Genotyping by Target Sequencing(GBTS)technology,known for its flexibility,high efficiency,high throughput,and low cost,has been increasingly employed in molecular breeding.However,there is still limited study on the d...Genotyping by Target Sequencing(GBTS)technology,known for its flexibility,high efficiency,high throughput,and low cost,has been increasingly employed in molecular breeding.However,there is still limited study on the design and development of high-throughput genotyping tools in watermelon.In this study,we identified 112000 high quality SNPs by analyzing the resequencing data of 43 cultivated watermelon accessions.11921 and 6094 SNPs were selected for developing two sets of watermelon liquid-phase chips with different marker densities,named Watermelon 10K and 5K,respectively.Furthermore,the SNPs and Indels of most mapped gene/QTLs for many agronomic important traits in watermelon were also integrated into the two chips for foreground selection.These chips have been tested using GBTS technology in various applications in watermelon.The genotyping of 76 accessions by Watermelon 5K liquid-phase chip showed an average detection rate of 99.28%and 81.78%for cultivated and wild watermelon accessions,respectively.This provided enough markers information for GWAS and two significant QTLs,ssc1.1 and ssc1.2,associated with soluble sugar content were detected.Furthermore,BSA-seq analysis for non-lobed leaf and dwarf traits were validated by liquid-phase chips,and the candidate region was consistent with our previous studies.Additionally,we precisely introduced the Cldw1 and Clbl genes into an elite inbred line WT2 using Watermelon 5K for assisted selection,resulting in the development of three new germplasm with good plant architecture.As a high-throughput genotyping liquid-phase SNP array,the Watermelon 10K and 5K chips will greatly facilitate functional studies and molecular breeding in watermelon.展开更多
A comprehensive understanding of the structure and dynamic evolution of catalytic active sites is vital for advancing the study of liquid-phase acetylene hydrochlorination.Here,we successfully developed a Ru-DIPEA/TMS...A comprehensive understanding of the structure and dynamic evolution of catalytic active sites is vital for advancing the study of liquid-phase acetylene hydrochlorination.Here,we successfully developed a Ru-DIPEA/TMS catalyst optimised through systematic composition and condition tuning,demonstrating exceptional performance with 95.5%C_(2)H_(2)conversion and sustaining over 91.1%activity along with nearly 100%selectivity for VCM during a continuous 900-h test.Using a combination of characterisation techniques,including UV–vis spectroscopy,FT-IR spectroscopy,X-ray photoelectron spectroscopy,singlecrystal X-ray diffraction,and X-ray absorption spectroscopy,along with density functional theory(DFT)calculations,the structure and dynamic behaviour of the active sites were thoroughly investigated under the synergistic influence of ligands and HCl.The results revealed that HCl activation induces a significant structural transformation of the active sites,leading to the formation of a hexacoordinate complex,Ru(CO)_(2)C_(12)(C_(6)H_(15)N·HCl)_(2).DFT calculations further elucidated the mechanism underlying active site formation,revealing that an increased electron density around the Ru centre and corresponding changes in its coordination environment play critical roles in enhancing catalyst stability and activity.This study contributes to a deeper understanding of the structural basis of active site evolution during acetylene hydrochlorination,offering both practical insights into industrial applications and foundational knowledge for advancing liquid-phase catalysis.展开更多
