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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

FT-IR spectra of mono-6A-azido-per(4-chloro-3-methyl)phenylcarbamate β-CD, mono-6A-azido-per(3-chloro-4-methyl)phenylcarbamate β-CD and mono-6A-azido-per(phenylcarbamate) β-CD.The inset showing the formation of intramolecular H-bonding between adjacent phenylcarbamate groups on neighbouring glucose units.
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f6: FT-IR spectra of mono-6A-azido-per(4-chloro-3-methyl)phenylcarbamate β-CD, mono-6A-azido-per(3-chloro-4-methyl)phenylcarbamate β-CD and mono-6A-azido-per(phenylcarbamate) β-CD.The inset showing the formation of intramolecular H-bonding between adjacent phenylcarbamate groups on neighbouring glucose units.

Mentions: The improvement in chiral recognition ability of phenylcarbamated CD clicked CSPs over CCN-CSP with the introduction of phenylcarbamoyl group on CD rims may be explained with FT-IR analysis. As shown in Fig. 6, all three phenylcarbamated β-CD derivatives exhibit two identical peaks at 3403 and 3319 cm−1 in FT-IR spectra, which was assigned to free NH for the former and hydrogen-bonded NH for the latter. The hydrogen-bonded NH is not only involved in intramolecular H-bonding between adjacent phenylcarbamate groups on neighbouring glucose units, leading to a more stable and regular higher order structure of CD CSPs, but also form H-bonding interaction with racemates. These both functions contribute to the improvement of the chiral recognition ability of perphenylcarbamated CD CSPs in comparision to native CD CSPs. For CCC3M4-CSP, the introdution of an electron-donating 4-methyl group and an electron-withdrawing 3-chloro substituent on phenyl ring will help to promote the configuration-dependent inclusion for maximum stability difference between two complexes.


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)

FT-IR spectra of mono-6A-azido-per(4-chloro-3-methyl)phenylcarbamate β-CD, mono-6A-azido-per(3-chloro-4-methyl)phenylcarbamate β-CD and mono-6A-azido-per(phenylcarbamate) β-CD.The inset showing the formation of intramolecular H-bonding between adjacent phenylcarbamate groups on neighbouring glucose units.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

f6: FT-IR spectra of mono-6A-azido-per(4-chloro-3-methyl)phenylcarbamate β-CD, mono-6A-azido-per(3-chloro-4-methyl)phenylcarbamate β-CD and mono-6A-azido-per(phenylcarbamate) β-CD.The inset showing the formation of intramolecular H-bonding between adjacent phenylcarbamate groups on neighbouring glucose units.
Mentions: The improvement in chiral recognition ability of phenylcarbamated CD clicked CSPs over CCN-CSP with the introduction of phenylcarbamoyl group on CD rims may be explained with FT-IR analysis. As shown in Fig. 6, all three phenylcarbamated β-CD derivatives exhibit two identical peaks at 3403 and 3319 cm−1 in FT-IR spectra, which was assigned to free NH for the former and hydrogen-bonded NH for the latter. The hydrogen-bonded NH is not only involved in intramolecular H-bonding between adjacent phenylcarbamate groups on neighbouring glucose units, leading to a more stable and regular higher order structure of CD CSPs, but also form H-bonding interaction with racemates. These both functions contribute to the improvement of the chiral recognition ability of perphenylcarbamated CD CSPs in comparision to native CD CSPs. For CCC3M4-CSP, the introdution of an electron-donating 4-methyl group and an electron-withdrawing 3-chloro substituent on phenyl ring will help to promote the configuration-dependent inclusion for maximum stability difference between two complexes.

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