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Engineering Cyclodextrin Clicked Chiral Stationary Phase for High-Efficiency Enantiomer Separation.

Tang J, Zhang S, Lin Y, Zhou J, Pang L, Nie X, Zhou B, Tang W - Sci Rep (2015)

Bottom Line: Insights on the impact of CD functionalities in structure design are provided.High-efficiency enantioseparation of a range of aryl alcohols and flavanoids with resolution values (Rs) over 10 were demonstrated by per(3-chloro-4-methyl)phenylcarbamated CD clicked CSP.Comparison study and molecular simulations suggest the improved enantioselectivity was attributed to higher interactions energy difference between the complexes of enantiomers and CSPs with phenylcarbamated CD bearing 3-chloro and 4-methyl functionalities.

View Article: PubMed Central - PubMed

Affiliation: 1] Key Laboratory of Soft Chemistry and Functional Materials (Ministry of Education), Nanjing University of Science and Technology, Nanjing 210094, People's Republic of China [2] Key Laboratory of Soft Chemistry and Functional Materials (Ministry of Education), Nanjing University of Science and Technology, Nanjing 210094, People's Republic of China.

ABSTRACT
The separation of racemic molecules is of crucial significance not only for fundamental research but also for technical application. Enantiomers remain challenging to be separated owing to their identical physical and chemical properties in achiral environments. Chromatographic techniques employing chiral stationary phases (CSPs) have been developed as powerful tools for the chiral analysis and preparation of pure enantiomers, most of which are of biological and pharmaceutical interests. Here we report our efforts in developing high-performance phenylcarbamated cyclodextrin (CD) clicked CSPs. Insights on the impact of CD functionalities in structure design are provided. High-efficiency enantioseparation of a range of aryl alcohols and flavanoids with resolution values (Rs) over 10 were demonstrated by per(3-chloro-4-methyl)phenylcarbamated CD clicked CSP. Comparison study and molecular simulations suggest the improved enantioselectivity was attributed to higher interactions energy difference between the complexes of enantiomers and CSPs with phenylcarbamated CD bearing 3-chloro and 4-methyl functionalities.

No MeSH data available.


Related in: MedlinePlus

Optimized structure of (a) CCC3M4-CSP complex with R-1-(4-bromophenyl)ethanol, (b) CCC3M4-CSP complex with S-1-(4-bromophenyl)ethanol, (c) CCP-CSP complex with R-1-(4-bromophenyl)ethanol, and (d) CCP-CSP complex with S-1-(4-bromophenyl)ethanol in MeOH/H2O (50:50), Elution order of 1-(4-bromophenyl)ethanol enantiomers with (e) CCC3M4-CSP and (f) CCP-CSP at 1.0 mL/min MeOH/H2O (50/50).
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f7: Optimized structure of (a) CCC3M4-CSP complex with R-1-(4-bromophenyl)ethanol, (b) CCC3M4-CSP complex with S-1-(4-bromophenyl)ethanol, (c) CCP-CSP complex with R-1-(4-bromophenyl)ethanol, and (d) CCP-CSP complex with S-1-(4-bromophenyl)ethanol in MeOH/H2O (50:50), Elution order of 1-(4-bromophenyl)ethanol enantiomers with (e) CCC3M4-CSP and (f) CCP-CSP at 1.0 mL/min MeOH/H2O (50/50).

Mentions: To further elucidate the enhanced enantioselectivity for CCC3M4-CSP over CCP-CSP with 3- and 4-fuctionalities on phenyl group, quantum mechanics calculation was employed to evaluate the intermolecular interactions between CD chiral selector and enantiomers. We herein selected 1-(4-bromophenyl)ethanol as model analyte. Fig. 7a–d depicts the PM3 optimized structure of the complex for each enantiomer with CCC3M4-CSP and CCP-CSP. The interaction energy of the complexes was calculated using Einteraction = Ecomplex-Efree-CD-Efree-analytes, where E is the total energy. The more negative the interaction energy, the stronger the interaction between (R/S)-1-(4-bromophenyl)ethanol and CSP, and the more stable is the inclusion complex.


