Switching between C2+ Products and CH4 in CO2 Electrolysis by Tuning the Composition and Structure of Rare-Earth/Copper Catalysts.

Rational regulation of the reaction pathway to produce the desired products is one of the most significant challenges in the electrochemical CO2 reduction reaction (CO2RR). Herein, we designed a series of rare-earth Cu catalysts with mixed phases. It was found that the products could be switched from C2+ to CH4 by tuning the composition and structure of the catalysts. Particularly at the Cu/Sm atomic ratio of 9/1 (Cu9Sm1-Ox), the Faradaic efficiency (FE) for C2+ products (FEC2+) could reach 81% at 700 mA cm-2 with negligible CH4. However, the FE of CH4 (FECH4) was 65% at 500 mA cm-2 over Cu1Sm9-Ox (Cu/Sm = 1/9), and the FEC2+ was extremely low. Experiments and theoretical studies indicated that the stable CuSm2O4 phase existed in all the catalysts within the Cu/Sm range of 9/1 to 1/9. At a high Cu content, the catalyst was composed of CuSm2O4 and Cu phases. The small amount of Sm could enhance the binding strength of *CO and facilitate C-C coupling. Conversely, at a high Sm content, the catalyst was composed of CuSm2O4 and Sm2O3 phases. Sm could effectively stabilize bivalent Cu and enrich proton donors, lowering the reaction energy of *CO for deep hydrogenation to generate CH4. In both pathways, the stable CuSm2O4 phase could cooperate with the Cu or Sm2O3 phases, which induced the formation of different microenvironments to generate different products. This strategy also had commonality with other Cu-rare-earth (La, Pr, and Eu) catalysts to boost the CO2RR for C2+ or CH4 production.

p-d Orbital Hybridization Induced by p-Block Metal-Doped Cu Promotes the Formation of C2+ Products in Ampere-Level CO2 Electroreduction.

Large-current electrolysis of CO2 to multi-carbon (C2+) products is critical to realize the industrial application of CO2 conversion. However, the poor binding strength of *CO intermediates on the catalyst surface induces multiple competing pathways, which hinder the C2+ production. Herein, we report that p-d orbital hybridization induced by Ga-doped Cu (CuGa) could promote efficient CO2 electrocatalysis to C2+ products at ampere-level current density. It was found that CuGa exhibited the highest C2+ productivity with a remarkable Faradaic efficiency (FE) of 81.5% at a current density of 0.9 A/cm2, and the potential at such a high current density was -1.07 V versus reversible hydrogen electrode. At 1.1 A/cm2, the catalyst still maintained a high C2+ productivity with an FE of 76.9%. Experimental and theoretical studies indicated that the excellent performance of CuGa results from the p-d hybridization of Cu and Ga, which not only enriches reactive sites but also enhances the binding strength of the *CO intermediate and facilitates C-C coupling. The p-d hybridization strategy can be extended to other p-block metal-doped Cu catalysts, such as CuAl and CuGe, to boost CO2 electroreduction for C2+ production. As far as we know, this is the first work to promote electrochemical CO2 reduction reaction to generate the C2+ product by p-d orbital hybridization interaction using a p-block metal-doped Cu catalyst.

Hydrogen Radical-Induced Electrocatalytic N2 Reduction at a Low Potential.

Realizing efficient hydrogenation of N2 molecules in the electrocatalytic nitrogen reduction reaction (NRR) is crucial in achieving high activity at a low potential because it theoretically requires a higher equilibrium potential than other steps. Analogous to metal hydride complexes for N2 reduction, achieving this step by chemical hydrogenation can weaken the potential dependence of the initial hydrogenation process. However, this strategy is rarely reported in the electrocatalytic NRR, and the catalytic mechanism remains ambiguous and lacks experimental evidence. Here, we show a highly efficient electrocatalyst (ruthenium single atoms anchored on graphdiyne/graphene sandwich structures) with a hydrogen radical-transferring mechanism, in which graphdiyne (GDY) generates hydrogen radicals (H•), which can effectively activate N2 to generate NNH radicals (•NNH). A dual-active site is constructed to suppress competing hydrogen evolution, where hydrogen preferentially adsorbs on GDY and Ru single atoms serve as the adsorption site of •NNH to promote further hydrogenation of NH3 synthesis. As a result, high activity and selectivity are obtained simultaneously at -0.1 V versus a reversible hydrogen electrode. Our findings illustrate a novel hydrogen transfer mechanism that can greatly reduce the potential and maintain the high activity and selectivity in NRR and provide powerful guidelines for the design concept of electrocatalysts.

