The selective hydrogenation of highly toxic phenolic compounds to generate alcohols with thermal stability,environmental friendliness,and non-toxicity is of great importance.Herein,a series of Co-based catalysts,named...The selective hydrogenation of highly toxic phenolic compounds to generate alcohols with thermal stability,environmental friendliness,and non-toxicity is of great importance.Herein,a series of Co-based catalysts,named Co@NCNTs,were designed and constructed by direct pyrolysis of hollow ZIF-67(HZIF-67)under H_(2)/Ar atmosphere.The evolution of the catalyst surface from the shell layer assembled by ZIF-67-derived particles to the in situ-grown hollow nitrogen-doped carbon nanotubes(NCNTs)with certain length and density is achieved by adjusting the pyrolysis atmosphere and temperature.Due to the synergistic effects of in situ-formed hollow NCNTs,well-dispersed Co nanoparticles,and intact carbon matrix,the as-prepared Co@NCNTs-0.10-450 catalyst exhibits superior catalytic performance in the hydrogenation of phenolic compounds to alcohols.The turnover frequency value of Co@NCNTs-0.10-450is 3.52 h^(-1),5.9 times higher than that of Co@NCNTs-0.40-450 and 4.5 times higher than that of Co@NCNTs-0.10-550,exceeding most previously reported non-noble metal catalysts.Our findings provide new insights into the development of non-precious metal,efficient,and cost-effective metal-organic framework-derived catalysts for the hydrogenation of phenolic compounds to alcohols.展开更多
Apparent critical current density(j_(Ac)^(a))of garnet all-solid-state lithium metal symmetric cells(ASSLSCs)is a fundamental parameter for designing all-solid-state lithium metal batteries.Nevertheless,how much the p...Apparent critical current density(j_(Ac)^(a))of garnet all-solid-state lithium metal symmetric cells(ASSLSCs)is a fundamental parameter for designing all-solid-state lithium metal batteries.Nevertheless,how much the possible maximum apparent current density that a given ASSLSC system can endure and how to reveal this potential still require study.Herein,a capacity perturbation strategy aiming to better measure the possible maximum j_(Ac)^(a)is proposed for the first time.With garnet-based plane-surface structure ASSLSCs as an exemplification,the j_(Ac)^(a)is quite small when the capacity is dramatically large.Under a perturbed capacity of 0.001 mA h cm^(-2),the j_(Ac)^(a)is determined to be as high as 2.35 mA cm^(-2)at room temperature.This investigation demonstrates that the capacity perturbation strategy is a feasible strategy for measuring the possible maximum j_(Ac)^(a)of Li/solid electrolyte interface,and hopefully provides good references to explore the critical current density of other types of electrochemical systems.展开更多
Bastnaesite((Ce,La,Pr,Nd)CO_(3)F) is a significant light rare earth mineral found in nature,known for its fine-grained properties.Flotation is commonly employed for the recovery of fine-grained bastnaesite particles.C...Bastnaesite((Ce,La,Pr,Nd)CO_(3)F) is a significant light rare earth mineral found in nature,known for its fine-grained properties.Flotation is commonly employed for the recovery of fine-grained bastnaesite particles.Collectors serve as an essential flotation reagent that enhance the surface hydrophobicity of target minerals.A novel collector,N-hydroxy-9-octadecenamide(N-OH-9-ODA),was synthesised in this study.N-OH-9-ODA exhibits superior selectivity compared to the traditional collector oleic acid in the flotation separation of bastnaesite and fluorite.The experimental and co mputational results indicate that N-OH-9-ODA exhibits superior selectivity due to its higher adsorption affinity for bastnaesite surface compared to fluorite surface.The zeta potential and the binding energies of the Ce 3d peaks in the X-ray photoelectron spectrum(XPS) of bastnaesite surface exhibit significant shifts.Conversely,fluorite surface demonstrates minimal alterations in its zeta potential and the binding energies of the Ca 2p peaks in its XPS after its interaction with N-OH-9-ODA.展开更多
