Substantial progress has been made in the understanding of gas-involving electrochemical reactions recently for the sake of clean,renewable,and efficient energy technologies.However,the specific influence mechanism of...Substantial progress has been made in the understanding of gas-involving electrochemical reactions recently for the sake of clean,renewable,and efficient energy technologies.However,the specific influence mechanism of the microenvironment at the reaction interface on the electrocatalytic performance(activity,selectivity,and durability)remains unclear.Here,we provide a comprehensive understanding of the interfacial microenvironment of gas-involving electrocatalysis,including carbon dioxide reduction reaction and nitrogen reduction reaction,and classify the factors affecting the reaction thermodynamics and kinetics into gas diffusion,proton supply,and electron transfer.This categorization allows a systematic survey of the literature focusing on electrolyzer-level(optimization of the device,control of the experimental condition,and design of the working electrode),electrolytelevel(increase of gas solubility,regulation of proton supply,and substitution of anodic reaction),and electrocatalyst-level strategies(promotion of gas affinity,adjustment of hydrophobicity,and enhancement of conductivity),aiming to retrieve the correlations between the microenvironment and electrochemical performance.Finally,priorities for future studies are suggested to support the comprehensive improvement of next-generation gas-involving electrochemical reactions.展开更多
Enhancer of zeste homolog 2(EZH2)is the catalytic subunit of polycomb repressive complex 2(PRC2).Dysregulation of EZH2 causes alteration of gene expression and functions,thereby promoting cancer development.Recent stu...Enhancer of zeste homolog 2(EZH2)is the catalytic subunit of polycomb repressive complex 2(PRC2).Dysregulation of EZH2 causes alteration of gene expression and functions,thereby promoting cancer development.Recent studies suggest that EZH2 has a potential prognostic role in patients with nonsmall cell lung cancer(NSCLC).However,the prognostic value of EZH2 expression levels in NSCLC is controversial.In this study,we evaluated the prognostic value in lung cancer(LC-LUAD/LUSC)based on data from The Cancer Genome Atlas(TCGA)database.Kruskal-Wallis test,Wilcoxon signed-rank test,and logistic regression were used to evaluate the relationship between EZH2 expression and clinicopathological features.Cox regression and the Kaplan-Meier method were adopted to evaluate prognosis-related factors.Gene set enrichment analysis(GSEA)was performed to identify the key pathways related to EZH2.The correlations between EZH2 and cancer immune infiltrates were investigated by single-sample Gene Set Enrichment Analysis(ssGSEA).EZH2 was found to be up regulated with amplification in tumor tissues in multiple LC cohorts.High EZH2 expression was associated with poorer overall survival(OS).GSEA suggested that EZH2 regulates innate immune system,ECM affiliated,matrisome,surfactant metabolism.Notably,ssGSEA indicated that EZH2 expression was positively correlated with infiltrating levels of Th2 cells and significantly negatively correlated with mast cell infiltration level.These results suggest that EZH2 is associated with LC immune infiltration and significantly over-expressed in lung cancer,and its diagnostic value is better than prognosis,which lays a foundation for further study of the immunomodulatory role of EZH2 in LC.展开更多
The retarded kinetics of oxygen evolution on electrodes is a bottleneck for electrochemical energy conversion and storage systems.NiFe-based electrocatalysts provide a cost-effective choice to confront this challenge....The retarded kinetics of oxygen evolution on electrodes is a bottleneck for electrochemical energy conversion and storage systems.NiFe-based electrocatalysts provide a cost-effective choice to confront this challenge.However,there is a lack of facile techniques for depositing compact catalytic films of high coverage and possessing a state-of-the-art performance,which is especially desired in