Strong metal-support interactions between highly dispersed Cu^(+) species and ceria via mix-MOF pyrolysis toward promoted water-gas shift reaction

The modulation of metal-support interfacial interaction is significant but challenging in the design of high-efficiency and high-stability supported catalysts.Here,we report a synthetic strategy to upgrade Cu-CeO_(2)interfacial interaction by the pyrolysis of mixed metal-organic framework(MOF)structure.The obtained highly dispersed Cu/CeO_(2)-MOF catalyst via this strategy was used to catalyze water-gas shift reaction(WGSR),which exhibited high activity of 40.5μmolCOgcat^(-1).s^(-1)at 300℃and high stability of about 120 h.Based on comprehensive studies of electronic structure,pyrolysis strategy has significant effect on enhancing metal-support interaction and then stabilizing interfacial Cu^(+)species under reaction conditions.Abundant Cu^(+)species and generated oxygen vacancies over Cu/CeO_(2)-MOF catalyst played a key role in CO molecule activation and H2O molecule dissociation,respectively.Both collaborated closely and then promoted WGSR catalytic performance in comparison with traditio nal supported catalysts.This study shall offer a robust approach to harvest highly dispersed catalysts with finely-tuned metal-support interactions for stabilizing the most interfacial active metal species in diverse heterogeneous catalytic reactions.

Outcomes of furazolidone-and amoxicillin-based quadruple therapy for Helicobacter pylori infection and predictors of failed eradication

AIM To evaluate the outcomes of furazolidone-and amoxicillin-based quadruple therapy for treatment of Helicobacter pylori(H. pylori) infection and identify predictors of failed eradication.METHODS Patients with H. pylori infection treated with furazolidone, amoxicillin, bismuth, and proton pump inhibitor therapy(January 2015 to December 2015) who received the ^(13)C-urea breath test > 4 wk after treatment were evaluated. Demographic and clinical data including prior H. pylori treatment attempts, medication adherence, alcohol and cigarette consumption during therapy, and treatment-related adverse events were recorded by reviewing medical records and telephone surveys. H. pylori eradication rates for overall and subgroups were evaluated. Multivariate analysis was performed to identify independent predictors of failed H. pylori eradication.RESULTS Of the 992 patients treated and retested for H. pylori infection, the overall eradication rate was 94.5% [95% confidence interval(CI): 94.1%-95.9%]. H. pylori eradication rate of primary therapy was 95.0%(95%CI: 93.5%-96.5%), while that of rescue therapy was 91.3%(95%CI: 86.8%-95.8%). Among the 859 patients who completed the study protocol, 144(17%) reported treatment-related adverse events including 24(3%) leading to premature discontinuation. On multivariate analysis, poor medication adherence [adjusted odds ratio(AOR) = 6.7, 95%CI: 2.8-15.8], two or more previous H. pylori treatments(AOR = 7.4, 95%CI: 2.2-24.9), alcohol consumption during therapy(AOR = 4.4, 95%CI: 1.5-12.3), and possibly smoking during therapy(AOR = 1.9, 95%CI: 0.9-4.3) were associated with failed H. pylori eradication. CONCLUSION Furazolidone-and amoxicillin-based quadruple therapy for H. pylori infection in an area with a high prevalence of clarithromycin resistance demonstrated high eradication rates as primary and rescue therapies with a favorable safety profile. Patient education targeting abstinence from alcohol during therapy and strict medication adherence may further optimize H. pylori eradication.

Fructo-oligosaccharide intensifies visceral hypersensitivity and intestinal inflammation in a stress-induced irritable bowel syndrome mouse model

