Seeding Atomic Silver into Internal Lattice Sites of Transition Metal Oxide for Advanced Electrocatalysis.

Transition metal oxides (TMOs) are widely studied for loading of various catalysts due to their low cost and high structure flexibility. However, the prevailing close-packed nature of most TMOs crystals has restricted the available loading sites to surface only, while their internal bulk lattice remains unactuated due to the inaccessible narrow space that blocks out most key reactants and/or particulate catalysts. Herein, using tunnel-structured MnO2, this study demonstrates how TMO's internal lattice space can be activated as extra loading sites for atomic Ag in addition to the conventional surface-only loading, via which a dual-form Ag catalyst within MnO2 skeleton is established. In this design, not only faceted Ag nanoparticles are confined onto MnO2 surface by coherent lattice-sharing, Ag atomic strings are also seeded deep into the sub-nanoscale MnO2 tunnel lattice, enriching the catalytically active sites. Tested for electrochemical CO2 reduction reaction (eCO2RR), such dual-form catalyst exhibits a high Faradaic efficiency (94%), yield (67.3 mol g-1 h-1) and durability (≈48 h) for CO production, exceeding commercial Ag nanoparticles and most Ag-based electrocatalysts. Theoretical calculations further reveal the concurrent effect of such dual-form catalyst featuring facet-dependent eCO2RR for Ag nanoparticles and lattice-confined eCO2RR for Ag atomic strings, inspiring the future design of catalyst-substrate configuration.

Two-dimensional Cu Plates with Steady Fluid Fields for High-rate Nitrate Electroreduction to Ammonia and Efficient Zn-Nitrate Batteries.

Nitrate electroreduction reaction (eNO3 -RR) to ammonia (NH3) provides a promising strategy for nitrogen utilization, while achieving high selectivity and durability at an industrial scale has remained challenging. Herein, we demonstrated that the performance of eNO3 -RR could be significantly boosted by introducing two-dimensional Cu plates as electrocatalysts and eliminating the general carrier gas to construct a steady fluid field. The developed eNO3 -RR setup provided superior NH3 Faradaic efficiency (FE) of 99 %, exceptional long-term electrolysis for 120 h at 200 mA cm-2, and a record-high yield rate of 3.14 mmol cm-2 h-1. Furthermore, the proposed strategy was successfully extended to the Zn-nitrate battery system, providing a power density of 12.09 mW cm-2 and NH3 FE of 85.4 %, outperforming the state-of-the-art eNO3 -RR catalysts. Coupled with the COMSOL multiphysics simulations and in situ infrared spectroscopy, the main contributor for the high-efficiency NH3 production could be the steady fluid field to timely rejuvenate the electrocatalyst surface during the electrocatalysis.

Recent Progress Toward Electrocatalytic Conversion of Nitrobenzene.

Despite that extensive efforts have been dedicated to the search for advanced catalysts to boost the electrocatalytic nitrobenzene reduction reaction (eNBRR), its progress is severely hampered by the limited understanding of the relationship between catalyst structure and its catalytic performance. Herein, this review aims to bridge such a gap by first analyzing the eNBRR pathway to present the main influential factors, such as electrolyte feature, applied potential, and catalyst structure. Then, the recent advancements in catalyst design for eNBRR are comprehensively summarized, particularly about the impacts of chemical composition, morphology, and crystal facets on regulating the local microenvironment, electron and mass transport for boosting catalytic performance. Finally, the future research of eNBRR is also proposed from the perspectives of performance enhancement, expansion of product scope, in-depth understanding of the reaction mechanism, and acceleration of the industrialization process through the integration of upstream and downstream technologies.

Electrocatalytic CO2 Reduction to Ethylene: From Advanced Catalyst Design to Industrial Applications.

