PdFe Single-Atom Alloy Metallene for N2 Electroreduction.

Single-atom alloys hold great promise for electrocatalytic nitrogen reduction reaction (NRR), while the comprehensive experimental/theoretical investigations of SAAs for the NRR are still missing. Herein, PdFe1 single-atom alloy metallene, in which the Fe single atoms are confined on a Pd metallene support, is first developed as an effective and robust NRR electrocatalyst, delivering exceptional NRR performance with an NH3 yield of 111.9 µg h-1 mg-1 , a Faradaic efficiency of 37.8 % at -0.2 V (RHE), as well as a long-term stability for 100 h electrolysis. In-depth mechanistic investigations by theoretical computations and operando X-ray absorption/Raman spectroscopy indentify Pd-coordinated Fe single atoms as active centers to enable efficient N2 activation via N2 -to-Fe σ-donation, reduced protonation energy barriers, suppressed hydrogen evolution and excellent thermodynamic stability, thus accounting for the high activity, selectivity and stability of PdFe1 for the NRR.

Synergistic Enhancement of Electrocatalytic Nitrogen Reduction Over Boron Nitride Quantum Dots Decorated Nb2 CTx -MXene.

Electrochemical N2 fixation represents a promising strategy toward sustainable NH3 synthesis, whereas the rational design of high-performance catalysts for the nitrogen reduction reaction (NRR) is urgently required but remains challenging. Herein, a novel hexagonal BN quantum dots (BNQDs) decorated Nb2 CTx -MXene (BNQDs@Nb2 CTx ) is explored as an efficient NRR catalyst. BNQDs@Nb2 CTx presents the optimum NRR activity with an NH3 yield rate of 66.3 µg h-1 mg-1 (-0.4 V) and a Faradaic efficiency of 16.7% (-0.3 V), outperforming most of the state-of-the-art NRR catalysts, together with an excellent stability. Theoretical calculations revealed that the synergistic interplay of BNQDs and Nb2 CTx enabled the creation of unique interfacial B sites serving as NRR catalytic centers capable of enhancing the N2 activation, lowering the reaction energy barrier and impeding the H2 evolution.

A Case of Bernard-Soulier Syndrome due to a Novel Homozygous Missense Mutation in an Exon of the GP1BA Gene.

Bernard-Soulier syndrome (BSS) is an extremely rare autosomal recessive bleeding disorder clinically characterized by macrothrombocytopenia and a mucocutaneous bleeding tendency. A 1-year-old Chinese patient who was born to consanguineous parents was diagnosed with early onset of BSS. Gene sequencing and bioinformatics analysis were conducted. We identified a novel homozygous missense mutation (c.790T>C) in the GP1BAgene that causes an amino acid residue substitution of a cysteine with an arginine that might have a deleterious effect on the protein function as predicted by bioinformatics analysis. If a patient has clinical manifestations that include recurrent mucocutaneous bleeding, a mean platelet volume and platelet-large cell ratio above normal levels, and giant platelets on a peripheral smear and has consanguineous parents, a diagnosis of BSS can be suspected. In these situations, gene sequencing for mutations in the GPIb-IX-V complex is necessary.

Dendritic-like MXene quantum dots@CuNi as an efficient peroxidase candidate for colorimetric determination of glyphosate.

Oxidized MXene quantum dots@CuNi bimetal (MQDs@CuNi) were firstly prepared through a simple hydrothermal method. Compared to the controlled samples, MQDs@CuNi1:1 showed the highest peroxidase-like activity. The catalytic mechanism of MQDs@CuNi1:1 was investigated using a steady-state fluorescence analysis, which showed that MQDs@CuNi1:1 efficiently decomposes H2O2 and produces highly reactive hydroxyl radicals (OH). Furthermore, theoretical calculations showed that the remarkable catalytic activity of MQDs@CuNi1:1 originates from the interaction between CuNi bimetal and MQDs to promote the activation and decomposition of H2O2, making it easier to combine with the hydrogen at the end of 3,3',5,5'-Tetramethylbenzidine (TMB). Accordingly, a sensitive colorimetric sensor is proposed to detect glyphosate (Glyp), displaying a low detection limit of 1.13 µM. The work will provide a new way for the development of high-performance nanozyme and demonstrate potential applicability for the determination of pesticide residues in environment.