photoelectrochemical(PEC)systems.Herein,we demonstrate a spray pyrolysis(SP)route to address this issue,featuring the kinetic selective preparation towards the desired catalytic-active material.Differing from reported SP protocols which only produce inactive oxides,this approach directly generates a unique composite film consisting of NiFe layered oxyhydroxides and amorphous oxides,exhibiting an overpotential as small as 255 mV(10 mA cm^(−2))and a turnover frequency of∼0.4 s^(−1)per metal atom.By using such a facile protocol,the surface rate-limiting issue of BiVO_(4)photoanodes can be effectively resolved,resulting in a charge injection efficiency of over 90%.Considering this deposition directly start from simple nitrates but only takes several seconds to complete,we believe it can be developed as a widely applicable and welcomed functionalization technique for diverse electrochemical devices.展开更多
An 83-year-old Chinese woman presented with a 3-month history of dysphagia.She also had a history of hypertension,type 2 diabetes,fundus hemorrhage,and cataract but no history of cutaneous,ocular,or other-site melanom...An 83-year-old Chinese woman presented with a 3-month history of dysphagia.She also had a history of hypertension,type 2 diabetes,fundus hemorrhage,and cataract but no history of cutaneous,ocular,or other-site melanomas.Upper gastrointestinal tract angiography revealed gastritis and duodenal diverticulum;thus,an endoscopic review was recommended.Enhanced computed tomography of the chest and upper abdomen revealed the following:(1)Esophageal space-occupying lesions and mediastinal lymph node enlargement(considering the high possibility of esophageal cancer,further endoscopy was recommended)and(2)A small amount of right pleural effusion,with no significant lymph node infiltration or distant metastasis.Esophagoscopy identified a bulge mass blocking the esophagus from 23 to 30 cm from the incisors.The upper mass had a spherical clustering,while the lower mass significantly festered.Pathological biopsy samples were obtained from the esophagus 23 and 28 cm from the incisors.Tissue biopsy showed proliferation of large round tumor cells and melanocytes.Immunohistochemistry showed positive findings for HMB45 and MelanA;partially positive findings for S100,CK7,CK5/6,CAM5.2,LCA,P63,and TTF-1;and negative findings for Syn.The Ki-67 positivity index was approximately 60%.Based on these findings,the patient was diagnosed with malignant esophageal melanoma with enlarged mediastinal lymph nodes.She was then treated with five cycles of camrelizumab therapy combined with chemotherapy from October 18,2019,to May 5,2020.Gastroscopy review following two courses of combination therapy revealed that the esophagus was 23-25 cm away from the incisors,and there were two continuous uplifted and beaded masses that had a smooth and black surface,with each of them having a length and diameter of approximately 1 cm.Melanosis of the mucosa around the lumen was observed at 40 cm from the incisors to the cardia;the dentate margin was clear;and the cardia had no stenosis.The patient then received five courses of combination therapy and became consistently stable after partial remission.No severe adverse events related to the immunotherapy were recorded.Camrelizumab may be a viable treatment option for patients with PMME.Additional evidence from future clinical trials and research is necessary to fully validate our findings.展开更多
Nitrogen chemisorption is a prerequisite for efficient ammonia synthesis under ambient conditions,but promoting this process remains a significant challenge.Here,by loading yttrium clusters onto a single-atom support,...Nitrogen chemisorption is a prerequisite for efficient ammonia synthesis under ambient conditions,but promoting this process remains a significant challenge.Here,by loading yttrium clusters onto a single-atom support,an electronic promoting effect is triggered to successfully eliminate the nitrogen chemisorption barrier and achieve highly efficient ammonia synthesis.Density functional theory calculations reveal that yttrium clusters with abundant electron orbitals can provide