The value-added chemicals, monoxide, methane, ethylene, ethanol, ethane, and so on, can be efficiently generated through the electrochemical CO2 reduction reaction (eCO2 RR) when equipped with suitable catalysts. Among them, ethylene is particularly important as a chemical feedstock for petrochemical manufacture. However, despite its high Faradaic efficiency achievable at relatively low current densities, the substantial enhancement of ethylene selectivity and stability at industrial current densities poses a formidable challenge. To facilitate the industrial implementation of eCO2 RR for ethylene production, it is imperative to identify key strategies and potential solutions through comprehending the recent advancements, remaining challenges, and future directions. Herein, the latest and innovative catalyst design strategies of eCO2 RR to ethylene are summarized and discussed, starting with the properties of catalysts such as morphology, crystalline, oxidation state, defect, composition, and surface engineering. The review subsequently outlines the related important state-of-the-art technologies that are essential in driving forward eCO2 RR to ethylene into practical applications, such as CO2 capture, product separation, and downstream reactions. Finally, a greenhouse model that integrates CO2 capture, conversion, storage, and utilization is proposed to present an ideal perspective direction of eCO2 RR to ethylene.

Accelerating ammonia synthesis in a membraneless flow electrolyzer through coupling ambient dinitrogen oxidation and water splitting.

An electrochemical approach for ammonia production is successfully developed by coupling the anodic dinitrogen oxidation reaction (NOR) and cathodic hydrogen evolution reaction (HER) within a well-designed membraneless flow electrolyzer. The obtained reactor shows the preferential yield of ammonia over nitrogen oxides on the vanadium nitride catalyst surface. At an applied oxidation potential of 2.25 V versus the reversible hydrogen electrode (vs RHE), a promoted ammonia production rate and Faradaic efficiency (FE) were obtained with 9.9 mmol g-1 h-1 (0.029 mmol cm-2 h-1) and 4.8%, respectively. Besides, the negative affection of ammonia contamination is efficiently alleviated. Density functional theory calculations revealed that the thermodynamic energy needed to produce ammonia (-0.63 eV) is far lower than that of producing nitrogen oxide (0.96 eV) from hydrogenated nitrogen oxides [∗N2OH] splitting, confirming the coupling of NOR and HER.

Microenvironment Engineering for the Electrocatalytic CO2 Reduction Reaction.

Rather than just focusing on the catalyst itself in the electrocatalytic CO2 reduction reaction (eCO2 RR), as previously reviewed elsewhere, we herein extend the discussion to the special topic of the microenvironment around the electrocatalytic center and present a comprehensive overview of recent research progress. We categorize the microenvironment based on the components relevant to electrocatalytic active sites, i.e., the catalyst surface, substrate, co-reactants, electrolyte, membrane, and reactor. Supported by most of the reported articles, the relevant factors affecting the catalytic performance of eCO2 RR are then discussed in detail, and existing challenges and potential solutions are mentioned. Perspectives for the future research on eCO2 RR, including the integration of different microenvironment factors, the extension to industrial application by coupling with carbon capture and conversion, and separation of products, are also discussed.

A novel coumarin-TPA based fluorescent probe for turn-on hypochlorite detection and lipid-droplet-polarity bioimaging in cancer cells.

A novel fluorescent compound, named C-TPA, based on coumarin (acceptor) and triphenylamine (donor) was facilely designed and fabricated through a one-step Suzuki coupling reaction. As a donor group, triphenylamine can efficiently enhance the fluorescence intensity and photostability of coumarin, and thus improve the detection efficiency. C-TPA-S was obtained from C-TPA treated with Lawesson's reagent and C-TPA-S can be used for the turn-on detection of hypochlorite through oxidative desulfurization with a low detection limit of 0.12 µM. Moreover, the intramolecular charge transfer process between the donor and acceptor group endows C-TPA with solvatochromism property and makes C-TPA a good candidate for polarity detection. The C-TPA with bright green fluorescence was highly efficient for imaging the microenvironment of polarity both in living cells and tissues with high selectivity and photostability, which can be applied in the diagnosis for the cancer cells.

New Functional Organic Materials and Their Photoelectric Applications: A New Open Special Issue of Materials.