PEGylation,the controlled covalent conjugation of polyethylene glycol to therapeutics,enhances therapeutic efficacy through optimized pharmacokinetics.However,to date no high-molecular-weight PE-Gylated small-molecule...PEGylation,the controlled covalent conjugation of polyethylene glycol to therapeutics,enhances therapeutic efficacy through optimized pharmacokinetics.However,to date no high-molecular-weight PE-Gylated small-molecule prodrugs have received regulatory approval.This technological gap can be partially attributed to the exponential proliferation of metabolic intermediates resulting from multi-payload conjugation strategies,which introduces unprecedented analytical complexities in metabolite profiling and pharmacokinetic characterization.To address this challenge,we developed a liquid chromatographytriple-quadrupole/time-of-flight mass spectrometry platform for PEG20k-(irinotecan)3,a Phase Ⅲ clinical candidate.Our methodology employs payload stoichiometry-based chromatographic resolution for clustering isomeric PEG species.Complementarily,diagnostic product ions at m/z 699.83,569.27,and 587.28enable systematic differentiation between double-loaded,single-loaded,and released irinotecan payload.This approach successfully identifies eight metabolic clusters spanning from PEG-conjugates,cleaved PEG segments,and released small-molecule species.Its demonstrated capacity to deconvolute complex metabolic profiles-through payload-stoichiometry based chromatographic resolution coupled with diagnostic ion analysis-positions this workflow as an attractive tool for accelerating the development of PE-Gylated small-molecule therapeutics.展开更多
Pt nanoparticles entrapped in ordered mesoporous CMK-3 carbons with p6mm symmetry were prepared using a facile impregnation method, and the resulting materials were characterized using X-ray diffraction spectroscopy, ...Pt nanoparticles entrapped in ordered mesoporous CMK-3 carbons with p6mm symmetry were prepared using a facile impregnation method, and the resulting materials were characterized using X-ray diffraction spectroscopy, N2 adsorption-desorption, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The Pt nanoparticles were highly dispersed in the CMK-3 with 43.7% dispersion. The Pt/CMK-3 catalyst was an effective catalyst for the liquid-phase hydrogenation of nitrobenzene and its derivatives under the experimental conditions studied here. The Pt/CMK-3 catalyst was more active than commercial Pt/C catalyst in most cases. A highest turnover frequency of 43.8 s-1 was measured when the Pt/CMK-3 catalyst was applied for the hydrogenation of 2-methyl-nitrobenzene in ethanol under optimal conditions. It is worthy of note that the Pt/CMK-3 catalyst could be recycled easily, and could be reused at least fourteen times without any loss in activity or selectivity for the hydrogenation of nitrobenzene in ethanol.展开更多
An efficient poly(ethylene glycol) (PEG)-supported liquid-phase parallel approach to di(aryloxyacetyl)thiosemicarbazides is described. PEG-bound phenol reacted with chloroacetic acid to afford PEG-bound phenyloxyaceti...An efficient poly(ethylene glycol) (PEG)-supported liquid-phase parallel approach to di(aryloxyacetyl)thiosemicarbazides is described. PEG-bound phenol reacted with chloroacetic acid to afford PEG-bound phenyloxyacetic acid, which was readily converted into corresponding phenyloxyacetyl chloride. Subsequent nucleophilic substitution with ammonium thiocyanate followed by addition of aryloxyacetic acid hydrazides gave PEG-bound di(aryloxyacetyl)thiosemi-carbazides, which were easily cleaved to give the resulting library of 1-aryloxyacetyl-4-(4'-methoxylcarbonylphenyloxyacetyl)thiosemicarbazides in good to high yield and high purity.展开更多
Liquid phase oxidation of toluene is an environmental benign route for the production of benzoic acid.In a φ48mm bubble column reactor,the commercial process of toluene liquid phase oxidation was conducted with Co(CH...Liquid phase oxidation of toluene is an environmental benign route for the production of benzoic acid.In a φ48mm bubble column reactor,the commercial process of toluene liquid phase oxidation was conducted with Co(CH3COO)2.4H2O as catalyst.The Co2+ concentration [Co2+] was determined by extraction spectrophotometry and hereby the Co3+ concentration [Co3+] was obtained by mass balance.The results showed that [Co3+] reached the maximum at about 25-30min.[Co3+] increased with increasing Co catalyst amount at total Co concentration<150 mg.L-1 of toluene.The conversion of toluene,yield and selectivity of benzoic acid increased with the increasing [Co3+/Co2+] max.A high [Co3+] and a high [Co3+]/[Co2+] ratio are beneficial to the reaction.展开更多