By rational modification of electronic and steric properties of pincer ligands,a Co/Fe dual catalyst system is developed for one-pot sequential Markovnikov alkyne hydrosilylation and stereoselective alkene isomerizati...By rational modification of electronic and steric properties of pincer ligands,a Co/Fe dual catalyst system is developed for one-pot sequential Markovnikov alkyne hydrosilylation and stereoselective alkene isomerization.The protocol provides an atom-economical and efficient approach to trisubstituted(E)-alkenyl silanes from widely accessible terminal alkynes with high regio-and stereoselectivities under mild conditions.The utility of this reaction was demonstrated by gram-scale synthesis and derivatization of bioactive molecules.The radical clock and trapping experiments indicated that radical pathway might be operative in the alkene isomerization step.展开更多
Locoregional recurrence and distant metastasis of breast cancer still pose a significant risk for patients’survival.To address the clinical challenge,functional absorbable sponges(HA-SH/PP-Dox/Lap/COL I(HCNPs))were c...Locoregional recurrence and distant metastasis of breast cancer still pose a significant risk for patients’survival.To address the clinical challenge,functional absorbable sponges(HA-SH/PP-Dox/Lap/COL I(HCNPs))were constructed by biomimetic extracellular matrix of collagen I/hyaluronic acid complex conjugated with doxorubicin/lapatinib(Dox/Lap)-loaded nanoparticles.The HCNPs sponge exhibited excellent clotting ability and blood absorption rate.Worthily,Dox/Lap-loaded nanoparticles were synchronously endowed with a large number of oligo hyaluronic acid segments after degradation,which thus enhanced the ability of targeting into CD44-overexpressed tumor cells.The implantable HCNPs sponge in resected cavity of postoperative 4T1 models inhibited the spread of scattered tumor cells by absorbing the inevitable bleeding.More importantly,CD44 targeted nanoparticle with suitable Dox/Lap proportion continuously released from sponge to kill tumor cells of surrounding HCNPs and those remaining at surgical margin,thus prevented local recurrence as well as distant metastasis.Therefore,the functional HCNPs sponge might provide a safer and more effective strategy for postoperative treatment of cancer.展开更多
Polycomb group proteins are important repressors of numerous genes in higher eukaryotes. However, the mechanism by which Polycomb group proteins are recruited to specific genes is poorly understood. In Arabidopsis, LI...Polycomb group proteins are important repressors of numerous genes in higher eukaryotes. However, the mechanism by which Polycomb group proteins are recruited to specific genes is poorly understood. In Arabidopsis, LIKE HETEROCHROMATIN PROTEIN 1 （LHP1）, also known as TERMINAL FLOWER 2, was originally proposed as a subunit of polycomb repressive complex 1 （PRC1） that could bind the tri-methylated lysine 27 of histone H3 （H3K27me3） established by the PRC2. In this work, we show that LHP1 mainly functions with PRC2 to establish H3K27me3, but not with PRC1 to catalyze monoubiquitination at lysine 119 of histone H2A. Our results show that complexes of the transcription factors ASYMMETRIC LEAVES 1 （AS1） and AS2 could help to establish the H3K27me3 modification at the chromatin regions of Class-I KNOTTED＇t-like homeobox （KNOX） genes BREVIPEDICELLU5 and KNAT2 via direct interactions with LHP1. Additionally, our transcriptome analysis indicated that there are probably more common target genes of AS1 and LHP1 besides Class-I KNOX genes during leaf development in Arabidopsis.展开更多