New Functional Organic Materials and Their Photoelectric Applications is a new open Special Issue of Materials, which focuses on designing and fabricating advanced functional organic optoelectronic materials and makes great contributions to investigating their properties, related applications, and underlying mechanisms [...].

[Moxibustion on plaque psoriasis of blood stasis: a randomized controlled trial].

OBJECTIVE: To observe the short-term and long-term effects of moxibustion on plaque psoriasis of blood stasis, and to compare the curative effect between moxibustion and calcipotriol ointment. METHODS: A total of 80 patients with plaque psoriasis of blood stasis were randomly divided into an observation group (40 cases, 2 cases dropped off) and a control group (40 cases, 4 cases dropped off). Both groups were given routine medical vaseline topical emollient basic treatment. In the observation group, moxibustion was applied to ashi point (target skin lesions), Zusanli (ST 36), Xuehai (SP 10) and Qihai (CV 6) for 30 min each time, 3 times a week. The control group was treated with calcipotriol ointment (0.25 g each time, once in the morning and evening) on the target skin lesions. Both groups were treated for 8 weeks. The psoriasis area and severity index (PASI) score before and after treatment, main clinical symptoms of TCM score and dermatology life quality index (DLQI) score before and after treatment and 3 and 6 moths follow-up were observed in the two groups; the clinical efficacy after treatment was evaluated and the recurrence rates of the two groups were followed up for 3 and 6 months after treatment. RESULTS: After treatment, the PASI scores in the both groups were lower than before treatment (P<0.01). After treatment and 3 and 6 months follow-up, the main clinical symptoms of TCM scores and DLQI scores of the two groups were lower than those before treatment (P<0.05), and at 3 and 6 months follow-up, those in the observation group were lower than the control group (P<0.01). There was no statistically significant difference between the observation group and the control group in overall effective rate and target skin lesion effective rate (P>0.05). At 3 and 6 months follow-up, the overall recurrence rate and target skin lesion recurrence rate in the observation group were lower than those in the control group (P<0.05). CONCLUSION: Both moxibustion and calcipotriol ointment have good short-term effects on plaque psoriasis of blood stasis. Moxibustion has more advantages in reducing the recurrence rate of psoriasis, improving the main clinical symptoms of TCM and quality of life.

Efficacy and Safety of Jueyin Granules for Patients with Mild-to-Moderate Psoriasis Vulgaris: Protocol for a Multicenter Randomized Placebo-Controlled Trial.

Introduction. The etiology and pathogenesis of psoriasis are complex. Blood-heat syndrome is the core pathogenesis of psoriasis. Based on theories of Chinese medicine (CM), heat-clearing and blood-cooling (HCBC) are the primary treatment. Very few studies have investigated the pharmacological mechanism of the CM HCBC method for treating psoriasis. This multicenter randomized controlled trial will focus on treating psoriasis blood-heat syndrome with the HCBC method using Jueyin granules (JYKL). This will be an objective and standardized evaluation of the efficacy, safety, and reproducibility of the HCBC method to obtain objective evidence meeting international standards that aim to establish a clinical standard suitable for the popular application of CM for treating psoriasis. Methods and Analysis. A five-center randomized double-blind placebo-controlled clinical design will be used in this study. At least 196 participants will be randomly assigned to receive either JYKL or placebo treatment approximately 30 minutes after meals in the morning and evening (one sachet per time, twice daily for 8 consecutive weeks). The study duration will be 17 weeks, including 1 week of screening, 8 weeks of intervention, and 8 weeks of follow-up. The patients will be evaluated every 2 weeks, and the measures will be compared with baseline values. The primary outcome measure will be the psoriasis lesion area severity index. We will also observe the recurrence rate, body surface area, physician global assessment, dermatology life quality index, quality of life index, visual analogue scale score, CM symptom score, combined drug use, and adverse events. This trial is registered with NCT03961230.

