Sulfur-Tuned Main-Group Sb-N-C Catalysts for Selective 2-Electron and 4-Electron Oxygen Reduction.

The selective oxygen reduction reaction (ORR) is important for various energy conversion processes such as the fuel cells and metal-air batteries for the 4e- pathway and hydrogen peroxide (H2O2) electrosynthesis for the 2e- pathway. However, it remains a challenge to tune the ORR selectivity of a catalyst in a controllable manner. Herein, an efficient strategy for introducing sulfur dopants to regulate the ORR selectivity of main-group Sb-N-C single-atom catalysts  is reported. Significantly, Sb-N-C with the highest sulfur content follows a 2e- pathway with high H2O2 selectivity (96.8%) and remarkable mass activity (96.1 A g-1 at 0.65 V), while the sister catalyst with the lowest sulfur content directs a 4e- pathway with a half-wave potential (E1/2 = 0.89 V) that is more positive than commercial Pt/C. In addition, practical applications for these two 2e-/4e- ORR catalysts are demonstrated by bulk H2O2 electrosynthesis for the degradation of organic pollutants and a high-power zinc-air battery, respectively. Combined experimental and theoretical studies reveal that the excellent selectivity for the sulfurized Sb-N-Cs is attributed to the optimal adsorption-desorption of the ORR intermediates realized through the electronic structure modulation by the sulfur dopants.

Effectiveness of musculoskeletal manipulations in patients with neck pain: a protocol for a systematic review and network meta-analysis.

INTRODUCTION: Neck pain is a common problem that severely affects physical and mental health. While musculoskeletal manipulations are recommended as the first-line treatment for adults with neck pain, the comparative effectiveness of different musculoskeletal manipulations remains unclear. This systematic review and network meta-analysis of randomised controlled trials (RCTs) will compare the effectiveness of different types of musculoskeletal manipulations, with the overarching aim of guiding clinical practice. METHODS AND ANALYSIS: Two independent reviewers will search four English electronic databases (Web of Science, Cochrane Library, EMBASE, PubMed) and three Chinese electronic databases (China National Knowledge Infrastructure, China Science and Technology Journal Database, Wanfang) for relevant RCTs published from 1 January 2013 to 30 April 2023. The Clinical Trials Registry (ClinicalTrials.gov) will be searched for completed but unpublished RCTs. English and Chinese will be used to search English databases and Chinese databases, respectively. RCTs of musculoskeletal manipulations for adults (aged ≥18 years) with neck pain will be considered eligible for inclusion. A pairwise meta-analysis and network meta-analysis will be performed, and pooled risk ratios, standardised mean differences and 95% CIs will be determined. ETHICS AND DISSEMINATION: Ethics approval is not required as this study is a literature review. The results of this review will be published in peer-reviewed journals or disseminated at conferences. PROSPERO REGISTRATION NUMBER: CRD42023420775.

Highly Durable and Efficient Seawater Electrolysis Enabled by Defective Graphene-Confined Nanoreactor.

Direct seawater electrolysis is a promising technology for massive green hydrogen production but is limited by the lack of durable and efficient electrocatalysts toward the oxygen evolution reaction (OER). Herein, we develop a core-shell nanoreactor as a high-performance OER catalyst consisting of NiFe alloys encapsulated within defective graphene layers (NiFe@DG) by a facile microwave shocking strategy. This catalyst needs overpotentials of merely 218 and 276 mV in alkalized seawater to deliver current densities of 10 and 100 mA cm-2, respectively, and operates continuously for 2000 h with negligible activity decay (1.0%), making it one of the best OER catalysts reported to date. Detailed experimental and theoretical analyses reveal that the excellent durability of NiFe@DG originates from the formation of the built-in electric field triggered by the defective graphene coating against chloride ions at the electrode/electrolyte interface, thus protecting the active NiFe alloys at the core from dissolution and aggregation under harsh operation conditions. Further, a highly stable and efficient seawater electrolyzer is assembled with the NiFe@DG anode and the Pt/C cathode to demonstrate the practicability of the catalysts.

Bibliometric Analysis of Research Trends on Tuina Manipulation for Neck Pain Treatment Over the Past 10 Years.

