Enantioselective recognition mechanism of ofloxacin via Cu(II)-modulated DNA.
The specific interactions of Cu(2+) with self-complementary DNA sequences involving d[G4C4(GC)2G4C4], d[(GC)10], and d[(AT)10], as well as the chiral recognition mechanism of ofloxacin enantiomers via the Cu(II)-modulated DNAs, were investigated using characterizations of circular dichroism, gel electrophoresis, FT-IR spectroscopy, UV melting measurement, electron paramagnetic resonance, and HPLC. The Cu(II)-coordinated GC-rich DNAs exhibit amplified enantioselectivity toward the S-enantiomer of ofloxacin. Especially in the case of d[G4C4(GC)2G4C4], ofloxacin enantiomers intercalate into the two adjacent guanine bases through the minor groove mediated by Cu(2+), which leads to a more favorable binding between S-ofloxacin and DNA. The highest ee value of ofloxacin enantiomers in the permeate after being adsorbed by the Cu(II)-DNA complex is obtained as 49.2% in the R-enantiomer at the [Cu(2+)]/[base] molar ratio of 0.25, while at the [Cu(2+)]/[base] molar ratio of 0.05 the highest ee value of ofloxacin enantiomers in the retentate reaches 26.3% in the S-enantiomer. This work illustrates a novel promising route to construct DNA-based chiral selectors toward certain drug enantiomers through the programmable enantioselective recognition on the basis of DNA chirality and the specific binding of transition metal ions.
Key Laboratory for Green Chemical Technology MOE and ‡Key Laboratory of Systems Bioengineering MOE, School of Chemical Engineering and Technology, Tianjin University, Collaborative Innovation Center of Chemical Science and Chemical Engineering (Tianjin) , Tianjin 300072, People's Republic of China.
Wei
W
Li
Xiongfei
X
Chen
Yan
Y
Fu
Jinli
J
Zhang
Wei
W
Li
D000327:Adsorption; D001483:Base Sequence; D001665:Binding Sites; D002942:Circular Dichroism; D003300:Copper / Q000737:chemistry*; D004247:DNA / Q000737:chemistry* / Q000378:metabolism; D004578:Electron Spin Resonance Spectroscopy; D056004:Molecular Dynamics Simulation; D009690:Nucleic Acid Conformation; D015242:Ofloxacin / Q000737:chemistry* / Q000378:metabolism; D009841:Oligonucleotides / Q000737:chemistry / Q000378:metabolism; D017550:Spectroscopy, Fourier Transform Infrared; D013237:Stereoisomerism
D009841:Oligonucleotides; D003300:Copper; D004247:DNA; D015242:Ofloxacin