Filter-Free Selective Light Monitoring by Organic Field-Effect Transistor Memories with a Tunable Blend Charge-Trapping Layer.

Integration of selective photodetection and signal storage in a single device, such as organic field-effect transistor (OFET) memories, meets the demands for radiation monitoring and protection. A new strategy is developed to achieve filter-free and selective light monitoring by adopting a solution-processed blend charge-trapping layer in OFET memories, where the charge-trapping layer is composed of phenyl-C61-butyric acid methyl ester (PCBM) dispersed in a polymer electret thin film. The OFET memory without PCBM shows response only to ultraviolet light, whereas the spectral response edges are extended to the visible and near-infrared regions in the corresponding devices with relatively low and high contents of PCBM in the charge-trapping layer, respectively. A set of OFET memories with different PCBM contents is used to qualitatively evaluate the light composition in an optical source. The tunable spectral response in the OFET memories is ascribed to the additional photoassisted charge-trapping paths depending on the blend ratio in the charge-trapping layer. This mechanism may inspire alternative approaches to organic-based optical sensing and monitoring in flexible and wearable electronics.

Formation of carbon-nitrogen bonds in carbon monoxide electrolysis.

The electroreduction of CO2 is a promising technology for carbon utilization. Although electrolysis of CO2 or CO2-derived CO can generate important industrial multicarbon feedstocks such as ethylene, ethanol, n-propanol and acetate, most efforts have been devoted to promoting C-C bond formation. Here, we demonstrate that C-N bonds can be formed through co-electrolysis of CO and NH3 with acetamide selectivity of nearly 40% at industrially relevant reaction rates. Full-solvent quantum mechanical calculations show that acetamide forms through nucleophilic addition of NH3 to a surface-bound ketene intermediate, a step that is in competition with OH- addition, which leads to acetate. The C-N formation mechanism was successfully extended to a series of amide products through amine nucleophilic attack on the ketene intermediate. This strategy enables us to form carbon-heteroatom bonds through the electroreduction of CO, expanding the scope of products available from CO2 reduction.

Changes in seroprevalence of hepatitis A after the implementation of universal childhood vaccination in Shandong Province, China: A comparison between 2006 and 2014.

OBJECTIVES: The hepatitis A vaccine (HepA) has been included in the national expanded program on immunization (EPI) in China since 2008. This study was performed to evaluate the change in dynamics of the seroepidemiology of hepatitis A virus (HAV) before and after the introduction of the program. METHODS: The trends in seroepidemiology of anti-HAV antibodies were examined in Shandong Province, China, drawing on two population-based samples of persons aged 1-59 years, one obtained in the year 2006 (n = 6682) and the other in 2014 (n = 5095). RESULTS: A dramatic increase in seroprevalence of anti-HAV antibodies from 30.76% (95% confidence interval (CI) 26.24-35.28%) to 77.46% (95% CI 74.04-80.87%) among children aged 1.5-7 years (born after HepA was recommended for routine childhood immunization), as well as an increase from 35.32% (95% CI 29.31-41.33%) to 66.69% (95% CI 55.59-77.80%) in subjects aged 8-14 years, was observed in 2014 when compared with 2006. By contrast, a decline in seroprevalence among subjects aged 15-29 years, as seen particularly in those 20-29 years of age, from 85.72% (95% CI 80.29-91.14%) to 69.24% (95% CI 62.02-76.45%), was found in this study. There was no statistically significant difference in seroprevalence between 2006 and 2014 among the subjects older than 30 years of age. CONCLUSIONS: The national HepA routine immunization program has had a positive effect, leading to an increase in anti-HAV seroprevalence among children in Shandong Province, China. More attention should be paid to young adults in the province.

A Highly Porous Copper Electrocatalyst for Carbon Dioxide Reduction.

