The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to C...The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to CO is positively correlated with the efficiency of both hydroesterification and hydroformylation,which is found facilitated in the presence of chloride additives with a decreasing order of BmimCl~B3MimCl>BmmimCl~LiCl.Taking the hydroesterification with MeOH as a representative example,BmimCl bearing C-H functionality at the C^(2)site of the cation assists the reduction of CO_(2)to CO as a hydrogen donor medium,with the anion and cation acting in a synergistic fashion.Subsequent insertion of CO_(2)into the formed Ru-H bond with the assistance of chloride anion produces the Ru-COOH species,which ultimately accelerates the activation of CO_(2).展开更多
BACKGROUND Major depressive disorder(MDD)with comorbid anxiety is an intricate psychiatric condition,but limited research is available on the degree centrality(DC)between anxious MDD and nonanxious MDD patients.AIM To...BACKGROUND Major depressive disorder(MDD)with comorbid anxiety is an intricate psychiatric condition,but limited research is available on the degree centrality(DC)between anxious MDD and nonanxious MDD patients.AIM To examine changes in DC values and their use as neuroimaging biomarkers in anxious and non-anxious MDD patients.METHODS We examined 23 anxious MDD patients,30 nonanxious MDD patients,and 28 healthy controls(HCs)using the DC for data analysis.RESULTS Compared with HCs,the anxious MDD group reported markedly reduced DC values in the right fusiform gyrus(FFG)and inferior occipital gyrus,whereas elevated DC values in the left middle frontal gyrus and left inferior parietal angular gyrus.The nonanxious MDD group exhibited surged DC values in the bilateral cerebellum IX,right precuneus,and opercular part of the inferior frontal gyrus.Unlike the nonanxious MDD group,the anxious MDD group exhibited declined DC values in the right FFG and bilateral calcarine(CAL).Besides,declined DC values in the right FFG and bilateral CAL negatively correlated with anxiety scores in the MDD group.CONCLUSION This study shows that abnormal DC patterns in MDD,especially in the left CAL,can distinguish MDD from its anxiety subtype,indicating a potential neuroimaging biomarker.展开更多
Electrocatalytic reduction of CO_(2)(CO_(2)RR)to multi-electron(>2e–)products provides a green and sustainable route for producing fuels and chemicals.Introducing the second metal element is a feasible strategy fo...Electrocatalytic reduction of CO_(2)(CO_(2)RR)to multi-electron(>2e–)products provides a green and sustainable route for producing fuels and chemicals.Introducing the second metal element is a feasible strategy for"managing"the key intermediate on Cu-based materials to further improve the CO_(2)RR catalytic performance.In this work,palladium,which promises the generation of CO,was introduced into the poly(ionic liquid)-based copper hybrid(Cu@PIL)to construct a novel Cu-Pd bimetallic electrocatalyst(Cu@PIL@Pd).Remarkably,with a small dosage of palladium(2.0 mol%compared with Cu),a high faradaic efficiency(FE)for C_(2+)products(68.7%)was achieved at–1.01 V(with respect to the reversible hydrogen electrode(RHE),the same below)with a high partial current density of 178.3 mA cm^(-2).Meanwhile,high selectivity towards CH4(FE=42.5%)and corresponding partial current density of 172.8 mA cm^(-2)were obtained on the same catalyst at–1.24 V,signifying a significant potential-dependent selectivity.Mechanistic studies reveal that both copper and palladium oxides are reduced to metallic states during the CO_(2)RR.The presence of the adjoint copper phase and the highly dispersed electrostatic layer promote the generation of CO on the palladium components(both the PdO_(2)phase and the Pd(II)site).Besides,the local CO^(*)was enriched by the significant diffusion resistance of CO in the PIL layer.The spillover of CO^(*)from Pd sites to the adjoint Cu sites,accompanied by the increased local concentration of CO^(*)around Cu sites,accounted for the observed good CO_(2)RR catalytic performance,especially the high C_(2+)product selectivity.展开更多
Nutrition contributes to honey bee caste differentiation,but the role of individual nutrients is still unclear.Most essential amino acid contents,except that of methionine(Met),are greater in royal jelly than worker j...Nutrition contributes to honey bee caste differentiation,but the role of individual nutrients is still unclear.Most essential amino acid contents,except that of methionine(Met),are greater in royal jelly than worker jelly.After〜3.5 i the Met content in the latter was slightly greater than in the former.Met is the major raw material used in the synthesis of S-adenosyl-L-methionine,an active methyl donor for DNA methylation,which is an epigenetic driver of caste differentiation.Here,we tested whether Met regulates caste differentiation in honey bees by determining its effects on the caste development of bees receiving four diets:the basic,basic+0.2%Met,basic+0.2%Met+20 mg/kg 5-azacytidine,and basic+20 mg/kg 5-azacytidine.The presence of Met decreased the adult bee body length and the numbers of ovarioles,indicating that Met may direct the development of female larvae toward worker bees.The upregulated expression of SAMS,Dnmtl,and Dnmt3 caused by Met exposure in 4-d-old larvae indicated that the worker-inductive effects of Met may occur through the promotion of DNA methylation.We investigated the co-effects of Met and glucose on bee development,and found that the effects of an increased glucose level on the number of ovarioles and body length did not strengthen the worker-inductive effects caused by Met.Our results contribute to caste development theory and suggest that Met-as a methyl donor一plays a regulatory,but not decisive,role in caste differentiation.展开更多