considerable electrons and greatly promote electron backdonation to the N2 antibonding orbitals,making the chemisorption process exothermic.Moreover,according to the“hot atom”mechanism,the energy released during exothermic N2 chemisorption would benefit subsequent N2 cleavage and hydrogenation,thereby dramatically reducing the energy barrier of the overall process.As expected,the proof-of-concept catalyst achieves a prominent NH3 yield rate of 48.1μg·h^(−1)·mg^(−1)at−0.2 V versus the reversible hydrogen electrode,with a Faradaic efficiency of up to 69.7%.This strategy overcomes one of the most serious obstacles for electrochemical ammonia synthesis,and provides a promising method for the development of catalysts with high catalytic activity and selectivity.展开更多
In this communication,a new supramolecualr amphiphile was successfully constructed based on water soluble pillar[5]arene and a unique guest which contain a CO_(2) responsive tertiary amine unit and a UV responsive cou...In this communication,a new supramolecualr amphiphile was successfully constructed based on water soluble pillar[5]arene and a unique guest which contain a CO_(2) responsive tertiary amine unit and a UV responsive coumarin group.When guest molecule 1 dispersed in water,it self-assembled into sheet-like structures.Upon bubbling CO_(2),1 transformed into 1 H due to the tertiary amine unit was protonated,accompany the nano-sheets transformed into vesicles.Further irradiation of 1 H with 365 nm light for 3 h,the coumarin group reacted with each other to form bola-type amphiphie 2 H.In this case,vesicles collapsed and re-assembled into nano-tubes.However,when addition of WPS into the solution of 1 H,the vesicles transformed into micelles,this is due to the formation of supramolecular amphiphile WP5&1 H.Upon irradiation of WP5&1 H with 365 nm light for 3 h,nano-ribbons observed instead of micelles in the solution.Notably,nanotubes from 2 H could also transform into nano-ribbons after adding WPS.The selfassembly process and the resultant assemblies were characterized by TEM,SEM,DLS,SAXS and NMR technologies.Due to both CO_(2) and light are "green" for living organisms,we anticipated our system can offer the possibilities in "on demand" drug absorption and release.展开更多
基金National Natural Science Foundationof China,Grant/Award Numbers:U21A20332,52103226,52071226Outstanding Youth Foundation of Jiangsu Province,Grant/Award Number:BK20220061+2 种基金Natural Science Foundation of Jiangsu Province,Grant/Award Number:BK20201171Key Research and Development Plan of Jiangsu Province,Grant/Award Number:BE2020003-3Fellowship of China Postdoctoral Science Foundation,Grant/Award Number:2021M702382。
文摘Substantial progress has been made in the understanding of gas-involving electrochemical reactions recently for the sake of clean,renewable,and efficient energy technologies.However,the specific influence mechanism of the microenvironment at the reaction interface on the electrocatalytic performance(activity,selectivity,and durability)remains unclear.Here,we provide a comprehensive understanding of the interfacial microenvironment of gas-involving electrocatalysis,including carbon dioxide reduction reaction and nitrogen reduction reaction,and classify the factors affecting the reaction thermodynamics and kinetics into gas diffusion,proton supply,and electron transfer.This categorization allows a systematic survey of the literature focusing on electrolyzer-level(optimization of the device,control of the experimental condition,and design of the working electrode),electrolytelevel(increase of gas solubility,regulation of proton supply,and substitution of anodic reaction),and electrocatalyst-level strategies(promotion of gas affinity,adjustment of hydrophobicity,and enhancement of conductivity),aiming to retrieve the correlations between the microenvironment and electrochemical performance.Finally,priorities for future studies are suggested to support the comprehensive improvement of next-generation gas-involving electrochemical reactions.
基金Supported by a grant from the Qingdao 2020 Medical Scientific Research Guidance Plan(No.2020-WJZD036).
