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ChemComm
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COMMUNICATION
similar procedure was used to prepare poly(L-DOPA) thin film on same concentration of 0.5 mM, and the pure ethanol was used for
glass (Figure S5 and S6). Both of L-DOPA and poly(L-DOPA) have
positive CD signal (Figure 3) demonstrating the chiral L-DOPA and
poly(L-DOPA). However, the CD peak of poly(L-DOPA) thin film is at
DOI: 10.1039/C6CC08342K
the baseline. Under the same measurement condition, the mass
2
uptakes of poly(L-DOPA) thin film were ~2.32 µg/cm for S-
2
naproxen and ~1.57 µg/cm for R-naproxen, respectively (Figure 4).
3
60 nm, which is different from that of L-DOPA (294 nm). This may
The CD spectra (Figure S8) for pol(L-DOPA) thin film after loading R-
naproxen and S-naproxen also showed pol(L-DOPA) can adsorption
the drug molecules. The enantioslective adsorption ability can be
calculated by the equation of e = (m -m )/m × 100%, where e
be due to the chromophore groups around the chiral centre was
changed when there is a self-polymerization process from L-DOPA
molecules to poly(L-DOPA).
S
R
S
3
2
2
1
1
0
5
0
5
0
5
0
5
denotes the enantioselectivity, mS and mR is the uptake of S-
naproxen and R-naproxen enantiomers, respectively. Thus, the
eantioselectivity of naproxen in this poly(L-DOPA) thin film was
calculated to be ~32%. In contract, the substrate and L-DOPA
loaded HKUST-1 with tiny porosity (Figure S9) could not provide the
space for adsorption of naproxen. In addition, the subequal uptake
of R-/S-naproxen in the pristine HKUST-1 thin film (Figure S10)
showed there was scarcely enantioselectivity.
In summary, we have successfully developed a new method
toward the synthesis of homochiral polymer thin film by using
SURMOF template. The resulting homochiral poly(L-DOPA) thin film
can effectively separate R-/S-naproxen with enantioselecitivity of
-
-
-
-
10
L-DOPA
porous poly(L-DOPA) thin film
15
20
2
00
300
400
500
600
3
2%. This work leads a SURMOF-templated approach for preparing
wavelength / nm
porous homochiral polymer thin film.
Figure 3. CD of powder L-DOPA and resulted porous poly(L-DOPA)
thin film.
As a chiral and water stable porous polymer, porous poly(L-DOPA) Acknowledgements
thin film provides a good candidate for the drug recognition and
This work is supported by NSFC (21425102, 21601189 and
1521061) and NSF of Fujian Province (2016J01085).
separation. In order to investigate of the enatioselective adsorption
of porous poly(L-DOPA) thin film, a pair of drug molecule R-/S-
naproxen was chosen and the enantiomers was demonstrated by
2
CD signal in Figure S7. The pharmacological activity resides in S-
naproxen, while R-naproxen can cause some undesired side effects.
Therefore, it is beneficial to distinguish and separate R-/S-naproxen
in the modern pharmaceutical industry.
Notes and references
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Figure 4. The uptake of R-naproxen and S-naproxen adsorption in
chiral poly(L-DOPA) thin film.
2
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9
In order to demonstrate the porosity of obtained thin film, the
ethanol adsorptions of pristine HKUST-1, poly(L-DOPA)@HKUST-1
and poly(L-DOPA) thin film were carried out by QCM (Figure S8).
The decreased uptake (from 5.6 μgcm
demonstrated that the L-DOPA was loaded in the pores. After
removing the MOF framework, the uptake increased to 3.7 μgcm ,
which showed there was a porous poly(L-DOPA) thin film.
A quartz crystal microbalance (QCM) is applied for investigating
the enantioselective adsorption in homochiral thin films.
both R- and S-naproxen was diluted into ethanol for preparing the
,
9
-2
-2
10. S. M. Xie, Z. J. Zhang, Z. Y. Wang and L. M. Yuan, J. Am. Chem.
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to 0.6 μgcm )
-2
1
Here
1
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,
1
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