Electrochemical reduction of carbon dioxide (CO2 ) is an appealing approach toward tackling climate change associated with atmospheric CO2 emissions. This approach uses CO2 as the carbon feedstock to produce value-added chemicals, resulting in a carbon-neutral (or even carbon-negative) process for chemical production. Many efforts have been devoted to the development of CO2 electrolysis devices that can be operated at industrially relevant rates; however, limited progress has been made, especially for valuable C2+ products. Herein, a nanoporous copper CO2 reduction catalyst is synthesized and integrated into a microfluidic CO2 flow cell electrolyzer. The CO2 electrolyzer exhibits a current density of 653 mA cm-2 with a C2+ product selectivity of ≈62% at an applied potential of -0.67 V (vs reversible hydrogen electrode). The highly porous electrode structure facilitates rapid gas transport across the electrode-electrolyte interface at high current densities. Further investigations on electrolyte effects reveal that the surface pH value is substantially different from the pH of bulk electrolyte, especially for nonbuffering near-neutral electrolytes when operating at high currents.

Oxygen Species on Nitrogen-Doped Carbon Nanosheets as Efficient Active Sites for Multiple Electrocatalysis.

Designing and synthesizing nanomaterials with high coverages of active sites is one of the most-pivotal factors in the construction of state-of-the-art electrocatalysts with high performance. Herein, we proposed a facile in situ templated method for the fabrication of oxygen-species-modified nitrogen-doped carbon nanosheets (O-N-CNs). The epoxy oxygen and ketene oxygen combined with graphitic-nitrogen defects in O-N-CNs gave more active sites for the oxygen-reduction reaction (ORR) and the oxygen-evolution reaction (OER), as proven via theoretical and experimental results, while the carbonyl-oxygen and epoxy-oxygen species showed more efficient electrocatalytic activity for the hydrogen evolution reaction (HER). Hence, the O-N-CNs showed highly active electrocatalytic performance toward ORR, OER, and HER. More importantly, the superior multifunctional electrocatalytic activity of O-N-CNs allowed their use in the construction of Zn-air batteries to power the corresponding water-splitting cells. This work can offer an understanding of underlying mechanisms of oxygen species on N-doped carbon materials toward multiple electrocatalysis and facilitate the engineering of electrocatalysts for energy-storage and -conversion devices.

Controlled deposition of palladium nanodendrites on the tips of gold nanorods and their enhanced catalytic activity.

Plasmonic Au-Pd nanostructures have drawn significant attention for use in heterogeneous catalysis. In this study, palladium nanodendrite-tipped gold nanorods (PdND-T-AuNRs) were subjected to a facile fabrication under mild reaction conditions. The palladium amounts on the two tips were tunable. In the preparation of PdND-T-AuNRs, dense capped AuNRs, a low reaction temperature, and suitable stabilizing agents were identified as critical reaction parameters for controlling palladium nanodendrites deposited on both ends of AuNRs. After overgrowth with palladium nanodendrites, the longitudinal surface plasmonic resonance peaks of PdND-T-AuNRs were red-shifted from 810 nm to 980 nm. The electrocatalytic activity of PdND-T-AuNRs for ethanol oxidation was examined, which was a bit weaker than that of cuboid core-shell Au-Pd nanodendrites; however, PdND-T-AuNRs were more stable in ethanol electrooxidation. Moreover, the photocatalytic activity of PdND-T-AuNRs for Suzuki cross-coupling reactions was investigated. At room temperature, nearly 100% yield was obtained under laser irradiation. The results can further enhance our capability of fine-tuning the optical, electronic, and catalytic properties of the bimetallic Au-Pd nanostructures.

Use of human aortic extracellular matrix as a scaffold for construction of a patient-specific tissue engineered vascular patch.