Correlating Single-Atomic Ruthenium Interdistance with Long-Range Interaction Boosts Hydrogen Evolution Reaction Kinetics.

Correlated single-atom catalysts (c-SACs) with tailored intersite metal-metal interactions are superior to conventional catalysts with isolated metal sites. However, precise quantification of the single-atomic interdistance (SAD) in c-SACs is not yet achieved, which is essential for a crucial understanding and remarkable improvement of the correlated metal-site-governed catalytic reaction kinetics. Here, three Ru c-SACs are fabricated with precise SAD using a planar organometallic molecular design and π-π molecule-carbon nanotube confinement. This strategy results in graded SAD from 2.4 to 9.3 Å in the Ru c-SACs, wherein tailoring the Ru SAD into 7.0 Å generates an exceptionally high turnover frequency of 17.92 H2 s-1 and a remarkable mass activity of 100.4 A mg-1 under 50 and 100 mV overpotentials, respectively, which is superior to all the Ru-based catalysts reported previously. Furthermore, density functional theory calculations confirm that Ru SAD has a negative correlation with its d-band center owing to the long-range interactions induced by distinct local atomic geometries, resulting in an appropriate electrostatic potential and the highest catalytic activity on c-SACs with 7.0 Å Ru SAD. The present study promises an attractive methodology for experimentally quantifying the metal SAD to provide valuable insights into the catalytic mechanism of c-SACs.

Sub-nm RuOx Clusters on Pd Metallene for Synergistically Enhanced Nitrate Electroreduction to Ammonia.

The electrochemical nitrate reduction to ammonia reaction (NO3RR) has emerged as an appealing route for achieving both wastewater treatment and ammonia production. Herein, sub-nm RuOx clusters anchored on a Pd metallene (RuOx/Pd) are reported as a highly effective NO3RR catalyst, delivering a maximum NH3-Faradaic efficiency of 98.6% with a corresponding NH3 yield rate of 23.5 mg h-1 cm-2 and partial a current density of 296.3 mA cm-2 at -0.5 V vs RHE. Operando spectroscopic characterizations combined with theoretical computations unveil the synergy of RuOx and Pd to enhance the NO3RR energetics through a mechanism of hydrogen spillover and hydrogen-bond interactions. In detail, RuOx activates NO3- to form intermediates, while Pd dissociates H2O to generate *H, which spontaneously migrates to the RuOx/Pd interface via a hydrogen spillover process. Further hydrogen-bond interactions between spillovered *H and intermediates makes spillovered *H desorb from the RuOx/Pd interface and participate in the intermediate hydrogenation, contributing to the enhanced activity of RuOx/Pd for NO3--to-NH3 conversion.

B-doped MoS2 for nitrate electroreduction to ammonia.

Electrocatalytic nitrate-to-ammonia conversion (NO3RR) is a promising route to achieve both NH3 electrosynthesis and wastewater treatment. Herein, we report B-doped MoS2 nanosheet arrays as an efficient NO3RR catalyst, delivering an NH3-Faradaic efficiency of 92.3 % with the corresponding NH3 yield of 10.8 mg h-1 cm-2 at -0.7 V (RHE). Theoretical computations identify B-dopants as the pivotal active sites to enhance NO3- activation and optimize the free energies of reaction intermediates, leading to the expedited NO3RR activity. Meanwhile, the undesired hydrogen evolution can be well suppressed on B-MoS2 to render a high NO3RR selectivity.

Metal-free BN quantum dots/graphitic C3N4 heterostructure for nitrogen reduction reaction.

