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
锝-99m(^(99m)Tc)是核医学中应用最广泛的放射性核素之一,其独特的物理和化学性质使其成为诊断成像的理想选择。受到部分生产堆退役的影响,未来国际上^(99m)Tc可能面临紧缺问题,而基于加速器生产^(99m)Tc的方法受到越来越多关注。本研...锝-99m(^(99m)Tc)是核医学中应用最广泛的放射性核素之一,其独特的物理和化学性质使其成为诊断成像的理想选择。受到部分生产堆退役的影响,未来国际上^(99m)Tc可能面临紧缺问题,而基于加速器生产^(99m)Tc的方法受到越来越多关注。本研究旨在建立来源于质子打靶产生的^(99)Mo与其衰变产物^(99m)Tc分离的方法,为利用加速器生产^(99m)Tc打下良好基础。本文以高铼酸钾作为高锝酸根的模拟物,比较活性炭、Tetravalent Actinides and Technetium树脂(以下称TEVA树脂)和氧化铝对钼-锝(铼)的分离效果,通过电感耦合等离子体质谱(ICP-MS)分析洗脱液中钼和铼的浓度,评估不同方法的分离效率。研究表明,活性炭在中性或碱性条件下无法有效分离钼和铼。相比之下,TEVA树脂在酸性条件下表现出优异的分离性能,使用8 mol/L硝酸可以有效地从TEVA洗脱高铼酸根。此外,研究发现,氧化铝在pH≤7时对钼酸根具有强吸附作用,而生理盐水可有效洗脱高铼酸根。基于上述结果,本研究设计了一种氧化铝与TEVA树脂组合的分离流程,即先利用氧化铝柱吸附钼酸根,再用生理盐水洗脱高铼酸根,最后通过TEVA树脂进一步纯化。该方法实现了高铼酸根的平均回收率为69.7%~81.4%,而钼含量低于1%,从而为钼-锝分离提供了一种高效、可行的技术路线,为基于加速器生产^(99m)Tc打下良好基础。展开更多
核级锆(Zr)和核级铪(Hf)是保障核工业发展的重要基础材料。溶剂萃取分离是制备核级锆铪的技术关键。本文从溶液化学平衡角度,阐释了酸性介质有利于抑制锆铪离子的水解聚合,提高其反应活度。根据软硬酸碱理论和活性功能基差异,总结了近...核级锆(Zr)和核级铪(Hf)是保障核工业发展的重要基础材料。溶剂萃取分离是制备核级锆铪的技术关键。本文从溶液化学平衡角度,阐释了酸性介质有利于抑制锆铪离子的水解聚合,提高其反应活度。根据软硬酸碱理论和活性功能基差异,总结了近年来研发的萃取剂主要有含O, N, P和S等不同类型,并评价了其主要优点和不足。结合有机膦酸类萃取剂的二聚体结构特征,阐述了具有电子给体特征的惰性有机溶剂对该类萃取剂的“解聚”作用机制。并且,从界面化学反应平衡角度,解释了具有一定溶解度的有机溶剂,对提升萃取反应效率的必要性。除此之外,还结合软硬酸碱理论和霍夫迈斯特序列,综述了锆铪溶剂萃取分离体系助萃剂、盐析剂和反萃剂等选用的基本原则,以期为锆铪高效溶剂萃取分离体系的研发和应用提供基础理论指导。展开更多
^(99)Mo是重要的医用放射性核素,溶剂萃取法是反应堆辐照^(235)U靶生产裂变^(99)Mo的分离方法之一。为探讨离子液体Cyphos IL 101用于裂变^(99)Mo分离的可能性,本研究评价了离子液体Cyphos IL 101在硝酸体系中对Mo(Ⅵ)的萃取行为,重点...^(99)Mo是重要的医用放射性核素,溶剂萃取法是反应堆辐照^(235)U靶生产裂变^(99)Mo的分离方法之一。为探讨离子液体Cyphos IL 101用于裂变^(99)Mo分离的可能性,本研究评价了离子液体Cyphos IL 101在硝酸体系中对Mo(Ⅵ)的萃取行为,重点考察了稀释剂、水相初始pH、萃取时间、温度、离子液体浓度等对萃取Mo(Ⅵ)的影响。结果表明,选用甲苯作为稀释剂时,Cyphos IL 101对Mo(Ⅵ)的萃取效果最好,在pH=3条件下,萃取率高达98.87%;萃取为自发进行的过程,且可在5 min达到平衡;选用1 mol/L Na_(2)CO_(3)作为反萃剂,一次反萃可将负载有机相中96.56%的Mo反萃到水相中。构建的离子液体Cyphos IL 101萃取体系对Mo与主要杂质Sr、Cs、Te等有很好的分离效果,体现了其对Mo(Ⅵ)的高选择性萃取能力。以上结果可为将离子液体Cyphos IL 101引入裂变^(99)Mo的分离工艺流程提供参考。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.