High-Rate CO2 Electrolysis to Formic Acid over a Wide Potential Window: An Electrocatalyst Comprised of Indium Nanoparticles on Chitosan-Derived Graphene.

Realizing industrial-scale production of HCOOH from the CO2 reduction reaction (CO2 RR) is very important, but the current density as well as the electrochemical potential window are still limited to date. Herein, we achieved this by integration of chemical adsorption and electrocatalytic capabilities for the CO2 RR via anchoring In nanoparticles (NPs) on biomass-derived substrates to create In/X-C (X=N, P, B) bifunctional active centers. The In NPs/chitosan-derived N-doped defective graphene (In/N-dG) catalyst had outstanding performance for the CO2 RR with a nearly 100 % Faradaic efficiency (FE) of HCOOH across a wide potential window. Particularly, at 1.2 A ⋅ cm-2 high current density, the FE of HCOOH was as high as 96.0 %, and the reduction potential was as low as -1.17 V vs RHE. When using a membrane electrode assembly (MEA), a pure HCOOH solution could be obtained at the cathode without further separation and purification. The FE of HCOOH was still up to 93.3 % at 0.52 A ⋅ cm-2 , and the HCOOH production rate could reach 9.051 mmol ⋅ h-1 ⋅ cm-2 . Our results suggested that the defects and multilayer structure in In/N-dG could not only enhance CO2 chemical adsorption capability, but also trigger the formation of an electron-rich catalytic environment around In sites to promote the generation of HCOOH.

The Modulatory Effect of Motor Cortex Astrocytes on Diabetic Neuropathic Pain.

Diabetic neuropathic pain (DNP) is a common complication of diabetes characterized by persistent pain. Emerging evidence links astrocytes to mechanical nociceptive processing, and the motor cortex (MCx) is a cerebral cortex region that is known to play a key role in pain regulation. However, the association between MCx astrocytes and DNP pathogenesis remains largely unexplored. Here, we studied this association using designer receptors exclusively activated by designer drugs to specifically manipulate MCx astrocytes. We proved that the selective inhibition of MCx astrocytes reduced DNP in streptozocin (STZ)-induced DNP models and discovered a potential mechanism by which astrocytes release cytokines, including TNF-α and IL-1ß, to increase neuronal activation in the MCx, thereby regulating pain. Together, these results demonstrate a pivotal role for MCx astrocytes in DNP pathogenesis and provide new insight into DNP treatment strategies.

Design and Preparation of Electrocatalysts by Electrodeposition for CO2 Reduction.

With the increasing emission of carbon dioxide (CO2 ), the conversion and utilization of CO2 have become a topic of increasing concern. Electrochemical CO2 reduction reaction (CO2 RR) is an attractive and sustainable approach for solving energy and environmental problems. Design of efficient catalysts is crucial for achieving highly efficient CO2 RR. Different methods to prepare catalysts have been reported and used. Among them, electrodeposition is one of the common approaches, which has some obvious advantages, such as requiring simple equipment, environmentally benign. Especially, it can direct deposit catalysts on different substrates to prepare electrodes for CO2 RR. In this review, we discuss recent advances in design and preparation of the catalysts by electrodeposition and their applications in CO2 RR. Furthermore, the perspective of this promising area is also discussed.

Biogenetic cantharidin is a promising leading compound to manage insecticide resistance of Mythimna separata (Lepidoptera: Noctuidae).