Exploring high-efficiency metal-free electrocatalysts towards N2 reduction reaction (NRR) is of great interest for the development of electrocatalytic N2 fixation technology. Herein, we combined boron nitride quantum dots (BNQDs) and graphitic carbon nitride (C3N4) to design a metal-free BNQDs/C3N4 heterostructure as an effective and durable NRR catalyst. The electronically coupled BNQDs/C3N4 presented an NH3 yield as high as 72.3 µg h-1 mg-1 (-0.3 V) and a Faradaic efficiency of 19.5% (-0.2 V), far superior to isolated BNQDs and C3N4, and outperforming nearly all previously reported metal-free catalysts. Theoretical computations unveiled that the N2 activation could be drastically enhanced at the BNQDs-C3N4 interface where interfacial BNQDs and C3N4 cooperatively adsorb N2 and stabilize *N2H intermediate, leading to the significantly promoted NRR process with an ultra-low overpotential of 0.23 V.

A Chinese boy with familial Duchenne muscular dystrophy owing to a novel hemizygous nonsense mutation (c.6283C>T) in an exon of the DMD gene.

Duchenne muscular dystrophy is a severe, X-linked, progressive neuromuscular disorder clinically characterised by muscle weakening and extremely high serum creatine kinase levels. A 1-year-old Chinese patient was diagnosed with early-onset Duchenne muscular dystrophy. Next-generation gene sequencing was conducted and the Sanger method was used to validate sequencing. We identified a novel nonsense mutation (c.6283C>T) in DMD that caused the replacement of native arginine at codon 2095 with a premature termination codon (p.R2095X), which may have had a pathogenic effect against dystrophin in our patient's muscle cell membranes. We discovered a novel nonsense mutation in DMD that will expand the pathogenic mutation spectrum for Duchenne muscular dystrophy.

A vacancy engineered MnO2-x electrocatalyst promotes nitrate electroreduction to ammonia.

The NO3- reduction reaction (NO3RR) has recently emerged as a potential approach for sustainable and efficient NH3 production, whereas exploring high-performance NO3RR electrocatalysts is highly desirable yet challenging. Herein, we attempted to construct O-vacancies (OVs) on MnO2 nanosheets and the resulting OV-rich MnO2-x showed a high NH3 yield of 3.34 mg h-1 cm-2 (at -1.0 V vs. RHE) and an excellent FE of 92.4% (at -0.9 V vs. RHE), together with the outstanding stability. DFT calculations reveal that OVs on MnO2 serve as catalytic centers to enhance NO3- adsorption and dissociation, reduce the energy barriers of hydrogenation steps and thus promote NO3--to-NH3 conversion.

High-Efficiency N2 Electroreduction Enabled by Se-Vacancy-Rich WSe2-x in Water-in-Salt Electrolytes.

Electrocatalytic nitrogen reduction reaction (NRR) is a promising approach for renewable NH3 production, while developing the NRR electrocatalysis systems with both high activity and selectivity remains a significant challenge. Herein, we combine catalyst and electrolyte engineering to achieve a high-efficiency NRR enabled by a Se-vacancy-rich WSe2-x catalyst in water-in-salt electrolyte (WISE). Extensive characterizations, theoretical calculations, and in situ X-ray photoelectron/Raman spectroscopy reveal that WISE ensures suppressed H2 evolution, improved N2 affinity on the catalyst surface, as well as an enhanced π-back-donation ability of active sites, thereby promoting both activity and selectivity for the NRR. As a result, an excellent faradaic efficiency of 62.5% and NH3 yield of 181.3 µg h-1 mg-1 is achieved with WSe2-x in 12 m LiClO4, which is among the highest NRR performances reported to date.

Boosted nitrate electroreduction to ammonia on Fe-doped SnS2 nanosheet arrays rich in S-vacancies.