文摘Enhancer of zeste homolog 2(EZH2)is the catalytic subunit of polycomb repressive complex 2(PRC2).Dysregulation of EZH2 causes alteration of gene expression and functions,thereby promoting cancer development.Recent studies suggest that EZH2 has a potential prognostic role in patients with nonsmall cell lung cancer(NSCLC).However,the prognostic value of EZH2 expression levels in NSCLC is controversial.In this study,we evaluated the prognostic value in lung cancer(LC-LUAD/LUSC)based on data from The Cancer Genome Atlas(TCGA)database.Kruskal-Wallis test,Wilcoxon signed-rank test,and logistic regression were used to evaluate the relationship between EZH2 expression and clinicopathological features.Cox regression and the Kaplan-Meier method were adopted to evaluate prognosis-related factors.Gene set enrichment analysis(GSEA)was performed to identify the key pathways related to EZH2.The correlations between EZH2 and cancer immune infiltrates were investigated by single-sample Gene Set Enrichment Analysis(ssGSEA).EZH2 was found to be up regulated with amplification in tumor tissues in multiple LC cohorts.High EZH2 expression was associated with poorer overall survival(OS).GSEA suggested that EZH2 regulates innate immune system,ECM affiliated,matrisome,surfactant metabolism.Notably,ssGSEA indicated that EZH2 expression was positively correlated with infiltrating levels of Th2 cells and significantly negatively correlated with mast cell infiltration level.These results suggest that EZH2 is associated with LC immune infiltration and significantly over-expressed in lung cancer,and its diagnostic value is better than prognosis,which lays a foundation for further study of the immunomodulatory role of EZH2 in LC.
基金financially supported by the National Natural Science Foundation of China(NSFC,21805298,21905288,51904288)the Zhejiang Provincial Natural Science Foundation(Z21B030017)+2 种基金the K.C.Wong Education Foundation(GJTD-201913)the Ningbo major special projects of the Plan‘‘Science and Technology Innovation 2025”(2018B10056,2019B10046)the Ningbo 3315 Program。
文摘The retarded kinetics of oxygen evolution on electrodes is a bottleneck for electrochemical energy conversion and storage systems.NiFe-based electrocatalysts provide a cost-effective choice to confront this challenge.However,there is a lack of facile techniques for depositing compact catalytic films of high coverage and possessing a state-of-the-art performance,which is especially desired in photoelectrochemical(PEC)systems.Herein,we demonstrate a spray pyrolysis(SP)route to address this issue,featuring the kinetic selective preparation towards the desired catalytic-active material.Differing from reported SP protocols which only produce inactive oxides,this approach directly generates a unique composite film consisting of NiFe layered oxyhydroxides and amorphous oxides,exhibiting an overpotential as small as 255 mV(10 mA cm^(−2))and a turnover frequency of∼0.4 s^(−1)per metal atom.By using such a facile protocol,the surface rate-limiting issue of BiVO_(4)photoanodes can be effectively resolved,resulting in a charge injection efficiency of over 90%.Considering this deposition directly start from simple nitrates but only takes several seconds to complete,we believe it can be developed as a widely applicable and welcomed functionalization technique for diverse electrochemical devices.
基金Supported by a grant from the Qingdao 2020 Medical Scientific Research Guidance Plan(No.2020-WJZD036)。
文摘An 83-year-old Chinese woman presented with a 3-month history of dysphagia.She also had a history of hypertension,type 2 diabetes,fundus hemorrhage,and cataract but no history of cutaneous,ocular,or other-site melanomas.Upper gastrointestinal tract angiography revealed gastritis and duodenal diverticulum;thus,an endoscopic review was recommended.Enhanced computed tomography of the chest and upper abdomen revealed the following:(1)Esophageal space-occupying lesions and mediastinal lymph node enlargement(considering the high possibility of esophageal cancer,further endoscopy was recommended)and(2)A small amount of right pleural effusion,with no significant lymph node infiltration or distant metastasis.Esophagoscopy identified a bulge mass blocking the esophagus from 23 to 30 cm from the incisors.The upper mass had a spherical clustering,while the lower mass significantly festered.Pathological biopsy samples were obtained from the esophagus 23 and 28 cm from the incisors.Tissue biopsy showed proliferation of large round tumor cells and melanocytes.Immunohistochemistry showed positive findings for HMB45 and MelanA;partially positive findings for S100,CK7,CK5/6,CAM5.2,LCA,P63,and TTF-1;and negative findings for Syn.The Ki-67 positivity index was approximately 60%.Based on these findings,the patient was diagnosed with malignant esophageal melanoma with enlarged mediastinal lymph nodes.She was then treated with five cycles of camrelizumab therapy combined with chemotherapy from October 18,2019,to May 5,2020.Gastroscopy review following two courses of combination therapy revealed that the esophagus was 23-25 cm away from the incisors,and there were two continuous uplifted and beaded masses that had a smooth and black surface,with each of them having a length and diameter of approximately 1 cm.Melanosis of the mucosa around the lumen was observed at 40 cm from the incisors to the cardia;the dentate margin was clear;and the cardia had no stenosis.The patient then received five courses of combination therapy and became consistently stable after partial remission.No severe adverse events related to the immunotherapy were recorded.Camrelizumab may be a viable treatment option for patients with PMME.Additional evidence from future clinical trials and research is necessary to fully validate our findings.
