibition of TNF-α, NF-κB, and VEGF levels. CONCLUSIONS: ASP may markedly inhibit GBC-SD cell growth by significantly reducing TNF-α, NF-κB and VEGF expression.

Evolution of Chemical Bonding and Crystalline Swelling-Shrinkage of Montmorillonite upon Temperature Changes Probed by in Situ Fourier Transform Infrared Spectroscopy and X-ray Diffraction.

Clay minerals are distributed in Earth's crust and troposphere and in Martian crust where temperature varies. Understanding the changes of chemical bonding and crystalline swelling-shrinkage of montmorillonite (Mnt) upon temperature changes is fundamental for studying its surface reactivity and interaction in specific surroundings. However, such an issue remains poorly understood. Here, in situ high- and low-temperature Fourier transform infrared (HT- and LT-FTIR) spectroscopy and X-ray diffraction (HT- and LT-XRD) were performed to study the evolution of chemical bonding and crystalline swelling-shrinkage of sodium-montmorillonite (NaMnt) upon temperature changes. The FTIR results show that the hydroxyl content in NaMnt decreased when the temperature increased from 20 to 700 °C, while it is independent of temperature from 0 to -150 °C. The formation of hydroxyls at the "broken" layer edges of NaMnt is related to adsorbed water molecules on the surfaces, and its content increased when the particle size of the NaMnt decreased. The water molecules in the interlayer space of NaMnt could bond to the tetrahedral sheet of NaMnt through Si2O-H2O bonds. HT- and LT-XRD results reveal that all of those water molecules in NaMnt were removed after heating to 100 °C in the heating chamber. The NaMnt was transformed from a state of monolayer interlayer water molecules at 20 °C to a dehydrated state at 100 °C, and then to a dehydroxylated state at 700 °C. Accordingly, the basal spacings of NaMnt were changed from 1.27 to 0.97 nm and then to 0.96 nm, respectively. When NaMnt was cooled from 20 to -268 °C, a crystalline swelling of NaMnt occurred with an increase of 0.03 nm of basal spacing. This work demonstrates that high/low temperature has a remarkable effect on the hydroxyls and the water molecules in NaMnt, which in turn affects its swelling-shrinkage performance. These findings provide some in-depth understanding of the changes of chemical bonding and crystalline swelling-shrinkage of montmorillonite upon temperature changes and the reasons behind these, which might be helpful for the design of engineering Mnt in high-/low-temperature applications.

Calcium carbonate: controlled synthesis, surface functionalization, and nanostructured materials.

Calcium carbonate (CaCO3) is an important inorganic mineral in biological and geological systems. Traditionally, it is widely used in plastics, papermaking, ink, building materials, textiles, cosmetics, and food. Over the last decade, there has been rapid development in the controlled synthesis and surface modification of CaCO3, the stabilization of amorphous CaCO3 (ACC), and CaCO3-based nanostructured materials. In this review, the controlled synthesis of CaCO3 is first examined, including Ca2+-CO32- systems, solid-liquid-gas carbonation, water-in-oil reverse emulsions, and biomineralization. Advancing insights into the nucleation and crystallization of CaCO3 have led to the development of efficient routes towards the controlled synthesis of CaCO3 with specific sizes, morphologies, and polymorphs. Recently-developed surface modification methods of CaCO3 include organic and inorganic modifications, as well as intensified surface reactions. The resultant CaCO3 can then be further engineered via template-induced biomineralization and layer-by-layer assembly into porous, hollow, or core-shell organic-inorganic nanocomposites. The introduction of CaCO3 into nanostructured materials has led to a significant improvement in the mechanical, optical, magnetic, and catalytic properties of such materials, with the resultant CaCO3-based nanostructured materials showing great potential for use in biomaterials and biomedicine, environmental remediation, and energy production and storage. The influences that the preparation conditions and additives have on ACC preparation and stabilization are also discussed. Studies indicate that ACC can be used to construct environmentally-friendly hybrid films, supramolecular hydrogels, and drug vehicles. Finally, the existing challenges and future directions of the controlled synthesis and functionalization of CaCO3 and its expanding applications are highlighted.