Tuina is an effective treatment for neck pain (NP). However, there has been no bibliometric analysis of the global application and emerging trends of tuina performed for NP. Therefore, this study aimed to provide an overview of the current state and future trends in the field. Articles about tuina for NP, published from January 1, 2013, to January 1, 2023, were searched in the Web of Science Core Collection database. CiteSpace (6.1.R6) and VOSviewer (1.6.18) software were used to analyze annual trends in literature posts, countries, institutions, authors, cited references, and knowledge graphs of keyword co-occurrence, clustering, and burst using standard bibliometric indicators. The final analysis comprised 505 valid documents. The results demonstrate that the number of articles in the field of tuina therapy for NP has gradually increased over the years, showing the most active countries, institutions, journals, and authors. There were 323 keywords in the field, 322 research authors, and 292 research institutions, with the USA having the most publications (n = 140). The most published institution is Vrije University Amsterdam, and the most published journal is the Cochrane Database of Systematic Reviews. Peter R Blanpied is the most influential and most-cited author. Interventions (dry needling, massage therapy, and muscle energy techniques), common treatment sites for NP (upper trapezius), and complications (cervicogenic headache) are the top three frontiers mentioned in the field of tuina research for NP. The bibliometric study showed the current status and trends in clinical research on treating patients with NP using tuina, which may help researchers identify topics of interest and scope for future research in this field.

Amorphous/crystalline heterophase electrocatalysts: synthesis, applications and perspectives.

Phase engineering is arising as an effective strategy to regulate the properties, functions and applications of nanomaterials. In particular, amorphous/crystalline (a/c) heterophase nanostructures with enriched active sites, unsaturated coordination structures and abundant phase boundaries have exhibited some intriguing properties in various catalytic applications. This review briefly summarizes the recent advances on the synthetic strategies (e.g., wet-chemical synthesis, thermal annealing, electrochemical strategy, ultrafast heating method and other strategies) and electrocatalytic applications (e.g., water splitting, oxygen reduction reaction, carbon dioxide reduction reaction, nitrogen reduction reaction and organic electrooxidation reaction) of a/c heterophase catalysts. Finally, some challenges and personal perspectives for the a/c heterophase electrocatalysts are provided.

Investigation of the Key Genes Associated with Anthocyanin Accumulation during Inner Leaf Reddening in Ornamental Kale (Brassica oleracea L. var. acephala).

Ornamental kale (Brassica oleracea L. var. acephala) is a popular decorative plant in late autumn and winter. However, only during low-temperature color-changed periods below rough 15 °C can the plant accumulate anthocyanins and exhibit a diverse array of foliar color patterns. In this study, we probed into the potential mechanism of inner leaf reddening in a red-leaf pure line of ornamental kale by physiological, metabolic, and transcriptomic analyses. Determination of anthocyanin contents in the uncolored new white leaves (S0), the light red leaves (S1) in the reddening period and the red leaves (S2) completing color change, and analysis of anthocyanin metabolites at stage S2, revealed that the coloring of red leaves was mainly attributed to the accumulation of cyanidins. We further used transcriptomic sequencing between the pairwise S0, S1, and S2 stages to identify 21 differentially expressed genes (DEGs) involved in anthocyanin biosynthesis, among which the expression level of 14 DEGs was positively correlated with anthocyanin accumulation, and 6 DEGs were negatively correlated with anthocyanin accumulation. A total of 89 co-expressed genes were screened out, from which three DEGs (BoCHI, Bo4CL3, and BoF3H) were identified as hub genes in co-expression DEGs network. BoDFR and BoCHI were the DEGs with the highest expressions at S2. Moreover, two co-expressed DEGs related to stress response (BoBBX17 and BoCOR47) also exhibited upregulated expressions and positive correlations with anthocyanin accumulation. A deep dive into the underlying regulatory network of anthocyanin accumulation comprising these six upregulated DEGs from S0 to S2 was performed via trend, correlation, and differentially co-expression analysis. This study uncovered the DEGs expression profiles associated with anthocyanin accumulation during ornamental kale inner leaf reddening, which provided a basis for further dissecting the molecular mechanisms of leaf color characteristic change in ornamental kale at low temperatures.

A General Strategy to Remove Metal Aggregates toward Metal-Nitrogen-Carbon Catalysts with Exclusive Atomic Dispersion.

Metal- and nitrogen-doped nanocarbons (M-N-Cs) are promising alternatives to precious metals for catalyzing electrochemical energy conversion processes. However, M-N-Cs synthesized by high-temperature pyrolysis frequently suffer from compositional heterogeneity with the simultaneous presence of atomically dispersed M-Nx sites and crystalline metal nanoparticles (NPs), which hinders the identification of active sites and rational optimization in performance. Herein, a universal and efficient strategy is reported to obtain both precious- and nonprecious-metal-based M-N-Cs (M = Pt, Fe, Co, Ni, Mn, Cu, Zn) with exclusive atomic dispersion by making use of ammonium iodide as the etchant to remove excessive metal aggregates at high temperature. Taking Pt-N-C as a proof-of-concept demonstration, the complete removal of Pt NPs in Pt-N-C enables clarification on the contributions of the atomic Pt-Nx moieties and Pt NPs to the catalytic activity toward the hydrogen evolution reaction. Combined electrochemical measurements and theoretical calculations identify that the atomic Pt-Nx moieties by themselves possess negligible activity, but they can significantly boost the activity of the Pt NPs via the synergistic effect.