The homogeneous liquid was separated into two phases, （Fe, Co）-rich LI and Cu-rich L2, once the melt was undercooled below a liquid-phase separation temperature Tsep. If the duration from Tsep to Tsl （solidificatio...The homogeneous liquid was separated into two phases, （Fe, Co）-rich LI and Cu-rich L2, once the melt was undercooled below a liquid-phase separation temperature Tsep. If the duration from Tsep to Tsl （solidification temperature of LI phase）, termed the liquid-phase separation interval Δt, exceeded a critical value, an eggtype structure was observed. By utilizing differential thermal analyses （DTA）, the solidification process of the undercooled Fe-Co-Cu alloys was studied. Additionally, an immiscible boundary was obtained, which was a convex parabola with a symmetrical axis of XCu=0.52. Depending on the relative amounts of LI and L2, the minor phase was nucleated firstly to form liquid droplets and separated from the original liquids at the beginning of liquid-phase separation.展开更多
The liquid-phase furfural （FAL） hydrogenation to furfuryl alcohol （FOL） and tetrahydrofurfuryl alcohol （THFOL） was investigated using sulfonate group （-SO3H） grafted activated carbon （AC） supported Ni cataly...The liquid-phase furfural （FAL） hydrogenation to furfuryl alcohol （FOL） and tetrahydrofurfuryl alcohol （THFOL） was investigated using sulfonate group （-SO3H） grafted activated carbon （AC） supported Ni catalyst, which was prepared and activated simultaneously by liquid phase reduction method. This functionalized nickel catalyst demonstrated an enhanced catalytic performance for selective hydrogenation of FAL, in which almost 100% FOL （〈80℃） and THFOL （〉100℃） selectivity with complete conversion was obtained, respectively. More importantly, the conversion of transfer hydrogenation of FAL to FOL also can reach almost 100% under optimal conditions （140℃, 4.0h）. The effect of -SO3H was evaluated and systematically analyzed by the combination of reaction performance and physico-chemical characterizations. Cycling test proved the prepared catalyst could be recycled and reused for several times without noticeably reducing catalytic activity of hvdrogenation.展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.32172602,32472739)the Major Science and Technology Project of Henan Province(Grant No.221100110400)+3 种基金the Funding of Joint Research on Agricultural Varietie Improvement of Henan Province(Grant No.2022010503)the Natural Science Foundation of Henan(Grant No.242300421030)the Key Scientifc and Technological Project of Henan Province(Grant Nos.242102111124,242102111115)the Key Research and Development Program of Xinjiang Uygur autonomous region(2023B02017-2).
文摘Genotyping by Target Sequencing(GBTS)technology,known for its flexibility,high efficiency,high throughput,and low cost,has been increasingly employed in molecular breeding.However,there is still limited study on the design and development of high-throughput genotyping tools in watermelon.In this study,we identified 112000 high quality SNPs by analyzing the resequencing data of 43 cultivated watermelon accessions.11921 and 6094 SNPs were selected for developing two sets of watermelon liquid-phase chips with different marker densities,named Watermelon 10K and 5K,respectively.Furthermore,the SNPs and Indels of most mapped gene/QTLs for many agronomic important traits in watermelon were also integrated into the two chips for foreground selection.These chips have been tested using GBTS technology in various applications in watermelon.The genotyping of 76 accessions by Watermelon 5K liquid-phase chip showed an average detection rate of 99.28%and 81.78%for cultivated and wild watermelon accessions,respectively.This provided enough markers information for GWAS and two significant QTLs,ssc1.1 and ssc1.2,associated with soluble sugar content were detected.Furthermore,BSA-seq analysis for non-lobed leaf and dwarf traits were validated by liquid-phase chips,and the candidate region was consistent with our previous studies.Additionally,we precisely introduced the Cldw1 and Clbl genes into an elite inbred line WT2 using Watermelon 5K for assisted selection,resulting in the development of three new germplasm with good plant architecture.As a high-throughput genotyping liquid-phase SNP array,the Watermelon 10K and 5K chips will greatly facilitate functional studies and molecular breeding in watermelon.