Cantharidin (CTD) is a natural toxin with effective toxicity to lepidopteran pests. Nevertheless, little information is available on whether pests develop resistance to CTD. After being exposed to CTD (50 mg/L to 90 mg/L) or 10 generations, the resistance ratio of laboratory selected cantharidin-resistant Mythimna separata (Cantharidin-SEL) strain was only elevated 1.95-fold. Meanwhile, the developmental time for M. separata was prolonged (delayed1.65 in males and 1.84 days in females). The reported CTD target, the serine/threonine phosphatases (PSPs), have not been shown significant activity variation during the whole process of CTD-treatment. The activity of detoxification enzymes (cytochrome monooxygenase P450, glutathione-S-transferase (GST) and carboxylesterase) were affected by CTD selection, but this change was not mathematically significant. More importantly, no obvious cross-resistance with other commonly used insecticides was observed in the M. separata population treated with CTD for 10 generations (resistance ratios were all lower 2.5). Overall, M. separata is unlikely to produce target-site insensitivity resistance, metabolic resistance to CTD. Meanwhile, cantharidin-SEL is not prone to develop cross-resistance with other insecticides. These results indicate that CTD is a promising biogenetic lead compound which can be applied in the resistance management on M. separata.

Fast compressive beamforming with a modified fast iterative shrinkage-thresholding algorithm.

Compressive beamforming has been successfully applied to direction-of-arrival estimation with sensor arrays. The results demonstrated that this technique achieves superior performance when compared with traditional high-resolution beamforming methods. The existing compressive beamforming methods use classical iterative optimization algorithms in their compressive sensing theories. However, the computational complexity of the existing compressive beamforming methods tend to be excessively high, which has limited the use of compressive beamforming in applications with limited computing resources. To address this issue, this paper proposes a fast compressive beamforming method which combines the shift-invariance of the array beam patterns with a fast iterative shrinkage-thresholding algorithm. The evaluation shows that the proposed fast compressive beamforming method successfully reduces the number of floating-point operations by 3 orders of magnitude when compared with the existing methods. In addition, both the simulations and experiments demonstrate that the resolution limit for discerning closely spaced sources of the introduced fast method is comparable to those of the existing compressive beamforming methods, which use classical iterative optimization algorithms.

Comparison of Awake and Asleep Deep Brain Stimulation for Parkinson's Disease: A Detailed Analysis Through Literature Review.

OBJECTIVES: Deep brain stimulation (DBS) for Parkinson's disease (PD) has been applied to clinic for approximately 30 years. The goal of this review is to explore the similarities and differences between "awake" and "asleep" DBS techniques. METHODS: A comprehensive literature review was carried out to identify relevant studies and review articles describing applications of "awake" or "asleep" DBS for Parkinson's disease. The surgical procedures, clinical outcomes, costs and complications of each technique were compared in detail through literature review. RESULTS: The surgical procedures of awake and asleep DBS surgeries rely upon different methods for verification of intended target acquisition. The existing research results demonstrated that the stereotactic targeting accuracy of lead placement obtained by either method is reliable. There were no significant differences in clinical outcomes, costs, or complications between the two techniques. CONCLUSION: The surgical and clinical outcomes of asleep DBS for PD are comparable to those of awake DBS.

Hollow Metal-Organic-Framework-Mediated In†Situ Architecture of Copper Dendrites for Enhanced CO2 Electroreduction.

Electrocatalytic reduction of CO2 to a single product at high current densities and efficiencies remains a challenge. However, the conventional electrode preparation methods, such as drop-casting, usually suffer from low intrinsic activity. Herein, we report a synthesis strategy for preparing heterogeneous electrocatalyst composed of 3D hierarchical Cu dendrites that derived from an in situ electrosynthesized hollow copper metal-organic framework (MOF), for which the preparation of the Cu-MOF film took only 5 min. The synthesis strategy preferentially exposes active sites, which favor's the reduction of CO2 to formate. The current density could be as high as 102.1 mA cm-2 with a selectivity of 98.2 % in ionic-liquid-based electrolyte and a commonly used H-type cell.

Photooxidative Generation of Dodecaborate-Based Weakly Coordinating Anions.