Sb2S3-templated synthesis of sulfur-doped Sb-N-C with hierarchical architecture and high metal loading for H2O2 electrosynthesis.

Selective two-electron (2e-) oxygen reduction reaction (ORR) offers great opportunities for hydrogen peroxide (H2O2) electrosynthesis and its widespread employment depends on identifying cost-effective catalysts with high activity and selectivity. Main-group metal and nitrogen coordinated carbons (M-N-Cs) are promising but remain largely underexplored due to the low metal-atom density and the lack of understanding in the structure-property correlation. Here, we report using a nanoarchitectured Sb2S3 template to synthesize high-density (10.32 wt%) antimony (Sb) single atoms on nitrogen- and sulfur-codoped carbon nanofibers (Sb-NSCF), which exhibits both high selectivity (97.2%) and mass activity (114.9 A g-1 at 0.65 V) toward the 2e- ORR in alkaline electrolyte. Further, when evaluated with a practical flow cell, Sb-NSCF shows a high production rate of 7.46 mol gcatalyst-1 h-1 with negligible loss in activity and selectivity in a 75-h continuous electrolysis. Density functional theory calculations demonstrate that the coordination configuration and the S dopants synergistically contribute to the enhanced 2e- ORR activity and selectivity of the Sb-N4 moieties.

Fine Mapping of BoVl Conferring the Variegated Leaf in Ornamental Kale (Brassica oleracea var. acephala)

Ornamental kale, as a burgeoning landscaping plant, is gaining popularity for its rich color patterns in leaf and cold tolerance. Leaf variegation endows ornamental kale with unique ornamental characters, and the mutants are ideal materials for exploring the formation mechanisms of variegated phenotype. Herein, we identified a novel variegated leaf kale mutant 'JC007-2B' with green margins and white centers. Morphological observations and physiological determinations of the green leaf stage (S1), albino stage (S2) and variegated leaf stage (S3) demonstrated that the chloroplast structure and photosynthetic pigment content in the white sectors (S3_C) of variegated leaves were abnormal. Genetic analysis revealed that a single dominant nuclear gene (BoVl) controlled the variegated leaf trait of 'JC007-2B', and three candidate genes for BoVl were fine-mapped to a 6.74 Kb interval on chromosome C03. Multiple sequence alignment among the green-leaf mapping parent 'BS', recombinant individuals, mutant parent 'JC007-2B' and its same originated DH line population established that the mutation sites in Bo3g002080 exhibited a complete consensus. Bo3g002080, homologous to Arabidopsis MED4, was identified as the candidate gene for BoVl. Expression analysis showed that Bo3g002080 displayed a 2158.85-fold higher expression at albino stage than that in green leaf stage. Transcriptome analysis showed that related pathways of photosynthesis and chloroplast development were significantly enriched in the white sectors, and relevant DEGs involved in these pathways were almost down-regulated. Overall, our study provides a new gene resource for cultivar breeding in ornamental kale and contributes to uncovering the molecular genetic mechanism underlying the variegated leaf formation.

Engineering the Morphology and Microenvironment of a Graphene-Supported Co-N-C Single-Atom Electrocatalyst for Enhanced Hydrogen Evolution.

Graphene-supported single-atom catalysts (SACs) are promising alternatives to precious metals for catalyzing the technologically important hydrogen evolution reaction (HER), but their performances are limited by the low intrinsic activity and insufficient mass transport. Herein, a highly HER-active graphene-supported Co-N-C SAC is reported with unique design features in the morphology of the substrate and the microenvironment of the single metal sites: i) the crumpled and scrolled morphology of the graphene substrate circumvents the issues encountered by stacked nanoplatelets, resulting in improved exposure of the electrode/electrolyte interfaces (≈10 times enhancement); ii) the in-plane holes in graphene preferentially orientate the Co atoms at the edge sites with low-coordinated Co-N3 configuration that exhibits enhanced intrinsic activity (≈2.6 times enhancement compared to the conventional Co-N4 moiety), as evidenced by detailed experiments and density functional theory calculations. As a result, this catalyst exhibits significantly improved HER activity with an overpotential (η) of merely 82 mV at 10 mA cm-2 , a small Tafel slope of 59.0 mV dec-1 and a turnover frequency of 0.81 s-1 at η = 100 mV, ranking it among the best Co-N-C SACs.

Traditional Chinese medicine intervention for autism spectrum disorders: A protocol for systematic review and network meta-analysis.