AIM To determine whether fructo-oligosaccharide(FOS) affects visceral sensitivity, inflammation, and production of intestinal short-chain fatty acids(SCFA) in an irritable bowel syndrome(IBS) mouse model.METHODS Mice were randomly assigned to daily oral gavage of saline solution with or without FOS(8 g/kg body weight) for 14 d. Mice were further assigned to receive either daily one-hour water avoidance stress(WAS) or sham-WAS for the first 10 d. After 2 wk, visceral sensitivity was measured by abdominal withdrawal reflex in response to colorectal distension and mucosal inflammation was evaluated. Gas chromatography, real-time reverse transcription PCR, and immunohistochemistry assays were used to quantify cecal concentrations of SCFA, intestinal cytokine expression, and number of intestinal mast cells per high-power field(HPF), respectively.RESULTS Mice subjected to WAS exhibited visceral hypersensitivity and low-grade inflammation. Among mice subjected to WAS, FOS increased visceral hypersensitivity and led to higher cecal concentrations of acetic acid(2.49 ± 0.63 mmol/L vs 1.49 ± 0.72 mmol/L, P < 0.05), propionic acid(0.48 ± 0.09 mmol/L vs 0.36 ± 0.05 mmol/L, P < 0.01), butyric acid(0.28 ± 0.09 mmol/L vs 0.19 ± 0.003 mmol/L, P < 0.05), as well as total SCFA(3.62 ± 0.87 mmol/L vs 2.27 ± 0.75 mmol/L, P < 0.01) compared to saline administration. FOS also increased ileal interleukin(IL)-23 mR NA(4.71 ± 4.16 vs 1.00 ± 0.99, P < 0.05) and colonic IL-1β mR NA(2.15 ± 1.68 vs 0.88 ± 0.53, P < 0.05) expressions as well as increased mean mast cell counts in the ileum(12.3 ± 2.6 per HPF vs 8.3 ± 3.6 per HPF, P < 0.05) and colon(6.3 ± 3.2 per HPF vs 3.4 ± 1.2 per HPF, P < 0.05) compared to saline administration in mice subjected to WAS. No difference in visceral sensitivity, intestinal inflammation, or cecal SCFA levels was detected with or without FOS administration in mice subjected to sham-WAS.CONCLUSION FOS administration intensifies visceral hypersensitivity and gut inflammation in stress-induced IBS mice, but not in the control mice, and is also associated with increased intestinal SCFA production.

Genetic diversity and phylogenetic analysis of EG95 sequences of Echinococcus granulosus:Implications for EG95 vaccine application

Objective:To analyse the genetic variability of EG95 sequences and provide guidance for EG95 vaccine application against Echinococcus granulosus(E. granulosus). Methods:We analysed EG95 polymorphism by collecting total 97 different E. granulosus isolates from 12 different host species that originated from 10 different countries. Multiple sequence alignments and the homology were performed by Lasergene 1(DNASTAR Inc.,Madison,WI),and the phylogenetic analysis was performed by using MEGA5.1(CEMI,Tempe,AZ,USA). In addition,linear and conformational epitopes were analysed,including secondary structure,NXT/S glycosylation,fibronectin type ecoⅢ(Fnndary Ⅲ) domain and glycosylphosphatidylinositol anchor signal(GPIanchor). The s structure was predicted by PSIPRED method. Results:Our results indicated that most isolates overall shared 72.6-100% identity in EG95 gene sequence with the published standard EG95 sequence,X90928. However,EG95 gene indeed has polymorphism in different isolates. Phylogenetic analysis showed that different isolates could be divided into three subgroups. Subgroup 1 contained 87 isolates while Subgroup 2 and Subgroup 3 consisted of 3 and 7 isolates,respectively. Four sequences cloned from oncosphere shared a high identity with the parental sequence of the current vaccine,X90928,and they belonged to Subgroup 1. However,in comparison to X90928,several amino acid mutations occurred in most isolates besides oncosphere,which potentially altered the immunodominant linear epitopes,glycosylation sites and secondary structures in EG95 genes. All these variations might change their previous antigenicity and thereby affecting the efficacy of current EG95 vaccine. Conclusions:This study reveals the genetic variability of EG95 sequences in different E. granulosus isolates,and proposed that more vaccination trials would be needed to test the effectiveness of current EG95 vaccine against distinct isolates in different countries.