基金supported by the National Natural Science Foundation of China(Nos.U21A20332,52103226,and 52071226)the Outstanding Youth Foundation of Jiangsu Province(No.BK20220061)+2 种基金the Natural Science Foundation of Jiangsu Province(No.BK20201171)the Key Research and Development Plan of Jiangsu Province(No.BE2020003-3)the Fellowship of China Postdoctoral Science Foundation(No.2021M702382).
文摘Nitrogen chemisorption is a prerequisite for efficient ammonia synthesis under ambient conditions,but promoting this process remains a significant challenge.Here,by loading yttrium clusters onto a single-atom support,an electronic promoting effect is triggered to successfully eliminate the nitrogen chemisorption barrier and achieve highly efficient ammonia synthesis.Density functional theory calculations reveal that yttrium clusters with abundant electron orbitals can provide considerable electrons and greatly promote electron backdonation to the N2 antibonding orbitals,making the chemisorption process exothermic.Moreover,according to the“hot atom”mechanism,the energy released during exothermic N2 chemisorption would benefit subsequent N2 cleavage and hydrogenation,thereby dramatically reducing the energy barrier of the overall process.As expected,the proof-of-concept catalyst achieves a prominent NH3 yield rate of 48.1μg·h^(−1)·mg^(−1)at−0.2 V versus the reversible hydrogen electrode,with a Faradaic efficiency of up to 69.7%.This strategy overcomes one of the most serious obstacles for electrochemical ammonia synthesis,and provides a promising method for the development of catalysts with high catalytic activity and selectivity.
基金the National Natural Science Foundation of China(21603157)Young Elite Scientists Sponsorship Program by CAST(2018QNRC001)the support of Suzhou Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies and Soochow University Analysis and Testing Center。
基金supported by the National Natural Science Foundation of China(Nos.21801139,21871227)Natural Science Foundation of Jiangsu Province(No.BK20180942)the Natural Science Foundation of Nantong University for High-Level Talent(No.03083004)。
文摘In this communication,a new supramolecualr amphiphile was successfully constructed based on water soluble pillar[5]arene and a unique guest which contain a CO_(2) responsive tertiary amine unit and a UV responsive coumarin group.When guest molecule 1 dispersed in water,it self-assembled into sheet-like structures.Upon bubbling CO_(2),1 transformed into 1 H due to the tertiary amine unit was protonated,accompany the nano-sheets transformed into vesicles.Further irradiation of 1 H with 365 nm light for 3 h,the coumarin group reacted with each other to form bola-type amphiphie 2 H.In this case,vesicles collapsed and re-assembled into nano-tubes.However,when addition of WPS into the solution of 1 H,the vesicles transformed into micelles,this is due to the formation of supramolecular amphiphile WP5&1 H.Upon irradiation of WP5&1 H with 365 nm light for 3 h,nano-ribbons observed instead of micelles in the solution.Notably,nanotubes from 2 H could also transform into nano-ribbons after adding WPS.The selfassembly process and the resultant assemblies were characterized by TEM,SEM,DLS,SAXS and NMR technologies.Due to both CO_(2) and light are "green" for living organisms,we anticipated our system can offer the possibilities in "on demand" drug absorption and release.