Synthetic or biologic materials are usually used to repair vascular malformation in congenital heart defects; however, non-autologous materials show both mismatch compliance and antigenicity, as well as a lack of recellularization on its surface. Here, we constructed a tissue-engineered vascular patch (TEVP) using decellularized extracellular matrix (ECM) scaffold obtained from excised human aorta during surgery, which was seeded with patient-derived bone marrow CD34-positive (CD34+) progenitor cells. While cellular components were removed, the decellularized ECM scaffold retained native ECM composition, similar mechanical performance to undecellularized aortic tissue, and supported the adhesion, survival and proliferation of CD34+ progenitor cells. Interestingly, after in vitro seeding of decellularized aortic ECM scaffold for 21 d, CD34+ progenitor cells differentiated into mature vascular endothelial cells without addition of any growth factors, as confirmed by the increased levels of endothelial surface markers (CD31, Von Willebrand factor (VWF), VE-cadherin and ICAM-2) and upregulated gene levels (CD31, VWF and eNOS) concurrently with decreased expression of stem cell markers (CD133 and CD34), thus, resulting in surface endothelialization of decellularized ECM scaffold. Consequently, the patient-specific TEVP constructed in this study holds great potential for clinical use in pediatric patients with vascular malformation.

Incorporating Nitrogen-Doped Graphene Quantum Dots and Ni3 S2 Nanosheets: A Synergistic Electrocatalyst with Highly Enhanced Activity for Overall Water Splitting.

A noble-metal-free electrocatalyst is fabricated via in situ formation of nanocomposite of nitrogen-doped graphene quantum dots (NGQDs) and Ni3 S2 nanosheets on the Ni foam (Ni3 S2 -NGQDs/NF). The resultant Ni3 S2 -NGQDs/NF can serve as an active, binder-free, and self-supported catalytic electrode for direct water splitting, which delivers a current density of 10 mA cm-2 at an overpotential of 216 mV for oxygen evolution reaction and 218 mV for hydrogen evolution reaction in alkaline media. This bifunctional electrocatalyst enables the construction of an alkali electrolyzer with a low cell voltage of 1.58 V versus reversible hydrogen electrode (RHE) at 10 mA cm-2 . The experimental results and theoretical calculations demonstrate that the synergistic effects of the constructed active interfaces are the key factor for excellent performance. The nanocomposite of NGQDs and Ni3 S2 nanosheets can be promising water splitting electrocatalyst for large-scale hydrogen generation or other energy storage and conversion applications.

[Correlation Research on HGF and c-Met of Chronic Erosive Gastritis Patients].

Objective To observe the correlation of hepatocyte growth factor (HGF) and Hepato- cyte growth factor receptor (c-Met ) in serum and gastric mucosa tissues of chronic erosive gastritis pa- tients. Methods Totally 70 patients with chronic erosive gastritis were selected and assigned to turbidity toxin intrinsic syndrome group and Gan-wei disharmony syndrome group, HGF expression level of ser- um,and HGF,c-Met expression level of gastric mucosa tissues were measured;the correlation of HGF and c-Met in gastric mucosa tissues, and the correlation of HGF in serum and gastric mucosa tissues were analyzed. Results The expression level of HGF and c-Met in turbidity toxin intrinsic syndrome group was higher than that in Gan-wei disharmony syndrome group (P <0. 05) ; the expression level of HGF in gastric mucosa tissues was positively correlated with c-Met(r =0. 831 , P <0. 05) ; the expression level of HGF in serum was positively correlated with that of gastric mucosa tissues(r =0. 656, P <0. 05). Conclusions There was correlation between turbidity toxin intrinsic syndrome of Chronic Erosive Gastri- tis patients and the expression level of HGF and c-Met.

Facile synthesis of three-dimensional Pt-Pd alloyed multipods with enhanced electrocatalytic activity and stability for ethylene glycol oxidation.

A facile one-pot solvothermal method was developed for the fabrication of well-defined three-dimensional highly branched Pt-Pd alloyed multipods, using ethylene glycol as a solvent and a reducing agent, along with N-methylimidazole as a structure-directing agent, without any seed, template, or surfactant. The as-prepared nanocrystals exhibited a relatively large electrochemically active surface area, improved electrocatalytic activity and superior stability for ethylene glycol oxidation in alkaline media, compared with commercial Pt black and Pd black, making them promising electrocatalysts in fuel cells.