Redox-active proanions of the type B12(OCH2Ar)12 [Ar = C6F5 (1), 4-CF3C6H4 (2), 3,5-(CF3)2C6H3 (3)] are introduced in the context of an experimental and computational study of the visible-light-initiated polymerization of a family of styrenes. Neutral, air-stable proanions 1-3 were found to initiate styrene polymerization through single-electron oxidation under blue-light irradiation, resulting in polymers with number-average molecular weights (Mn) ranging from ∼6 to 100 kDa. Shorter polymer products were observed in the majority of experiments, except in the case of monomers containing 4-X (X = F, Cl, Br) substituents on the styrene monomer when polymerized in the presence of 1 in CH2Cl2. Only under these specific conditions are longer polymers (>100 kDa) observed, strongly supporting the formulation that reaction conditions significantly modulate the degree of ion pairing between the dodecaborate anion and cationic chain end. This also suggests that 1-3 behave as weakly coordinating anions (WCA) upon one-electron reduction because no incorporation of the cluster-based photoinitiators is observed in the polymeric products analyzed. Overall, this work is a conceptual realization of a single reagent that can serve as a strong photooxidant, subsequently forming a WCA.

Epidermal Growth Factor Reverses the Inhibitory Effects of the Bisphosphonate, Zoledronic Acid, on Human Oral Keratinocytes and Human Vascular Endothelial Cells In Vitro via the Epidermal Growth Factor Receptor (EGFR)/Akt/Phosphoinositide 3-Kinase (PI3K) Signaling Pathway.

BACKGROUND Medication-related osteonecrosis of the jaw (MRONJ) is due to the direct effects of drug toxicity and the effects on angiogenesis. The aims of this study were to evaluate the effects of treatment with the bisphosphonate, zoledronic acid, on human oral keratinocytes (HOKs) and human umbilical vein endothelial cells (HUVECs) in vitro, and whether epidermal growth factor (EGF) could alter these effects. MATERIAL AND METHODS HOKs and HUVECs were incubated with zoledronic acid or EGF. Cell viability was assessed by the cell counting kit-8 (CCK-8), cell apoptosis was studied using Annexin-V conjugated to fluorescein isothiocyanate (FITC). Angiogenesis was studied by observing HUVEC tube formation and cell migrations using a transwell assay. A scratch wound assay investigated cell migration of HOKs. Western blot measured expression levels of phosphorylated epidermal growth factor receptor (EGFR), Akt, phosphoinositide 3-kinase (PI3K), the mechanistic target of rapamycin (mTOR), and endothelial nitric oxide synthase (eNOS). RESULTS Zoledronic acid treatment (5 µmol/L) significantly inhibited cell viability and cell migration of HOKs and HUVECs and angiogenesis of HUVECS (P<0.05); EGF partially reversed these effects (P<0.05). Zoledronic acid treatment of HOKs and HUVECs had no significant effects on apoptosis (P>0.05), but significantly reduced expression levels of p-EGFR, p-Akt, p-PI3K, p-mTOR), and p-eNOS (P<0.05); EGF partially reversed these effects and increased the expression levels (P<0.05). CONCLUSIONS EGF partially reversed the effects of the bisphosphonate, zoledronic acid, on HOKs and HUVECs in vitro via the EGFR/Akt/PI3K signaling pathway. Further studies are required to determine the effects of EGF on MRONJ including bisphosphonate-related osteonecrosis of the jaw.

In Silico Discovery of a Small Molecule Suppressing Lung Carcinoma A549 Cells Proliferation and Inducing Autophagy via mTOR Pathway Inhibition.

Mammalian target of rapamycin (mTOR) kinase is vital to the regulation of cell growth and proliferation, and it has been taken as a promising target to develop cancer therapies. By reference to the crystal structure of mTOR-PP242, we explored to discover potential ATP-competitive inhibitors of mTOR. Through the integrated use of multiple in silico screenings, the tremendous amount of compounds from the SPECS database were finally reduced to 30. After several rounds of convincing biological tests in A549 cells, the newfound C-4 was identified as a potential ATP-competitive inhibitor of mTOR. Besides A549 cell proliferation suppression caused by C-4, autophagy was also determined through autophagosome observation and autophagy flux detection in C-4 treated A549 cells. We demonstrated that C-4 could inhibit cell growth and proliferation, and this inhibition may be associated with autophagy.

Bioinformatic analysis of PFN2 dysregulation and its prognostic value in head and neck squamous carcinoma.