Engineering Cyclodextrin Clicked Chiral Stationary Phase for High-Efficiency Enantiomer Separation.

Tang J, Zhang S, Lin Y, Zhou J, Pang L, Nie X, Zhou B, Tang W - Sci Rep (2015)

Optimized structure of (a) CCC3M4-CSP complex with R-1-(4-bromophenyl)ethanol, (b) CCC3M4-CSP complex with S-1-(4-bromophenyl)ethanol, (c) CCP-CSP complex with R-1-(4-bromophenyl)ethanol, and (d) CCP-CSP complex with S-1-(4-bromophenyl)ethanol in MeOH/H2O (50:50), Elution order of 1-(4-bromophenyl)ethanol enantiomers with (e) CCC3M4-CSP and (f) CCP-CSP at 1.0 mL/min MeOH/H2O (50/50).
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4530664&req=5

f7: Optimized structure of (a) CCC3M4-CSP complex with R-1-(4-bromophenyl)ethanol, (b) CCC3M4-CSP complex with S-1-(4-bromophenyl)ethanol, (c) CCP-CSP complex with R-1-(4-bromophenyl)ethanol, and (d) CCP-CSP complex with S-1-(4-bromophenyl)ethanol in MeOH/H2O (50:50), Elution order of 1-(4-bromophenyl)ethanol enantiomers with (e) CCC3M4-CSP and (f) CCP-CSP at 1.0 mL/min MeOH/H2O (50/50).
Mentions: To further elucidate the enhanced enantioselectivity for CCC3M4-CSP over CCP-CSP with 3- and 4-fuctionalities on phenyl group, quantum mechanics calculation was employed to evaluate the intermolecular interactions between CD chiral selector and enantiomers. We herein selected 1-(4-bromophenyl)ethanol as model analyte. Fig. 7a–d depicts the PM3 optimized structure of the complex for each enantiomer with CCC3M4-CSP and CCP-CSP. The interaction energy of the complexes was calculated using Einteraction = Ecomplex-Efree-CD-Efree-analytes, where E is the total energy. The more negative the interaction energy, the stronger the interaction between (R/S)-1-(4-bromophenyl)ethanol and CSP, and the more stable is the inclusion complex.

Bottom Line: Insights on the impact of CD functionalities in structure design are provided.High-efficiency enantioseparation of a range of aryl alcohols and flavanoids with resolution values (Rs) over 10 were demonstrated by per(3-chloro-4-methyl)phenylcarbamated CD clicked CSP.Comparison study and molecular simulations suggest the improved enantioselectivity was attributed to higher interactions energy difference between the complexes of enantiomers and CSPs with phenylcarbamated CD bearing 3-chloro and 4-methyl functionalities.

View Article: PubMed Central - PubMed

Affiliation: 1] Key Laboratory of Soft Chemistry and Functional Materials (Ministry of Education), Nanjing University of Science and Technology, Nanjing 210094, People's Republic of China [2] Key Laboratory of Soft Chemistry and Functional Materials (Ministry of Education), Nanjing University of Science and Technology, Nanjing 210094, People's Republic of China.

ABSTRACT
The separation of racemic molecules is of crucial significance not only for fundamental research but also for technical application. Enantiomers remain challenging to be separated owing to their identical physical and chemical properties in achiral environments. Chromatographic techniques employing chiral stationary phases (CSPs) have been developed as powerful tools for the chiral analysis and preparation of pure enantiomers, most of which are of biological and pharmaceutical interests. Here we report our efforts in developing high-performance phenylcarbamated cyclodextrin (CD) clicked CSPs. Insights on the impact of CD functionalities in structure design are provided. High-efficiency enantioseparation of a range of aryl alcohols and flavanoids with resolution values (Rs) over 10 were demonstrated by per(3-chloro-4-methyl)phenylcarbamated CD clicked CSP. Comparison study and molecular simulations suggest the improved enantioselectivity was attributed to higher interactions energy difference between the complexes of enantiomers and CSPs with phenylcarbamated CD bearing 3-chloro and 4-methyl functionalities.

No MeSH data available.


Related in: MedlinePlus