Boosting the water gas shift reaction on Pt/CeO_(2)-based nanocatalysts by compositional modification: Support doping versus bimetallic alloying

The water gas shift reaction is of vital significance for the generation and transition of energy due to the application in hydrogen production and industries such as ammonia synthesis and fuel cells.The influence of support doping and bimetallic alloying on the catalytic performance of Pt/Ce O_(2)-based nanocatalysts in water gas shift reaction was reported in this work.Various lanthanide ions and 3d transition metals were respectively introduced into the Ce O_(2)support or Pt to form Pt/Ce O_(2):Ln(Ln=La,Nd,Gd,Tb,Yb)and Pt M/Ce O_(2)(M=Fe,Co,Ni)nanocatalysts.The sample of Pt/Ce O_(2):Tb showed the highest activity(TOF at 200℃=0.051 s^(-1))among the Pt/Ce O_(2):Ln and the undoped Pt/Ce O_(2)catalysts.Besides,the sample of Pt Fe/Ce O_(2)exhibited the highest activity(TOF at 200℃=0.12 s^(-1))among Pt M/Ce O_(2)catalysts.The results of the multiple characterizations indicated that the catalytic activity of Pt/Ce O_(2):Ln catalysts was closely correlated with the amount of oxygen vacancies in doped ceria support.However,the different activity of Pt M/Ce O_(2)bimetallic catalysts was owing to the various Pt oxidation states of the bimetals dispersed on ceria.The study of the reaction pathway indicated that both the samples of Pt/Ce O_(2)and Pt/Ce O_(2):Tb catalyzed the reaction through the formate pathway,and the enhanced activity of the latter derived from the increased concentration of oxygen vacancies along with promoted water dissociation.As for the sample of Pt Fe/Ce O_(2),its catalytic mechanism was the carboxyl route with a higher reaction rate due to the moderate valence of Pt along with improved CO activation.

A compressed variance component mixed model for detecting QTNs and QTN-by-environment and QTN-by-QTN interactions in genome-wide association studies

Although genome-wide association studies are widely used to mine genes for quantitative traits,the effects to be estimated are confounded,and the methodologies for detecting interactions are imperfect.To address these issues,the mixed model proposed here first estimates the genotypic effects for AA,Aa,and aa,and the genotypic polygenic background replaces additive and dominance polygenic backgrounds.Then,the estimated genotypic effects are partitioned into additive and dominance effects using a one-way analysis of variance model.This strategy was further expanded to cover QTN-by-environment interactions(QEIs)and QTN-by-QTN interactions(QQIs)using the same mixed-model framework.Thus,a three-variance-component mixed model was integrated with our multi-locus random-SNP-effect mixed linear model(mrMLM)method to establish a new methodological framework,3VmrMLM,that detects all types of loci and estimates their effects.In Monte Carlo studies,3VmrMLM correctly detected all types of loci and almost unbiasedly estimated their effects,with high powers and accuracies and a low false positive rate.In re-analyses of 10 traits in 1439 rice hybrids,detection of 269 known genes,45 known gene-by-environment interactions,and 20 known gene-by-gene interactions strongly validated 3VmrMLM.Further analyses of known genes showed more small(67.49%),minor-allele-frequency(35.52%),and pleiotropic(30.54%)genes,with higher repeatability across datasets(54.36%)and more dominance loci.In addition,a heteroscedasticity mixed model in multiple environments and dimension reduction methods in quite a number of environments were developed to detect QEIs,and variable selection under a polygenic background was proposed for QQI detection.This study provides a new approach for revealing the genetic architecture of quantitative traits.

mrMLM v4.0.2: An R Platform for Multi-locus Genome-wide Association Studies

Previous studies have reported that some important loci are missed in single-locus genome-wide association studies(GWAS),especially because of the large phenotypic error in field experiments.To solve this issue,multi-locus GWAS methods have been recommended.However,only a few software packages for multi-locus GWAS are available.Therefore,we developed an R software named mr MLM v4.0.2.This software integrates mr MLM,FASTmr MLM,FASTmr EMMA,p LARm EB,p KWm EB,and ISIS EM-BLASSO methods developed by our lab.There are four components in mr MLM v4.0.2,including dataset input,parameter setting,software running,and result output.The fread function in data.table is used to quickly read datasets,especially big datasets,and the do Parallel package is used to conduct parallel computation using multiple CPUs.In addition,the graphical user interface software mr MLM.GUI v4.0.2,built upon Shiny,is also available.To confirm the correctness of the aforementioned programs,all the methods in mr MLM v4.0.2 and three widely-used methods were used to analyze real and simulated datasets.The results confirm the superior performance of mr MLM v4.0.2 to other methods currently available.False positive rates are effectively controlled,albeit with a less stringent significance threshold.mr MLM v4.0.2 is publicly available at Bio Code(https://bigd.big.ac.cn/biocode/tools/BT007077)or R(https://cran.r-project.org/web/packages/mr MLM.GUI/index.html)as an open-source software.

