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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

The representative enantioseparation chromatograms of selected analytes.
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f4: The representative enantioseparation chromatograms of selected analytes.

Mentions: The peak resolutions of flavanone and methoxyflavanone with CCC3M4-CSP reached over 10. And the Rs values of all flavanoids with CCC3M4-CSP are about 4 ~ 5 times higher than those obtained with ealierly reported native and unfuctionalized perphenylcarbamated CD clicked CSPs18202112. And the Rs values are much higher than those in literature obtained with amylose tris(5-chloro-2-methylphenylcarbamate32, Chiralcel OD-H and Chiralpak AS-H CSPs33. Importantly, when we compare the enantioseparation results for flavanone, methoxyflavanones and hydroxylflavanones, one can find that the increased hydrophobicity with methoxy group resulted in higher resolution, while the increased hydrophility (with hydroxyl group) deteriorated the resolution. Similar behaviour was also found for hesperetin and naringenin, which presented lower chiral resolutions with the presence of hydroxy groups. The versatile enantioseparation of flavanoids with CCC3M4-CSP was evaluated at different mobile phases. The enantioseparations of flavanone with 1.0 mL/min acetonitrile/water (80/20) still achieved a Rs of 3.0, though it was rather lower than that with MeOH/H2O (80/20) (Rs = 11.2). The use of acetonitrile however led to shorter retention time than MeOH, due to the lower polarity of acetonitrile. The good resolution ability towards flavanoids can be explained with their interactions including inclusion complexation, dipole-dipole and hydrophobic interaction. The representative chromatograms for nine selected racemates are present in Fig. 4.


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)

The representative enantioseparation chromatograms of selected analytes.
© Copyright Policy - open-access
Related In: Results  -  Collection

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

f4: The representative enantioseparation chromatograms of selected analytes.
Mentions: The peak resolutions of flavanone and methoxyflavanone with CCC3M4-CSP reached over 10. And the Rs values of all flavanoids with CCC3M4-CSP are about 4 ~ 5 times higher than those obtained with ealierly reported native and unfuctionalized perphenylcarbamated CD clicked CSPs18202112. And the Rs values are much higher than those in literature obtained with amylose tris(5-chloro-2-methylphenylcarbamate32, Chiralcel OD-H and Chiralpak AS-H CSPs33. Importantly, when we compare the enantioseparation results for flavanone, methoxyflavanones and hydroxylflavanones, one can find that the increased hydrophobicity with methoxy group resulted in higher resolution, while the increased hydrophility (with hydroxyl group) deteriorated the resolution. Similar behaviour was also found for hesperetin and naringenin, which presented lower chiral resolutions with the presence of hydroxy groups. The versatile enantioseparation of flavanoids with CCC3M4-CSP was evaluated at different mobile phases. The enantioseparations of flavanone with 1.0 mL/min acetonitrile/water (80/20) still achieved a Rs of 3.0, though it was rather lower than that with MeOH/H2O (80/20) (Rs = 11.2). The use of acetonitrile however led to shorter retention time than MeOH, due to the lower polarity of acetonitrile. The good resolution ability towards flavanoids can be explained with their interactions including inclusion complexation, dipole-dipole and hydrophobic interaction. The representative chromatograms for nine selected racemates are present in Fig. 4.

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