BACKGROUND: Autism spectrum disorder (ASD) is a neurodevelopmental disorder characterized by impairments in social communication, social interaction, and restrictive or repetitive behaviors. Traditional Chinese medicine (TCM) has been used in the clinical management of ASD, especially in mainland China, where studies have shown promising efficacy. However, this remains to be further explored and clarified. Therefore, the purpose of this study was to evaluate the effectiveness and safety of conventional treatment-based TCM interventions for ASD. METHOD: The study will be conducted from January 2022, and the following electronic databases will be searched: China Biological Medicine Database, Chinese Scientific Journals Database, Wan Fang database, and China National Knowledge Infrastructure, the Cochrane Library, Web of Science, PubMed, and EMBASE Database. Only randomized controlled trials of TCM interventions for ASD will be included. The Autism Diagnostic Observation Scale, Autism Diagnostic Interview-Revised, and Childhood Autism Rating Scale will be the primary outcome indicators. The methodological quality of this Bayesian-based network meta-analysis will be performed using the "Risk of Bias" tool. Stata 14.0 and WinBUGS 1.4.3 will be used to analyze the data. In addition, assessment of heterogeneity, inconsistency, subgroups, sensitivity, and publication bias will be conducted using the Cochrane Collaboration's tools. RESULTS: The results of this study will be submitted to a peer-reviewed journal for publication. CONCLUSION: This study will help patients recover better, provide clinical evidence for practitioners, and promote the use of TCM in ASD interventions.

Electronic Structure Regulation of Single-Atom Catalysts for Electrochemical Oxygen Reduction to H2 O2.

Electrochemical synthesis of hydrogen peroxide (H2 O2 ) via the 2-electron oxygen reduction reaction (ORR) has emerged as a promising alternative to the energy-intensive anthraquinone process and catalysts combining high selectivity with superior activity are crucial for enhancing the efficiency of H2 O2 electrosynthesis. In recent years, single-atom catalysts (SACs) with the merits of maximum atom utilization efficiency, tunable electronic structure, and high mass activity have attracted extensive attention for the selective reduction of O2 to H2 O2 . Although considerable improvements are made in the performance of SACs toward the 2-electron ORR process, the principles for modulating the catalytic properties of SACs by adjusting the electronic structure remain elusive. In this review, the regulation strategies for optimizing the 2-electron ORR activity and selectivity of SACs by different methods of electronic structure tuning, including the altering of the central metal atoms, the modulation of the coordinated atoms, the substrate effect, and alloy engineering are summarized. Finally, the challenges and future prospects of advanced SACs for H2 O2 electrosynthesis via the 2-electron ORR process are proposed.

Iodine-Doping-Induced Electronic Structure Tuning of Atomic Cobalt for Enhanced Hydrogen Evolution Electrocatalysis.

The development of strategies for tuning the electronic structure of the metal sites in single-atom catalysts (SACs) is the key to optimizing their activity. Herein, we report that iodine doping within the carbon matrix of a cobalt-nitrogen-carbon (Co-N-C) catalyst can effectively modulate its electronic structure and catalytic activity toward the hydrogen evolution reaction (HER). The iodine-doped Co-N-C catalyst shows exceptional HER activity in acid with an overpotential of merely 52 mV at 10 mA cm-2, a small Tafel slope of 56.1 mV dec-1, making it among the best SACs based on both precious and nonprecious metals. Moreover, this catalyst possesses a high turnover frequency (TOF) value of 1.88 s-1 (η = 100 mV), which is about 1 order of magnitude larger than that (0.2 s-1) of the iodine-free counterpart. Experimental and theoretical studies demonstrate that the introduction of iodine dopants lowers the chemical oxidation state of the Co sites, resulting in the optimized hydrogen adsorption and facilitated HER kinetics. This work provides an alternative strategy to regulate the electronic structure of SACs for improved performance.

Design of Aligned Porous Carbon Films with Single-Atom Co-N-C Sites for High-Current-Density Hydrogen Generation.

Metal- and nitrogen-doped carbon (M-N-C) materials as a unique class of single-atom catalysts (SACs) have increasingly attracted attention as the replacement of platinum for the hydrogen evolution reaction (HER); however, their employment as HER electrodes at high current densities of industrial level remains a grand challenge. Herein, an aligned porous carbon film embedded with single-atom Co-N-C sites of exceptional activity and stability at high current densities is designed. Within the film, the atomic CoNx moieties exhibit high intrinsic activity, while the multiscale porosity of the carbon frameworks with vertically aligned microchannels afford facilitated mass transfer under the conditions of high production rate and ultrathick electrodes. Moreover, the superwetting properties of the film promote electrolyte wetting and ensure the timely removal of the evolving H2 gas bubbles. The as-designed film can work as an efficient HER electrode to deliver 500 and 1000 mA cm-2 in acid at overpotentials of 272 and 343 mV, respectively, and can operate uninterruptedly and stably at 1000 mA cm-2 for at least 32 h under static conditions. These findings pave the road toward the rational design of SACs with improved activity and stability at high current densities in gas-evolving electrocatalytic processes.