A series of new monobactam sulfonates is continuously synthesized and evaluated for their antimicrobial efficacies against Gram-negative bacteria.Compound 33a(IMBZ18G)is highly effective in vitro and in vivo against c...A series of new monobactam sulfonates is continuously synthesized and evaluated for their antimicrobial efficacies against Gram-negative bacteria.Compound 33a(IMBZ18G)is highly effective in vitro and in vivo against clinically intractable multi-drug-resistant(MDR)Gram-negative strains,with a highly druglike nature.The checkerboard assay reveals its significant synergistic effect withβ-lactamase inhibitor avibactam,and the MIC values against MDR enterobacteria were reduced up to 4—512folds.X-ray co-crystal and chemoproteomic assays indicate that the anti-MDR bacteria effect of 33a results from the dual inhibition of the common PBP3 and some class A and Cβ-lactamases.Accordingly,preclinical studies of 33a alone and 33a-avibactam combination as potential innovative candidates are actively going on,in the treatment ofβ-lactamase-producing MDR Gram-negative bacterial infections.展开更多
The conventional methods of using surfactants to synthesize noble metal nanoparticles usually introduce residues on the surface,which inevitably decreases nanoparticles’ surface enhanced Raman scattering(SERS) perfor...The conventional methods of using surfactants to synthesize noble metal nanoparticles usually introduce residues on the surface,which inevitably decreases nanoparticles’ surface enhanced Raman scattering(SERS) performance.Herein,we propose a surfactant-free and feasible approach of preparing cerium hexaboride-Ag nano-trees hybrids(CeB_(6)@Ag nano-trees) as the SERS substrate.First,the CeB_(6)was synthesized by a one-pot ionothermal method.Secondly,the CeB_(6)powder and silver nitrate were dispersed in an aqueous solution.Thereafter,the Ag+was reduced by the UV-light assisted photoreaction and deposited on the surface of the CeB_(6).The SERS performance of the CeB_(6)@Ag nano-trees was evaluated by using the Rhodamine 6 G as the Raman reporter.It shows that CeB_(6)@Ag nano-trees exhibit good SERS sensitivity with the enhancement factor of 2.45 × 10^(7) and detection limit of 10^(-10) mol/L.Moreover,uniformity evaluation of the SERS signal intensity on the substrate also shows that relatively good relative standard deviation values of 12.6%(Raman peak@612 cm^(-1)) and 14.1%(Raman peak@1652 cm^(-1))can be achieved.Finally,finite element simulation evidences that excellent SERS performance of the CeB_(6)@Ag nano-trees is produced by the strong coupled localized surface plasmon resonance generated under the Raman laser irradiation.展开更多
基金the National Key Research and Development Program(2021YFC3001103)the National Natural Science Foundation(22278209,22178165,21921006,22208149)+1 种基金the Natural Science Foundation of Jiangsu Province(BK20211262,BK20220354)a project funded by the priority academic program development of Jiangsu higher education institutions(PAPD)of China。
文摘The selective hydrogenation of highly toxic phenolic compounds to generate alcohols with thermal stability,environmental friendliness,and non-toxicity is of great importance.Herein,a series of Co-based catalysts,named Co@NCNTs,were designed and constructed by direct pyrolysis of hollow ZIF-67(HZIF-67)under H_(2)/Ar atmosphere.The evolution of the catalyst surface from the shell layer assembled by ZIF-67-derived particles to the in situ-grown hollow nitrogen-doped carbon nanotubes(NCNTs)with certain length and density is achieved by adjusting the pyrolysis atmosphere and temperature.Due to the synergistic effects of in situ-formed hollow NCNTs,well-dispersed Co nanoparticles,and intact carbon matrix,the as-prepared Co@NCNTs-0.10-450 catalyst exhibits superior catalytic performance in the hydrogenation of phenolic compounds to alcohols.The turnover frequency value of Co@NCNTs-0.10-450is 3.52 h^(-1),5.9 times higher than that of Co@NCNTs-0.40-450 and 4.5 times higher than that of Co@NCNTs-0.10-550,exceeding most previously reported non-noble metal catalysts.Our findings provide new insights into the development of non-precious metal,efficient,and cost-effective metal-organic framework-derived catalysts for the hydrogenation of phenolic compounds to alcohols.
