Chiral metal-organic frameworks(CMOFs)with enantiomeric subunits have been employed in chiral chemistry.In this study,a CMOF formed from 6-methoxyl-(8S,9R)-cinchonan-9-ol-3-carboxylic acid(HQA)and ZnCl_(2),{(HQA)(ZnCl...Chiral metal-organic frameworks(CMOFs)with enantiomeric subunits have been employed in chiral chemistry.In this study,a CMOF formed from 6-methoxyl-(8S,9R)-cinchonan-9-ol-3-carboxylic acid(HQA)and ZnCl_(2),{(HQA)(ZnCl_(2))(2.5H_(2)O)}n,was constructed as a chiral stationary phase(CSP)via an in situ fabrication approach and used for chiral amino acid and drug analyses for the first time.The{(HQA)(ZnCl_(2))(2.5H_(2)O)}n nanocrystal and the corresponding chiral stationary phase were systematically characterised using a series of analytical techniques including scanning electron microscopy,X-ray diffraction,Fourier transform infrared spectroscopy,circular dichroism,X-ray photoelectron spectroscopy,thermogravimetric analysis,and Brunauer-Emmett-Teller surface area measurements.In opentubular capillary electrochromatography(CEC),the novel chiral column exhibited strong and broad enantioselectivity toward a variety of chiral analytes,including 19 racemic dansyl amino acids and several model chiral drugs(both acidic and basic).The chiral CEC conditions were optimised,and the enantioseparation mechanisms are discussed.This study not only introduces a new high-efficiency member of the MOF-type CSP family but also demonstrates the potential of improving the enantioselectivities of traditional chiral recognition reagents by fully using the inherent characteristics of porous organic frameworks.展开更多
The increasing concentration of CO_(2) in atmosphere is deemed the main reason of global warming.Therefore,efficiently capturing CO_(2) from various sources with energy conservation is of great significance.Herein,a s...The increasing concentration of CO_(2) in atmosphere is deemed the main reason of global warming.Therefore,efficiently capturing CO_(2) from various sources with energy conservation is of great significance.Herein,a series of experiments were carried out to successfully test the slurry-based ab-adsorption method for continuously capturing CO_(2) in the large-scale cycled separation unit with cost-effect taking into account the scale-up criteria.A bubble column(with height 4900 mm and inner diameter 376 mm)and a desorption tank(with volume 310 L)are the essential components of the separation unit.The novel slurry used in this study was formed with zeolitic imidazolate framework-8 and 2-methylimidazole-water solution.The influence of operation conditions was investigated systematically.The results show that increasing sorption pressure and slurry height level,decreasing gas volume flow and sorption temperature are beneficial for separation processes.The volume fraction of CO_(2) in the feed gas was also studied.Although the scale-up effect had been observed and it was found that it exerted a negative effect on CO_(2) capture,depending on experimental conditions,CO_(2) removal efficiency could still reach 85%-95%and the maximum CO_(2) loading in the recycled slurry could be up to0.007 mol·L-1·kPa-1.Furthermore,the slurry-based method could be operated well even under very moderate regeneration conditions(333 K and 0.05 MPa),which means that the novel approach shows greater energy conservation than traditional amine absorption methods.展开更多
基金This study was funded by the National Natural Science Foundation of China(Grant No.:82003705)the Shanghai Science and Technology Innovation Foundation(Grant Nos.:23010500200 and 23ZR1422700).
文摘Chiral metal-organic frameworks(CMOFs)with enantiomeric subunits have been employed in chiral chemistry.In this study,a CMOF formed from 6-methoxyl-(8S,9R)-cinchonan-9-ol-3-carboxylic acid(HQA)and ZnCl_(2),{(HQA)(ZnCl_(2))(2.5H_(2)O)}n,was constructed as a chiral stationary phase(CSP)via an in situ fabrication approach and used for chiral amino acid and drug analyses for the first time.The{(HQA)(ZnCl_(2))(2.5H_(2)O)}n nanocrystal and the corresponding chiral stationary phase were systematically characterised using a series of analytical techniques including scanning electron microscopy,X-ray diffraction,Fourier transform infrared spectroscopy,circular dichroism,X-ray photoelectron spectroscopy,thermogravimetric analysis,and Brunauer-Emmett-Teller surface area measurements.In opentubular capillary electrochromatography(CEC),the novel chiral column exhibited strong and broad enantioselectivity toward a variety of chiral analytes,including 19 racemic dansyl amino acids and several model chiral drugs(both acidic and basic).The chiral CEC conditions were optimised,and the enantioseparation mechanisms are discussed.This study not only introduces a new high-efficiency member of the MOF-type CSP family but also demonstrates the potential of improving the enantioselectivities of traditional chiral recognition reagents by fully using the inherent characteristics of porous organic frameworks.
基金The authors gratefully acknowledge the financial supports received from the National Natural Science Foundation of China(21776301,21636009)the Science Foundation of China University of Petroleum,Beijing(2462018BJC004).
文摘The increasing concentration of CO_(2) in atmosphere is deemed the main reason of global warming.Therefore,efficiently capturing CO_(2) from various sources with energy conservation is of great significance.Herein,a series of experiments were carried out to successfully test the slurry-based ab-adsorption method for continuously capturing CO_(2) in the large-scale cycled separation unit with cost-effect taking into account the scale-up criteria.A bubble column(with height 4900 mm and inner diameter 376 mm)and a desorption tank(with volume 310 L)are the essential components of the separation unit.The novel slurry used in this study was formed with zeolitic imidazolate framework-8 and 2-methylimidazole-water solution.The influence of operation conditions was investigated systematically.The results show that increasing sorption pressure and slurry height level,decreasing gas volume flow and sorption temperature are beneficial for separation processes.The volume fraction of CO_(2) in the feed gas was also studied.Although the scale-up effect had been observed and it was found that it exerted a negative effect on CO_(2) capture,depending on experimental conditions,CO_(2) removal efficiency could still reach 85%-95%and the maximum CO_(2) loading in the recycled slurry could be up to0.007 mol·L-1·kPa-1.Furthermore,the slurry-based method could be operated well even under very moderate regeneration conditions(333 K and 0.05 MPa),which means that the novel approach shows greater energy conservation than traditional amine absorption methods.