The mitogen-activated protein kinase(MAPK)cascade pathway plays an important role in regulating stress responses.The function of the c-Jun NH_(2)-terminal kinase(JNK),a component of the MAPK cascade pathway,in Apis ce...The mitogen-activated protein kinase(MAPK)cascade pathway plays an important role in regulating stress responses.The function of the c-Jun NH_(2)-terminal kinase(JNK),a component of the MAPK cascade pathway,in Apis cerana cerana(Acc)remains unclear.Here,JNK was isolated and identified from Acc.Bioinformatics analyses revealed there is a typical serine/threonine protein kinase catalytic domain in the AccJNK protein.An expression profile analysis showed that AccJNK was significantly induced by pesticide treatments.To further explore the functional mechanisms of AccJNK,a yeast 2-hybrid screen was performed,activator protein-1(AP-1)was screened as the interaction partner of AccJNK,and the interaction relationship was further verified by pull-down assay.Quantitative real-time polymerase chain reaction showed the expression pattern of AccAP-I was similar to that of AccJNK.After a knockdown of AccJNK or AccAP-I by RNA interference,the survival rate of Acc after pesticide treatments increased.Additionally,the expression levels of antioxidant-related genes and the activities of antioxidant enzymes increased,suggesting that the knockdown of AccJNK or AccAP-I increased the antioxidant capacity of bees.Our study revealed that the JNK-mediated MAPK pathway responds to pesticide stress by altering the antioxidant capacity of Acc.展开更多
基金Financial support from National Natural Science Foundation of China (22078336, U1662133, 21773158, 22008238)Innovation Academy for Green Manufacture, CAS (IAGM2020C13) is gratefully acknowledged
文摘The Ru-catalyzed carbonylation of alkenes with CO_(2)as a C1 surrogate and imidazole chlorides as the promotor is investigated by a combination of computational and experimental study.The conversion rate of CO_(2)to CO is positively correlated with the efficiency of both hydroesterification and hydroformylation,which is found facilitated in the presence of chloride additives with a decreasing order of BmimCl~B3MimCl>BmmimCl~LiCl.Taking the hydroesterification with MeOH as a representative example,BmimCl bearing C-H functionality at the C^(2)site of the cation assists the reduction of CO_(2)to CO as a hydrogen donor medium,with the anion and cation acting in a synergistic fashion.Subsequent insertion of CO_(2)into the formed Ru-H bond with the assistance of chloride anion produces the Ru-COOH species,which ultimately accelerates the activation of CO_(2).
基金Supported by Hubei Provincial Department of Science and Technology Natural Fund,No.2024AFC056the Open Fund of the Mental Health Research Institute at Three Gorges University,No.YCXL-23-11.
文摘BACKGROUND Major depressive disorder(MDD)with comorbid anxiety is an intricate psychiatric condition,but limited research is available on the degree centrality(DC)between anxious MDD and nonanxious MDD patients.AIM To examine changes in DC values and their use as neuroimaging biomarkers in anxious and non-anxious MDD patients.METHODS We examined 23 anxious MDD patients,30 nonanxious MDD patients,and 28 healthy controls(HCs)using the DC for data analysis.RESULTS Compared with HCs,the anxious MDD group reported markedly reduced DC values in the right fusiform gyrus(FFG)and inferior occipital gyrus,whereas elevated DC values in the left middle frontal gyrus and left inferior parietal angular gyrus.The nonanxious MDD group exhibited surged DC values in the bilateral cerebellum IX,right precuneus,and opercular part of the inferior frontal gyrus.Unlike the nonanxious MDD group,the anxious MDD group exhibited declined DC values in the right FFG and bilateral calcarine(CAL).Besides,declined DC values in the right FFG and bilateral CAL negatively correlated with anxiety scores in the MDD group.CONCLUSION This study shows that abnormal DC patterns in MDD,especially in the left CAL,can distinguish MDD from its anxiety subtype,indicating a potential neuroimaging biomarker.
基金Key Research Program of Frontier Sciences,CAS(ZDBS-LY-JSC022)Excellent Young Scientists Fund(22022815)+1 种基金National Natural Science Foundation of China(U1704251 and 21776291)Zhengzhou High Level Talent Certificate(20180200052)is gratefully acknowledged.