Facile synthesis of Au embedded CuOx-CeO2 core/shell nanospheres as highly reactive and sinter-resistant catalysts for catalytic hydrogenation of p-nitrophenol

Exploring cost-effective catalysts with high catalytic performance and long-term stability has always been a general concern for environment protection and energy conversion.Here,Au nanoparticles(NPs)embedded CuOx-CeO2 core/shell nanospheres(Au@CuOx-CeO2 CSNs)have been successfully prepared through a versatile one-pot method at ambient conditions.The spontaneous auto-redox reaction between HAuCl4 and Ce(OH)3 in aqueous solution triggered the self-assembly growth of micro-/nanostructural Au@CuOx-CeO2 CSNs.Meanwhile,the CuOx clusters in Au@CuOx-CeO2 CSNs are capable of improving the anti-sintering ability of Au NPs and providing synergistic catalysis benefits.As a result,the confined Au NPs exhibited extraordinary thermal stability even at a harsh thermal condition up to 700℃.In addition,before and after the severe calcination process,Au@CuOx-CeO2 CSNs can exhibit enhanced catalytic activity and excellent recyclability towards the hydrogenation of p-nitrophenol compared to previously reported nanocatalysts.The synergistic catalysis path between Au/CuOx/CeO2 triphasic interfaces was revealed by density functional theory(DFT)calculations.The CuOx clusters around the embedded Au NPs can provide moderate adsorption strength of p-nitrophenol,while the adjacent CeO2-supported Au NPs can facilitate the hydrogen dissociation to form H*species,which contributes to achieve the efficient reduction of p-nitrophenol.This study opens up new possibilities for developing high-efficient and sintering-resistant micro-/nanostructural nanocatalysts by exploiting multiphasic systems.

PdRh双金属纳米立方体表面化学原位研究与CO氧化反应催化性能的关联（英文）

随着原位表征技术的进步,最新的研究结果表明,纳米催化剂在活化或催化反应条件下会发生表面结构或组分的变化,进而影响其催化性能.而开展以具有明确结构和组分纳米晶为模型催化剂的原位催化反应研究,对深入理解催化剂在反应中的活性中心状态和构效关系能起到重要推进作用.本研究利用水热法制备了具有一系列组成、相似尺寸及相同形貌的PdRh双金属纳米立方体,针对CO催化氧化反应,结合原位X射线光电子能谱技术,研究了不同预处理条件下和不同组成的纳米晶表面化学演化历程.研究发现Pd_(0.6)Rh_(0.4)和Pd_(0.8)Rh_(0.2)两种组分的纳米晶催化反应活性中心取决于其预活化条件,而PdRh体系的元素偏析现象仅在Pd_(0.6)Rh_(0.4)一种条件下发生.因此,本研究进一步明晰了双金属催化剂表面结构在反应条件下的演变与催化性能的关联.

碳-CeO2界面增强Pt纳米催化剂在催化氧化反应中的化学稳定性

为提高贵金属催化剂的活性与原子经济性,人们将其粒径降低至纳米/亚纳米尺度,甚至开发各类单原子材料.然而,这些材料的结构状态和催化性能难以在苛刻的催化环境下保持稳定.对于二氧化铈(CeO2)负载的Pt纳米粒子,载体扩散到Pt粒子表面的活性氧物种稳定吸附在Pt表面,导致金属Pt活性降低.本文采用表面部分碳修饰的多孔CeO2为载体,将纳米Pt选择性地生长在C-CeO2界面处形成特殊的三相界面结构,对CO氧化表现出低温段增强的活性和稳定性.石墨碳对纳米Pt的供电子效应和CeO2载体高密度纳米孔的限域效应共同贡献了纳米Pt的化学及结构稳定性.本文设计的独特三相界面结构综合了CeO2活化氧以及碳贡献电子能力的优点,为制备新型高效金属催化材料提供了新的思路.

