title: DNA Duplex Engineering for Enantioselective Fluorescent Sensor.
abstract: The rapid identification of biomacromolecule structure that has a specific association with chiral enantiomers especially from natural sources will be helpful in developing enantioselective sensor and in speeding up drug exploitation. Herein, owing to its existence also in living cells, apurinic/apyrimidinic site (AP site) was first engineered into ds-DNA duplex to explore its competence in enantiomer selectivity. An AP site-specific fluorophore was utilized as an enantioselective discrimination probe to develop a straightforward chiral sensor using natural tetrahydropalmatine (L- and D-THP) as enantiomer representatives. We found that only L-THP can efficiently replace the prebound fluorophore to cause a significant fluorescence increase due to its specific binding with the AP site (two orders magnitude higher in affinity than binding with D-THP). The AP site binding specificity of L-THP over D-THP was assessed via intrinsic fluorescence, isothermal titration calorimetry, and DNA stability. The enantioselective performance can be easily tuned by the sequences near the AP site and the number of AP sites. A single AP site provides a perfect binding pocket to differentiate the chiral atom-induced structure discrepancy. We expect that our work will inspire interest in engineering local structures into a ds-DNA duplex for developing novel enantioselective sensors.
authors.affiliation: Institute of Physical Chemistry, Zhejiang Normal University , Jinhua 321004, Zhejiang, China.
authors.forename: Yuehua
authors.initials: Y
authors.lastname: Hu
authors.affiliation: Institute of Physical Chemistry, Zhejiang Normal University , Jinhua 321004, Zhejiang, China.
authors.forename: Fan
authors.initials: F
authors.lastname: Lin
authors.affiliation: Institute of Physical Chemistry, Zhejiang Normal University , Jinhua 321004, Zhejiang, China.
authors.forename: Tao
authors.initials: T
authors.lastname: Wu
authors.affiliation: Institute of Physical Chemistry, Zhejiang Normal University , Jinhua 321004, Zhejiang, China.
authors.forename: Yufeng
authors.initials: Y
authors.lastname: Zhou
authors.affiliation: Institute of Physical Chemistry, Zhejiang Normal University , Jinhua 321004, Zhejiang, China.
authors.forename: Qiusha
authors.initials: Q
authors.lastname: Li
authors.affiliation: Institute of Physical Chemistry, Zhejiang Normal University , Jinhua 321004, Zhejiang, China.
authors.forename: Yong
authors.identifier: 0000-0003-0834-6244
authors.initials: Y
authors.lastname: Shao
authors.affiliation: School of Chemistry and Molecular Engineering, East China Normal University , Shanghai 200241, China.
authors.forename: Zhiai
authors.identifier: 0000-0002-4391-2507
authors.initials: Z
authors.lastname: Xu
mesh_terms: D001600:Berberine Alkaloids / Q000737:chemistry*; D004247:DNA / Q000737:chemistry*; D005456:Fluorescent Dyes / Q000737:chemistry*; D013050:Spectrometry, Fluorescence; D013237:Stereoisomerism; D044366:Transition Temperature
chemical_list: D001600:Berberine Alkaloids; D005456:Fluorescent Dyes; C014215:tetrahydropalmatine; D004247:DNA