文摘Electrocatalytic reduction of CO_(2)(CO_(2)RR)to multi-electron(>2e–)products provides a green and sustainable route for producing fuels and chemicals.Introducing the second metal element is a feasible strategy for"managing"the key intermediate on Cu-based materials to further improve the CO_(2)RR catalytic performance.In this work,palladium,which promises the generation of CO,was introduced into the poly(ionic liquid)-based copper hybrid(Cu@PIL)to construct a novel Cu-Pd bimetallic electrocatalyst(Cu@PIL@Pd).Remarkably,with a small dosage of palladium(2.0 mol%compared with Cu),a high faradaic efficiency(FE)for C_(2+)products(68.7%)was achieved at–1.01 V(with respect to the reversible hydrogen electrode(RHE),the same below)with a high partial current density of 178.3 mA cm^(-2).Meanwhile,high selectivity towards CH4(FE=42.5%)and corresponding partial current density of 172.8 mA cm^(-2)were obtained on the same catalyst at–1.24 V,signifying a significant potential-dependent selectivity.Mechanistic studies reveal that both copper and palladium oxides are reduced to metallic states during the CO_(2)RR.The presence of the adjoint copper phase and the highly dispersed electrostatic layer promote the generation of CO on the palladium components(both the PdO_(2)phase and the Pd(II)site).Besides,the local CO^(*)was enriched by the significant diffusion resistance of CO in the PIL layer.The spillover of CO^(*)from Pd sites to the adjoint Cu sites,accompanied by the increased local concentration of CO^(*)around Cu sites,accounted for the observed good CO_(2)RR catalytic performance,especially the high C_(2+)product selectivity.
基金Funds of Shandong Province"Double Tops"Program(2016-2020)Shandong Province Agricultural Fine Varieties Breeding Projects(2017LZN006)the earmarked fund for the China Agriculture Research System(No.CARS-44).
文摘Nutrition contributes to honey bee caste differentiation,but the role of individual nutrients is still unclear.Most essential amino acid contents,except that of methionine(Met),are greater in royal jelly than worker jelly.After〜3.5 i the Met content in the latter was slightly greater than in the former.Met is the major raw material used in the synthesis of S-adenosyl-L-methionine,an active methyl donor for DNA methylation,which is an epigenetic driver of caste differentiation.Here,we tested whether Met regulates caste differentiation in honey bees by determining its effects on the caste development of bees receiving four diets:the basic,basic+0.2%Met,basic+0.2%Met+20 mg/kg 5-azacytidine,and basic+20 mg/kg 5-azacytidine.The presence of Met decreased the adult bee body length and the numbers of ovarioles,indicating that Met may direct the development of female larvae toward worker bees.The upregulated expression of SAMS,Dnmtl,and Dnmt3 caused by Met exposure in 4-d-old larvae indicated that the worker-inductive effects of Met may occur through the promotion of DNA methylation.We investigated the co-effects of Met and glucose on bee development,and found that the effects of an increased glucose level on the number of ovarioles and body length did not strengthen the worker-inductive effects caused by Met.Our results contribute to caste development theory and suggest that Met-as a methyl donor一plays a regulatory,but not decisive,role in caste differentiation.
基金supported by the Shandong Provincial Natural Science Foundation(No.ZR2019MC050)special funds for the Efficient Ecological Agriculture Innovation Project of the Taishan Industry Leading Talent Program(No.LJNY202003)the earmarked fund for the China Agriculture Research System of Ministry of Finance and Ministry of Agriculture and Rural Affairs(No.CARS-44).
文摘The mitogen-activated protein kinase(MAPK)cascade pathway plays an important role in regulating stress responses.The function of the c-Jun NH_(2)-terminal kinase(JNK),a component of the MAPK cascade pathway,in Apis cerana cerana(Acc)remains unclear.Here,JNK was isolated and identified from Acc.Bioinformatics analyses revealed there is a typical serine/threonine protein kinase catalytic domain in the AccJNK protein.An expression profile analysis showed that AccJNK was significantly induced by pesticide treatments.To further explore the functional mechanisms of AccJNK,a yeast 2-hybrid screen was performed,activator protein-1(AP-1)was screened as the interaction partner of AccJNK,and the interaction relationship was further verified by pull-down assay.Quantitative real-time polymerase chain reaction showed the expression pattern of AccAP-I was similar to that of AccJNK.After a knockdown of AccJNK or AccAP-I by RNA interference,the survival rate of Acc after pesticide treatments increased.Additionally,the expression levels of antioxidant-related genes and the activities of antioxidant enzymes increased,suggesting that the knockdown of AccJNK or AccAP-I increased the antioxidant capacity of bees.Our study revealed that the JNK-mediated MAPK pathway responds to pesticide stress by altering the antioxidant capacity of Acc.