AIM: This study aimed to identify PFN2 expression profile, its prognostic value and the mechanism of its dysregulation in head and neck squamous cell carcinoma (HNSC). MATERIALS & METHODS: Bioinformatic analysis was performed using data in the Gene Expression Omnibus Datasets, Human Protein Atlas and The Cancer Genome Atlas-HNSC. RESULTS: PFN2 was upregulated in HNSC than in normal head and neck tissues. High PFN2 expression independently predicted poor overall survival in primary HNSC (hazard ratio: 1.548, 95% CI: 1.174-2.042; p = 0.002). Fourteen percent of HNSC cases had PFN2 amplification. PFN2 DNA methylation was negatively correlated with its mRNA expression (Pearson's r = -0.713). CONCLUSION: High PFN2 expression might serve as a valuable predictor for poor overall survival of HNSC. DNA amplification and hypomethylation might be two mechanisms of PFN2 dysregulation.

The Risk Factors that Can Increase Possibility of Mandibular Canal Wall Damage in Adult: A Cone-Beam Computed Tomography (CBCT) Study in a Chinese Population.

BACKGROUND The objective of this study was to analyze the factors that can increase the possibility of mandibular canal (MC) defect in Chinese people, to evaluate the risk of nerve impairment, and to choose the proper operative method to reduce the risk of mandibular alveolar nerve injury during the extraction of mandibular third molar (MTM). MATERIAL AND METHODS A total of 954 patients (1,304 MTMs) who underwent orthopantomography (OPG) and cone-beam computed tomography (CBCT) between July 2014 and December 2014 were included in this study. The age and gender of patients, impacted type (high impaction, moderate impaction, and low impaction), Winter classification of MTM, position of MTM relative to MC, vertical classification of MTM and MC, and the feature images of OPG were collected and compared to the imperfection of the MC wall in CBCT images. RESULTS The wall situation of MC was significantly correlated with the age of the patient, the depth of the molar, the position of the roots, and six imaging appearances on OPG. There was no significant difference based on gender. CONCLUSIONS Most incomplete walls of MCs could be inferred by OPG. However, images based on CBCT could clarify the defect of the MC and also could clearly display the spatial relationship between the root and inferior alveolar canal.

Capturing the multiscale dynamics of membrane protein complexes with all-atom, mixed-resolution, and coarse-grained models.

The structures and dynamics of protein complexes are often challenging to model in heterogeneous environments such as biological membranes. Herein, we meet this fundamental challenge at attainable cost with all-atom, mixed-resolution, and coarse-grained models of vital membrane proteins. We systematically simulated five complex models formed by two distinct G protein-coupled receptors (GPCRs) in the lipid-bilayer membrane on the ns-to-µs timescales. These models, which suggest the swinging motion of an intracellular loop, for the first time, provide the molecular details for the regulatory role of such a loop. For the models at different resolutions, we observed consistent structural stability but various levels of speed-ups in protein dynamics. The mixed-resolution and coarse-grained models show two and four times faster protein diffusion than the all-atom models, in addition to a 4- and 400-fold speed-up in the simulation performance. Furthermore, by elucidating the strengths and challenges of combining all-atom models with reduced resolution models, this study can serve as a guide to simulating other complex systems in heterogeneous environments efficiently.

A Hypothesis and Pilot Study of Age-Related Sensory Innervation of the Hard Palate: Sensory Disorder After Nasopalatine Nerve Division.

BACKGROUND The nasopalatine nerve may be injured during extraction of teeth embedded in the anterior hard palate. The neural recovery process and its impact on sensation in the anterior hard palatal region are controversial. In our clinical practice, we noticed a distinct recovery process in children compared with adolescents or adults after surgery. We hypothesized that the sensory innervations of the anterior palate might shift during later childhood and pre-adolescence, which is due to the development of the nasopalatine nerve along with the maxillary growth and permanent teeth eruption. MATERIAL AND METHODS Forty patients (20 females and 20 males, mean age 11.8±2.2) with impacted supernumerary teeth in anterior palatine area were included into our study, and were divided into 3 groups according to their age. A 24-week follow-up was conducted and the sensation in the anterior hard palate region was examined at every check point. All the data were collected and analyzed by Kaplan-Meier analysis. RESULTS Fourteen children did not complain of any numbness immediately after anesthetization, and other children with sensory disorders had shorter healing periods compared to adolescent/adult patients. CONCLUSIONS The results indicated that the dominant nerve of the anterior hard palate region was dramatically changed from the greater palatine nerve to the nasopalatine nerve, which is important in deciding when to operate and in selection of anesthesia method.