The electrochemical nitrate reduction reaction (NO3RR) not only holds great potential for the removal of NO3- contaminants from the environment, but also potentially provides a renewable-energy-driven NH3 synthesis method to replace the Haber-Bosch process. Herein, we report that Fe-doped SnS2 nanosheets enriched with S-vacancies can be used as an efficient NO3RR catalyst, showing a high NH3 yield of 7.2 mg h-1 cm-2 (at -0.8 V) and a faradaic efficiency of 85.6% (at -0.7 V). Density functional theory (DFT) calculations revealed that S-vacancies on Fe-SnS2 serve as the main active sites for the NO3RR and the Fe-doping can further regulate the electronic structure of S-vacancies to optimize the binding energies of NO3RR intermediates, resulting in reduced energy barriers and enhanced NO3RR activity.

MXene quantum dots decorated Ni nanoflowers for efficient Cr (VI) reduction.

Nickel@MXene quantum dots (Ni@MQDs), as novel flower-like hybrid materials, were firstly prepared through a simple reduction method. The Ni@MQDs exhibited an outstanding catalytic performance for Cr (VI) reduction with a low activation energy (Ea = 18.9 kJ mol-1) and a high kinetic constant (k = 0.4779 min-1) in the presence of formic acid (HCOOH). Density functional theory calculations demonstrated that Ni@MQDs exhibited an upshift of d-band center of active Ni atoms to promote the adsorption of both HCOOH and active H atoms, as well as an improved conductivity to boost the catalytic reaction kinetics, leading to the most favorable catalytic performance. This work may open up a new avenue towards the design and synthesis of novel MQDs-based hybrid catalysts for wastewater treatment.

MoS2 quantum dots for electrocatalytic N2 reduction.

We demonstrate that MoS2 quantum dots (QDs) can be an effective and durable catalyst for the electrocatalytic N2 reduction reaction (NRR), showing an NH3 yield of 39.6 µg h-1 mg-1 with a faradaic efficiency of 12.9% at -0.3 V, far superior to MoS2 nanosheets and outperforming most reported NRR catalysts. Density functional theory computations unravel that the MoS2 QDs can dramatically facilitate N2 adsorption and activation via side-on patterns, resulting in an energetically-favored enzymatic pathway with an ultra-low overpotential of 0.29 V.

Construction of a novel ceRNA network and identification of lncRNA ADAMTS9-AS2 and PVT1 as hub regulators of miRNA and coding gene expression in gastric cancer.

BACKGROUND: Studies on the interactions of single long non-coding RNA, microRNA, and mRNA have many limitations; therefore, it is necessary to study the complex regulatory network of gastric cancer (GC) pathogenesis systematically. METHODS: In this study, gene and miRNA expression data for GC were downloaded from The Cancer Genome Atlas and used for transcriptome profiling, differential gene analysis, and construction of an lncRNA-miRNA-mRNA regulatory network in conjunction with an online database to identify the key genes and subnetworks in GC pathogenesis. Real-time quantitative polymerase chain reaction was used to detect the expression of hub lncRNAs in 54 paired GC and matched normal mucosal tissues. RESULTS: We constructed an lncRNA-miRNA-mRNA competitive endogenous RNA regulatory network containing 1,626 network nodes and 2,704 interactions. LncRNA ADAMTS9-AS2 and PVT1 were identified as key node genes in this competitive endogenous RNA network. Quantitative reverse transcription-polymerase chain reaction revealed ADAMTS9-AS2 downregulation and PVT1 upregulation in 54 pairs of GC and normal tissues adjacent to the cancer tissues. CONCLUSIONS: This study systematically analysed the lncRNA-miRNA-mRNA regulatory network in GC and identified ADAMTS9-AS2 and PVT1 as key regulatory genes in this network, providing new understanding of GC pathogenesis and insights for its early diagnosis and treatment.

Nomograms combined with SERPINE1-related module genes predict overall and recurrence-free survival after curative resection of gastric cancer: a study based on TCGA and GEO data.