文摘锝-99m(^(99m)Tc)是核医学中应用最广泛的放射性核素之一,其独特的物理和化学性质使其成为诊断成像的理想选择。受到部分生产堆退役的影响,未来国际上^(99m)Tc可能面临紧缺问题,而基于加速器生产^(99m)Tc的方法受到越来越多关注。本研究旨在建立来源于质子打靶产生的^(99)Mo与其衰变产物^(99m)Tc分离的方法,为利用加速器生产^(99m)Tc打下良好基础。本文以高铼酸钾作为高锝酸根的模拟物,比较活性炭、Tetravalent Actinides and Technetium树脂(以下称TEVA树脂)和氧化铝对钼-锝(铼)的分离效果,通过电感耦合等离子体质谱(ICP-MS)分析洗脱液中钼和铼的浓度,评估不同方法的分离效率。研究表明,活性炭在中性或碱性条件下无法有效分离钼和铼。相比之下,TEVA树脂在酸性条件下表现出优异的分离性能,使用8 mol/L硝酸可以有效地从TEVA洗脱高铼酸根。此外,研究发现,氧化铝在pH≤7时对钼酸根具有强吸附作用,而生理盐水可有效洗脱高铼酸根。基于上述结果,本研究设计了一种氧化铝与TEVA树脂组合的分离流程,即先利用氧化铝柱吸附钼酸根,再用生理盐水洗脱高铼酸根,最后通过TEVA树脂进一步纯化。该方法实现了高铼酸根的平均回收率为69.7%~81.4%,而钼含量低于1%,从而为钼-锝分离提供了一种高效、可行的技术路线,为基于加速器生产^(99m)Tc打下良好基础。
文摘核级锆(Zr)和核级铪(Hf)是保障核工业发展的重要基础材料。溶剂萃取分离是制备核级锆铪的技术关键。本文从溶液化学平衡角度,阐释了酸性介质有利于抑制锆铪离子的水解聚合,提高其反应活度。根据软硬酸碱理论和活性功能基差异,总结了近年来研发的萃取剂主要有含O, N, P和S等不同类型,并评价了其主要优点和不足。结合有机膦酸类萃取剂的二聚体结构特征,阐述了具有电子给体特征的惰性有机溶剂对该类萃取剂的“解聚”作用机制。并且,从界面化学反应平衡角度,解释了具有一定溶解度的有机溶剂,对提升萃取反应效率的必要性。除此之外,还结合软硬酸碱理论和霍夫迈斯特序列,综述了锆铪溶剂萃取分离体系助萃剂、盐析剂和反萃剂等选用的基本原则,以期为锆铪高效溶剂萃取分离体系的研发和应用提供基础理论指导。
文摘^(99)Mo是重要的医用放射性核素,溶剂萃取法是反应堆辐照^(235)U靶生产裂变^(99)Mo的分离方法之一。为探讨离子液体Cyphos IL 101用于裂变^(99)Mo分离的可能性,本研究评价了离子液体Cyphos IL 101在硝酸体系中对Mo(Ⅵ)的萃取行为,重点考察了稀释剂、水相初始pH、萃取时间、温度、离子液体浓度等对萃取Mo(Ⅵ)的影响。结果表明,选用甲苯作为稀释剂时,Cyphos IL 101对Mo(Ⅵ)的萃取效果最好,在pH=3条件下,萃取率高达98.87%;萃取为自发进行的过程,且可在5 min达到平衡;选用1 mol/L Na_(2)CO_(3)作为反萃剂,一次反萃可将负载有机相中96.56%的Mo反萃到水相中。构建的离子液体Cyphos IL 101萃取体系对Mo与主要杂质Sr、Cs、Te等有很好的分离效果,体现了其对Mo(Ⅵ)的高选择性萃取能力。以上结果可为将离子液体Cyphos IL 101引入裂变^(99)Mo的分离工艺流程提供参考。