基金the financial support from the Natural Science Foundation for Distinguished Young Scholars of Hunan Province(2020JJ2047)the science and technology innovation Program of Hunan Province(2022RC3048)+2 种基金the Program of Huxiang Young Talents(2019RS2002)the Innovation-Driven Project of Central South University(2020CX027)the Fundamental Research Funds for the Central Universities of Central South University(2021zzts0125)。
文摘Apparent critical current density(j_(Ac)^(a))of garnet all-solid-state lithium metal symmetric cells(ASSLSCs)is a fundamental parameter for designing all-solid-state lithium metal batteries.Nevertheless,how much the possible maximum apparent current density that a given ASSLSC system can endure and how to reveal this potential still require study.Herein,a capacity perturbation strategy aiming to better measure the possible maximum j_(Ac)^(a)is proposed for the first time.With garnet-based plane-surface structure ASSLSCs as an exemplification,the j_(Ac)^(a)is quite small when the capacity is dramatically large.Under a perturbed capacity of 0.001 mA h cm^(-2),the j_(Ac)^(a)is determined to be as high as 2.35 mA cm^(-2)at room temperature.This investigation demonstrates that the capacity perturbation strategy is a feasible strategy for measuring the possible maximum j_(Ac)^(a)of Li/solid electrolyte interface,and hopefully provides good references to explore the critical current density of other types of electrochemical systems.
基金supported by National Natural Science Foundation of China (52104287,91962223)Hubei Key Laboratory for Efficient Utilisation and Agglomeration of Metallurgic Mineral ResourcesOpen Foundation of State Key Laboratory of Mineral Processing (BGRIMM-KJSKL-2022-14)。
文摘Bastnaesite((Ce,La,Pr,Nd)CO_(3)F) is a significant light rare earth mineral found in nature,known for its fine-grained properties.Flotation is commonly employed for the recovery of fine-grained bastnaesite particles.Collectors serve as an essential flotation reagent that enhance the surface hydrophobicity of target minerals.A novel collector,N-hydroxy-9-octadecenamide(N-OH-9-ODA),was synthesised in this study.N-OH-9-ODA exhibits superior selectivity compared to the traditional collector oleic acid in the flotation separation of bastnaesite and fluorite.The experimental and co mputational results indicate that N-OH-9-ODA exhibits superior selectivity due to its higher adsorption affinity for bastnaesite surface compared to fluorite surface.The zeta potential and the binding energies of the Ce 3d peaks in the X-ray photoelectron spectrum(XPS) of bastnaesite surface exhibit significant shifts.Conversely,fluorite surface demonstrates minimal alterations in its zeta potential and the binding energies of the Ca 2p peaks in its XPS after its interaction with N-OH-9-ODA.
基金the National Key R&D Program of China(2021YFA1500100)the National Natural Science Foundation of China(21825109,21821002,22072178,22293013)+3 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000)CAS Project for Young Scientists in Basic Research(YSBR-094)Science and Technology Commission of Shanghai Municipality(23JC1404400)CAS Youth Interdisciplinary Team(JCTD-2021-11).
文摘By rational modification of electronic and steric properties of pincer ligands,a Co/Fe dual catalyst system is developed for one-pot sequential Markovnikov alkyne hydrosilylation and stereoselective alkene isomerization.The protocol provides an atom-economical and efficient approach to trisubstituted(E)-alkenyl silanes from widely accessible terminal alkynes with high regio-and stereoselectivities under mild conditions.The utility of this reaction was demonstrated by gram-scale synthesis and derivatization of bioactive molecules.The radical clock and trapping experiments indicated that radical pathway might be operative in the alkene isomerization step.
基金sponsored by the National Natural Science Foundation of China(Nos.51973136 and 32071352)the Open Project Program of the Third Affiliated Hospital of Xinxiang Medical University(No.KFKTZD202102).
文摘Locoregional recurrence and distant metastasis of breast cancer still pose a significant risk for patients’survival.To address the clinical challenge,functional absorbable sponges(HA-SH/PP-Dox/Lap/COL I(HCNPs))were constructed by biomimetic extracellular matrix of collagen I/hyaluronic acid complex conjugated with doxorubicin/lapatinib(Dox/Lap)-loaded nanoparticles.The HCNPs sponge exhibited excellent clotting ability and blood absorption rate.Worthily,Dox/Lap-loaded nanoparticles were synchronously endowed with a large number of oligo hyaluronic acid segments after degradation,which thus enhanced the ability of targeting into CD44-overexpressed tumor cells.The implantable HCNPs sponge in resected cavity of postoperative 4T1 models inhibited the spread of scattered tumor cells by absorbing the inevitable bleeding.More importantly,CD44 targeted nanoparticle with suitable Dox/Lap proportion continuously released from sponge to kill tumor cells of surrounding HCNPs and those remaining at surgical margin,thus prevented local recurrence as well as distant metastasis.Therefore,the functional HCNPs sponge might provide a safer and more effective strategy for postoperative treatment of cancer.