基金supported by the National Natural Science Foundation of China(No.22378308)Jing-Jin-Ji Regional Integrated Environmental Improvement-National Science and Technology Major Project(No.2024ZD1200301–2)the Scientific and Technological Project of Yunnan Precious Metal Laboratory(No.YPML2023050202)。
文摘A comprehensive understanding of the structure and dynamic evolution of catalytic active sites is vital for advancing the study of liquid-phase acetylene hydrochlorination.Here,we successfully developed a Ru-DIPEA/TMS catalyst optimised through systematic composition and condition tuning,demonstrating exceptional performance with 95.5%C_(2)H_(2)conversion and sustaining over 91.1%activity along with nearly 100%selectivity for VCM during a continuous 900-h test.Using a combination of characterisation techniques,including UV–vis spectroscopy,FT-IR spectroscopy,X-ray photoelectron spectroscopy,singlecrystal X-ray diffraction,and X-ray absorption spectroscopy,along with density functional theory(DFT)calculations,the structure and dynamic behaviour of the active sites were thoroughly investigated under the synergistic influence of ligands and HCl.The results revealed that HCl activation induces a significant structural transformation of the active sites,leading to the formation of a hexacoordinate complex,Ru(CO)_(2)C_(12)(C_(6)H_(15)N·HCl)_(2).DFT calculations further elucidated the mechanism underlying active site formation,revealing that an increased electron density around the Ru centre and corresponding changes in its coordination environment play critical roles in enhancing catalyst stability and activity.This study contributes to a deeper understanding of the structural basis of active site evolution during acetylene hydrochlorination,offering both practical insights into industrial applications and foundational knowledge for advancing liquid-phase catalysis.
基金support from the National Natural Science Foundation of China(Nos.82030107,82304443,82373944)the Hainan Provincial Natural Science Foundation of China(No.825QN288).
文摘PEGylation,the controlled covalent conjugation of polyethylene glycol to therapeutics,enhances therapeutic efficacy through optimized pharmacokinetics.However,to date no high-molecular-weight PE-Gylated small-molecule prodrugs have received regulatory approval.This technological gap can be partially attributed to the exponential proliferation of metabolic intermediates resulting from multi-payload conjugation strategies,which introduces unprecedented analytical complexities in metabolite profiling and pharmacokinetic characterization.To address this challenge,we developed a liquid chromatographytriple-quadrupole/time-of-flight mass spectrometry platform for PEG20k-(irinotecan)3,a Phase Ⅲ clinical candidate.Our methodology employs payload stoichiometry-based chromatographic resolution for clustering isomeric PEG species.Complementarily,diagnostic product ions at m/z 699.83,569.27,and 587.28enable systematic differentiation between double-loaded,single-loaded,and released irinotecan payload.This approach successfully identifies eight metabolic clusters spanning from PEG-conjugates,cleaved PEG segments,and released small-molecule species.Its demonstrated capacity to deconvolute complex metabolic profiles-through payload-stoichiometry based chromatographic resolution coupled with diagnostic ion analysis-positions this workflow as an attractive tool for accelerating the development of PE-Gylated small-molecule therapeutics.
基金supported by the National Natural Science Foundation of China(21273076 and 21373089)the Open Research Fund of Top Key Discipline of Chemistry in Zhejiang Provincial Colleges and Key Laboratory of the Ministry of Education for Catalysis Materials(Zhejiang Normal University,ZJHX2013)Shanghai Leading Academic Discipline Project (B409)~~
文摘Pt nanoparticles entrapped in ordered mesoporous CMK-3 carbons with p6mm symmetry were prepared using a facile impregnation method, and the resulting materials were characterized using X-ray diffraction spectroscopy, N2 adsorption-desorption, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The Pt nanoparticles were highly dispersed in the CMK-3 with 43.7% dispersion. The Pt/CMK-3 catalyst was an effective catalyst for the liquid-phase hydrogenation of nitrobenzene and its derivatives under the experimental conditions studied here. The Pt/CMK-3 catalyst was more active than commercial Pt/C catalyst in most cases. A highest turnover frequency of 43.8 s-1 was measured when the Pt/CMK-3 catalyst was applied for the hydrogenation of 2-methyl-nitrobenzene in ethanol under optimal conditions. It is worthy of note that the Pt/CMK-3 catalyst could be recycled easily, and could be reused at least fourteen times without any loss in activity or selectivity for the hydrogenation of nitrobenzene in ethanol.