A combinatorial strategy to identify various types of QTLs for quantitative traits using extreme phenotype individuals in an F_(2)population

Theoretical and applied studies demonstrate the difficulty of detecting extremely over-dominant and smalleffect genes for quantitative traits via bulked segregant analysis(BSA)in an F_(2)population.To address this issue,we proposed an integrated strategy for mapping various types of quantitative trait loci(QTLs)for quantitative traits via a combination of BSA and whole-genome sequencing.In this strategy,the numbers of read counts of marker alleles in two extreme pools were used to predict the numbers of read counts of marker genotypes.These observed and predicted numbers were used to construct a new statistic,G_(w),for detecting quantitative trait genes(QTGs),and the method was named dQTG-seq1.This method was significantly better than existing BSA methods.If the goal was to identify extremely over-dominant and smalleffect genes,another reserved DNA/RNA sample from each extreme phenotype F_(2)plant was sequenced,and the observed numbers of marker alleles and genotypes were used to calculate G_(w)to detect QTGs;this method was named dQTG-seq2.In simulated and real rice dataset analyses,dQTG-seq2 could identify many more extremely over-dominant and small-effect genes than BSA and QTL mapping methods.dQTGseq2 may be extended to other heterogeneous mapping populations.The significance threshold of G_(w)in this study was determined by permutation experiments.In addition,a handbook for the R software dQTG.seq,which is available at https://cran.r-project.org/web/packages/dQTG.seq/index.html,has been provided in the supplemental materials for the users’convenience.This study provides a new strategy for identifying all types of QTLs for quantitative traits in an F_(2)population.

ⅢVmrMLM:The R and C++tools associated with 3VmrMLM,a comprehensive GWAS method for dissecting quantitative traits

Inmost existingmethods and softwares of genome-wide association studies(GWAS)fordetecting quantitative trait nucleotides(QTNs),QTN-by-environment interactions(QEls),and QTN-by-QTN interactions(QQIs),only the allele substitution effect and its interaction-related effects are detected and estimated,conditional on method-specific polygenic background control,leading to confounding in effect estimation and insufficient polygenic background control(Li et al.,2022;Supplemental Tables 1-3).

Multi-twinned gold nanoparticles with tensile surface steps for efficient electrocatalytic CO_(2) reduction

CO_(2) reduction reactions(CO_(2)RR) powered by renewable electricity can directly convert CO_(2) to hydrocarbons and fix the intermittent sustainable energy in portable chemical fuels. It is of great importance to develop advanced catalysts that can boost CO_(2)RR with high activity, selectivity, and efficiency at low overpotentials. Here, we report the solution synthesis using H_(2)O_(2) to modify the surface structures of gold multi-twinned nanoparticles(AuMPs) and create tensile surface steps. Calculations predicted significantly enhanced CO_(2) adsorption and boosted CO_(2)RR capabilities with inhibited hydrogen evolution reaction activity for the tensile surface steps with modified electronic structure. The H_(2)O_(2)-treated AuMPs with surface steps and 3.83% tensile lattices showed much higher activity and selectivity at lower overpotentials for CO_(2)RR than pristine gold nanoparticles.The CO-production current density reached about 98 mA cm^(-2) with a Faradaic efficiency of 95.7% at -0.30 V versus reversible hydrogen electrode in the flow cell, showing a half-cell energy efficiency as high as ~83%. Our strategy represents a rational catalyst design by engineering the surface structures of metal nanoparticles and may find more applicability in future electrocatalysis.

A trefoil-shaped macrocycle with [12]-imidazolium cations

A trefoil-like two-dimensional(2D)C_(3v) symmetric organic[12]-imidazolium cation H_(12)-2(PF_(6))_(12) featuring three[4]-imidazolium macrocycles was synthesized in three steps.The reaction of a dodecakis H_(12)-1(PF_(6))_(12) imidazolium salt with Ag_(2)O resulted in the formation of a hexanuclear AgI dodecacarbene assembly[Ag_(6)(1)](PF_(6))_(6).Upon UV irradiation,the photodimerization of the cinnamic ester pendants of[Ag_(6)(1)](PF_(6))_(6) led to the generation of a trefoil-like complex[Ag_(6)(2)](PF_(6))_(6) containing three closed metallacycles.Removal of metal ions allowed for the synthesis of the target molecule.All complexes were fully characterized by NMR spectroscopy(^(1)H,^(13)C{^(1)H}and 2D NMR)and high-resolution electrospray ionization mass spectrometry(HR-ESI-MS).