基金supported by the National Basic Research Program of China (2012CB910500 and 2011CB944600)the National Natural Science Foundation of China (31370752)
文摘Polycomb group proteins are important repressors of numerous genes in higher eukaryotes. However, the mechanism by which Polycomb group proteins are recruited to specific genes is poorly understood. In Arabidopsis, LIKE HETEROCHROMATIN PROTEIN 1 （LHP1）, also known as TERMINAL FLOWER 2, was originally proposed as a subunit of polycomb repressive complex 1 （PRC1） that could bind the tri-methylated lysine 27 of histone H3 （H3K27me3） established by the PRC2. In this work, we show that LHP1 mainly functions with PRC2 to establish H3K27me3, but not with PRC1 to catalyze monoubiquitination at lysine 119 of histone H2A. Our results show that complexes of the transcription factors ASYMMETRIC LEAVES 1 （AS1） and AS2 could help to establish the H3K27me3 modification at the chromatin regions of Class-I KNOTTED＇t-like homeobox （KNOX） genes BREVIPEDICELLU5 and KNAT2 via direct interactions with LHP1. Additionally, our transcriptome analysis indicated that there are probably more common target genes of AS1 and LHP1 besides Class-I KNOX genes during leaf development in Arabidopsis.
基金supported by CAMS Innovation Fund for Medical Sciences(2021-12M-1-070)National Natural Science Foundation of China(32141003)。
文摘A series of new monobactam sulfonates is continuously synthesized and evaluated for their antimicrobial efficacies against Gram-negative bacteria.Compound 33a(IMBZ18G)is highly effective in vitro and in vivo against clinically intractable multi-drug-resistant(MDR)Gram-negative strains,with a highly druglike nature.The checkerboard assay reveals its significant synergistic effect withβ-lactamase inhibitor avibactam,and the MIC values against MDR enterobacteria were reduced up to 4—512folds.X-ray co-crystal and chemoproteomic assays indicate that the anti-MDR bacteria effect of 33a results from the dual inhibition of the common PBP3 and some class A and Cβ-lactamases.Accordingly,preclinical studies of 33a alone and 33a-avibactam combination as potential innovative candidates are actively going on,in the treatment ofβ-lactamase-producing MDR Gram-negative bacterial infections.
基金Project supported by National Natural Science Foundation of China (62105172)the Fundamental Research Funds for the Provincial Universities of Zhejiang (ZX2022000300)。
文摘The conventional methods of using surfactants to synthesize noble metal nanoparticles usually introduce residues on the surface,which inevitably decreases nanoparticles’ surface enhanced Raman scattering(SERS) performance.Herein,we propose a surfactant-free and feasible approach of preparing cerium hexaboride-Ag nano-trees hybrids(CeB_(6)@Ag nano-trees) as the SERS substrate.First,the CeB_(6)was synthesized by a one-pot ionothermal method.Secondly,the CeB_(6)powder and silver nitrate were dispersed in an aqueous solution.Thereafter,the Ag+was reduced by the UV-light assisted photoreaction and deposited on the surface of the CeB_(6).The SERS performance of the CeB_(6)@Ag nano-trees was evaluated by using the Rhodamine 6 G as the Raman reporter.It shows that CeB_(6)@Ag nano-trees exhibit good SERS sensitivity with the enhancement factor of 2.45 × 10^(7) and detection limit of 10^(-10) mol/L.Moreover,uniformity evaluation of the SERS signal intensity on the substrate also shows that relatively good relative standard deviation values of 12.6%(Raman peak@612 cm^(-1)) and 14.1%(Raman peak@1652 cm^(-1))can be achieved.Finally,finite element simulation evidences that excellent SERS performance of the CeB_(6)@Ag nano-trees is produced by the strong coupled localized surface plasmon resonance generated under the Raman laser irradiation.