Effects of gastric bypass on FoxO1 expression in the liver and pancreas of diabetic rats.

AIM: To explore the mechanism by which gastric bypass surgery (GBS) ameliorates type 2 diabetes mellitus (T2DM) by investigating whether FoxO1 (a transcription factor that plays a crucial role in the regulation of glycolipid metabolism) expression is altered in the liver and pancreatic islet cells in a rat model of GBS-treated T2DM. METHODS: Sprague-Dawley rats were randomly divided into four groups (n = 10 rats each): diabetic rats treated by GBS (DM + GBS), diabetic rats subjected to sham operation (DM + sham), normal control rats (control), and diabetic rats without surgery (DM). Fasting levels of blood glucose (BG), insulin, and glucagon-like peptide-1 (GLP-1) were measured in all groups before and 4, 8, 16, and 24 weeks after operation. Rats were killed 24 weeks after surgery. Liver and pancreas expressions of FoxO1 were investigated by immunohistochemistry and Western blotting analyses. RESULTS: In the DM + GBS group, fasting BG before and 24 weeks after surgery decreased from 20.2 ± 2.1 to 7.7 ± 1.1 mmol/L, respectively; fasting insulin showed no change (2.9 ± 0.1 and 3.0 ± 0.1 mU/L, respectively); and fasting GLP-1 increased from 8.7 ± 0.9 to 23.5 ± 0.2 pmol/L, respectively. Fasting BG levels after surgery in the DM + GBS group were significantly lower than those in the DM + sham and DM groups. FoxO1 expression levels in the liver and pancreatic islets of the DM + GBS group were reduced compared to those in the DM + sham and DM groups. FoxO1 in the pancreatic ß-cells was expressed mainly in the cytoplasm. CONCLUSIONS: Gastric bypass may improve type 2 diabetes mellitus by changing FoxO1 expression in the liver and pancreatic islet cells.

Interactions of ß-Conglycinin (7S) with Different Phenolic Acids-Impact on Structural Characteristics and Proteolytic Degradation of Proteins.

p-Coumalic acid (PCA), caffeic acid (CA), gallic acid (GA) and chlorogenic acid (CGA) are the major phenolic acids that co-exist with soy protein components in foodstuffs. Surprisingly, there are only a handful of reports that describe their interaction with ß-Conglycinin (7S), a major soy protein. In this report, we investigated the interaction between phenolic acids and soy protein 7S and observed an interaction between each of these phenolic acids and soy protein 7S, which was carried out by binding. Further analysis revealed that the binding activity of the phenolic acids was structure dependent. Here, the binding affinity of CA and GA towards 7S was found to be stronger than that of PCA, because CA and GA have one more hydroxyl group. Interestingly, the binding of phenolic acids with soy protein 7S did not affect protein digestion by pepsin and trypsin. These findings aid our understanding of the relationship between different phenolic acids and proteins in complex food systems.

Response profiles of cytokines and chemokines against avian H9N2 influenza virus within the mouse lung.

The circulation of H9N2 viruses throughout the world, along with their expanded host range, poses a potential health risk to the public, but the host responses to H9N2 virus in mammals were little known. To obtain insight into the host immune responses to the avian H9N2 virus, the expressions of both cytokines and chemokines in the lungs of infected mice were examined by real-time polymerase chain reaction and enzyme-linked immunosorbent assay. We found that interferon gamma (IFN-γ) was the dominant antiviral component, and IFN-γ-induced protein 10 kDa, interleukin 6, chemokine (C-C motif) ligand 5 and macrophage inflammatory protein-1 alpha all played a role in pro-inflammatory responses to H9N2 viruses. In conclusion, this research can make us further understand the infection characteristics of H9N2 virus in mammalian host by providing the data on mice lung immune responses to the avian H9N2 virus.