Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated fo...Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.展开更多
This research explores the influence of crystallinity on gas chromatographic(GC) separation using covalent organic frameworks(COFs) as stationary phases.Three COF materials(CTF-DCBs) with varying crystallinity were sy...This research explores the influence of crystallinity on gas chromatographic(GC) separation using covalent organic frameworks(COFs) as stationary phases.Three COF materials(CTF-DCBs) with varying crystallinity were synthesized and characterized.CTF-DCB-1,with superior crystallinity,demonstrated highselectivity GC separation of benzene isomers as well as styrene/phenylacetylene mixtures,while CTFDCB-2 and CTF-DCB-3 exhibited lower crystallinity and worse separation performance.Thermodynamic and kinetic tests showed that CTF-DCB-1 had the worst thermodynamic adsorption but low diffusion mass transfer resistance,which resulted in the best separation.Therefore,optimizing the crystallinity of COFs is necessary for balancing the kinetic diffusion and thermodynamic interactions towards the analytes,achieving high-performance GC stationary phases.展开更多
基金supported by the National Natural Science Foundation of China (Nos.22064020,22364022,and 22174125)the Applied Basic Research Foundation of Yunnan Province (Nos.202101AT070101 and 202201AT070029)。
文摘Developing a chiral material as versatile and universal chiral stationary phase(CSP) for chiral separation in diverse chromatographic techniques simultaneously is of great significance.In this study,we demonstrated for the first time that a chiral metal-organic cage(MOC),[Zn_(6)M_(4)],as a universal chiral recognition material for both multi-mode high-performance liquid chromatography(HPLC) and capillary gas chromatography(GC) enantioseparation.Two novel HPLC CSPs with different bonding arms(CSP-A with a cationic imidazolium bonding arm and CSP-B with an alkyl chain bonding arm) were prepared by clicking of functionalized chiral MOC [Zn_(6)M_(4)] onto thiolated silica via thiol-ene click chemistry.Meanwhile,a capillary GC column statically coated with the chiral MOC [Zn_(6)M_(4)] was also fabricated.The results showed that the chiral MOC exhibits excellent enantioselectivity not only in normal phase HPLC(NP-HPLC) and reversed phase(RP-HPLC) but also in GC,and various racemates were well separated,including alcohols,diols,esters,ketones,ethers,amines,and epoxides.Importantly,CSP-A and CSP-B are complementary to commercially available Chiralcel OD-H and Chiralpak AD-H columns in enantioseparation,which can separate some racemates that could not be or could not well be separated by the two widely used commercial columns,suggesting the great potential of the two prepared CSPs in enantioseparation.This work reveals that the chiral MOC is potential versatile chiral recognition materials for both HPLC and GC,and also paves the way to expand the potential applications of MOCs.
基金supported by the National Natural Science Foundation of China (Nos.22174067,22204078,and 22374077)the Natural Science Foundation of Jiangsu Province of China (No.BK20220370)+3 种基金Jiangsu Provincial Department of Education (No.22KJB150009)State Key Laboratory of Analytical Chemistry for Life Science (No.SKLACLS2218)the Priority Academic Program Development of Jiangsu Higher Education Institutions,Jiangsu Association for Science and Technology (No.TJ-2023-076)Shanghai Synchrotron Radiation Facility Beamline BL17B1 (No.2021-NFPSPT-006657)。
文摘This research explores the influence of crystallinity on gas chromatographic(GC) separation using covalent organic frameworks(COFs) as stationary phases.Three COF materials(CTF-DCBs) with varying crystallinity were synthesized and characterized.CTF-DCB-1,with superior crystallinity,demonstrated highselectivity GC separation of benzene isomers as well as styrene/phenylacetylene mixtures,while CTFDCB-2 and CTF-DCB-3 exhibited lower crystallinity and worse separation performance.Thermodynamic and kinetic tests showed that CTF-DCB-1 had the worst thermodynamic adsorption but low diffusion mass transfer resistance,which resulted in the best separation.Therefore,optimizing the crystallinity of COFs is necessary for balancing the kinetic diffusion and thermodynamic interactions towards the analytes,achieving high-performance GC stationary phases.