文摘An efficient poly(ethylene glycol) (PEG)-supported liquid-phase parallel approach to di(aryloxyacetyl)thiosemicarbazides is described. PEG-bound phenol reacted with chloroacetic acid to afford PEG-bound phenyloxyacetic acid, which was readily converted into corresponding phenyloxyacetyl chloride. Subsequent nucleophilic substitution with ammonium thiocyanate followed by addition of aryloxyacetic acid hydrazides gave PEG-bound di(aryloxyacetyl)thiosemi-carbazides, which were easily cleaved to give the resulting library of 1-aryloxyacetyl-4-(4'-methoxylcarbonylphenyloxyacetyl)thiosemicarbazides in good to high yield and high purity.
基金Supported by the National Natural Science Foundation of China （20576081, 20736009） and the Ph.D. Programs Foundation of Ministry of Education of China （20070610128）.
文摘Liquid phase oxidation of toluene is an environmental benign route for the production of benzoic acid.In a φ48mm bubble column reactor,the commercial process of toluene liquid phase oxidation was conducted with Co(CH3COO)2.4H2O as catalyst.The Co2+ concentration [Co2+] was determined by extraction spectrophotometry and hereby the Co3+ concentration [Co3+] was obtained by mass balance.The results showed that [Co3+] reached the maximum at about 25-30min.[Co3+] increased with increasing Co catalyst amount at total Co concentration<150 mg.L-1 of toluene.The conversion of toluene,yield and selectivity of benzoic acid increased with the increasing [Co3+/Co2+] max.A high [Co3+] and a high [Co3+]/[Co2+] ratio are beneficial to the reaction.
基金supported by the Natural Science Foundation of China (Grant No.50771084)the Natural Science Foundation of the Education Department of Jiangsu province,China (Grant No.09KJB430004)
文摘The homogeneous liquid was separated into two phases, （Fe, Co）-rich LI and Cu-rich L2, once the melt was undercooled below a liquid-phase separation temperature Tsep. If the duration from Tsep to Tsl （solidification temperature of LI phase）, termed the liquid-phase separation interval Δt, exceeded a critical value, an eggtype structure was observed. By utilizing differential thermal analyses （DTA）, the solidification process of the undercooled Fe-Co-Cu alloys was studied. Additionally, an immiscible boundary was obtained, which was a convex parabola with a symmetrical axis of XCu=0.52. Depending on the relative amounts of LI and L2, the minor phase was nucleated firstly to form liquid droplets and separated from the original liquids at the beginning of liquid-phase separation.
基金the National Natural Science Foundation of China (Nos. 51502297, 51372248, and 51432009)Instrument Developing Project of the Chinese Academy of Sciences (No. yz201421)
文摘The liquid-phase furfural （FAL） hydrogenation to furfuryl alcohol （FOL） and tetrahydrofurfuryl alcohol （THFOL） was investigated using sulfonate group （-SO3H） grafted activated carbon （AC） supported Ni catalyst, which was prepared and activated simultaneously by liquid phase reduction method. This functionalized nickel catalyst demonstrated an enhanced catalytic performance for selective hydrogenation of FAL, in which almost 100% FOL （〈80℃） and THFOL （〉100℃） selectivity with complete conversion was obtained, respectively. More importantly, the conversion of transfer hydrogenation of FAL to FOL also can reach almost 100% under optimal conditions （140℃, 4.0h）. The effect of -SO3H was evaluated and systematically analyzed by the combination of reaction performance and physico-chemical characterizations. Cycling test proved the prepared catalyst could be recycled and reused for several times without noticeably reducing catalytic activity of hvdrogenation.