BACKGROUND: Serpin peptidase inhibitor, clade E, member 1 (SERPINE1) has been investigated as an oncogene and potential biomarker in several cancers, including gastric cancer (GC). This study aimed to investigate SERPINE1 expression and its diagnostic and prognostic value by analyzing data from The Cancer Genome Atlas (TCGA) and Gene Expression Omnibus (GEO) databases. METHODS: A meta-analysis was performed to investigate SERPINE1 expression levels in GC tissues and adjacent normal tissues. Gene set enrichment, multi experiment matrix (MEM), and protein-protein interaction (PPI) network analyses were performed to identify the most enriched signaling pathways and SERPINE1-related module genes. A Cox regression model was used to develop a nomogram that was able to predict the overall survival (OS) and recurrence-free survival (RFS) of individual patients. RESULTS: Meta-analyses revealed an elevated trend in SERPINE1 expression levels in TCGA [standard mean difference (SMD) =0.95; 95% confidence interval (CI), 0.53-1.36; P<0.001]. The diagnostic meta-analysis results indicated that the area under the curve (AUC) of the summary receiver operating characteristic (SROC) was 0.80 (95% CI, 0.77-0.84). The factors identified to predict OS were age ≥60 years [hazard ratio (HR), 2.14; 95% CI, 1.45-3.16; P<0.01], R2 margins (HR, 2.70; 95% CI, 1.41-5.14; P<0.05), lymph node-positive proportion (HR, 3.38; 95% CI, 2.03-5.63; P<0.001), patient tumor status (HR, 3.33; 95% CI, 2.28-4.87; P<0.001), and OS risk score (HR, 2.72; 95% CI, 1.82-4.05; P<0.05). The following variables were associated with RFS: male sex (HR, 2.55; 95% CI, 1.46-4.45; P<0.01), R2 margins (HR, 13.08; 95% CI, 4.26-40.15; P<0.001), lymph node-positive proportion (HR, 2.55; 95% CI, 1.20-5.45; P<0.05), and RFS risk score (HR, 2.70; 95% CI, 1.82-4.06; P<0.001). The discriminative ability of the final model for OS and RFS was assessed using C statistics (0.755 for OS and 0.745 for RFS). CONCLUSIONS: SERPINE1 was upregulated in GC, showed a high diagnostic value, and was associated with poorer OS and RFS. The OS and RFS risk for an individual patient could be estimated using these nomograms, which could lead to individualized therapeutic choices.

Genome-wide association study of esophageal squamous cell carcinoma in Chinese subjects identifies susceptibility loci at PLCE1 and C20orf54.

We performed a genome-wide association study of esophageal squamous cell carcinoma (ESCC) by genotyping 1,077 individuals with ESCC and 1,733 control subjects of Chinese Han descent. We selected 18 promising SNPs for replication in an additional 7,673 cases of ESCC and 11,013 control subjects of Chinese Han descent and 303 cases of ESCC and 537 control subjects of Chinese Uygur-Kazakh descent. We identified two previously unknown susceptibility loci for ESCC: PLCE1 at 10q23 (P(Han combined for ESCC) = 7.46 x 10(-56), odds ratio (OR) = 1.43; P(Uygur-Kazakh for ESCC) = 5.70 x 10(-4), OR = 1.53) and C20orf54 at 20p13 (P(Han combined for ESCC) = 1.21 x 10(-11), OR = 0.86; P(Uygur-Kazakh for ESCC) = 7.88 x 10(-3), OR = 0.66). We also confirmed association in 2,766 cases of gastric cardia adenocarcinoma cases and the same 11,013 control subjects (PLCE1, P(Han for GCA) = 1.74 x 10(-39), OR = 1.55 and C20orf54, P(Han for GCA) = 3.02 x 10(-3), OR = 0.91). PLCE1 and C20orf54 have important biological implications for both ESCC and GCA. PLCE1 might regulate cell growth, differentiation, apoptosis and angiogenesis. C20orf54 is responsible for transporting riboflavin, and deficiency of riboflavin has been documented as a risk factor for ESCC and GCA.