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ChemComm
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COMMUNICATION
Journal Name
DOI: 10.1039/C9CC01436E
In order to gain insight of AT-selective binding nature, three
other different sequenced duplex DNA were examined. Fig.9
showed that both drew DNA11 and 8AT quenched the fluorescence
at 520 nm and enhanced the emission at 375 nm, to different
extents; however, the addition of 12GC only quenched the
fluorescence at 520 nm but barely changed the emission at 375nm.
The curve of F375/F520nm as a function of [DNA]/[2] ratio was then
plotted (Fig.9d). Basically, within one periodical length of A-tracts
DNA (10-12 base pairs)12, the more AT base pair DNA contained,
the more significant the slope of titration curve was, which
indicated that 2 was an AT-DNA selective ligand.
the few cases that supramolecular catalyzed hydrazone-formation
reaction. Moreover, 2 represents a novel geometry-switch induced
uncharged AT-DNA probe. In view of these two points, our findings
may shed light on the assessment of catalytic properties of more
supramolecular macrocycles and pave the way for the search of
geometry-switchable “neutral” DNA ratiometric sensors.
We thank Natural Science Foundation of Liaoning Province
(20180550874), Foundation of Higher Education of Guangdong
(2016KTSCX146), Natural Science Foundation of Guangdong
Province (2018A0303130245).
300
(a)
300
(b)
~ 375 nm
~ 520 nm
~ 375 nm
200
100
0
200
100
0
~ 520 nm
Conflicts of interest
There are no conflicts to declare.
360
450
Wavelength(nm)
540
360
450
Wavelength(nm)
540
12
(d)
(c)
200
~ 520 nm
Notes and references
10
8
12AT
12GC
DrewAT
8AT
1
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6
100
0
4
~ 375 nm
2
0
360
450
540
0
1
2
3
4
5
2
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6974.
Wavelength(nm)
[DNA]/[2]
Fig.9. Fluorescence of 2 (5 μM) upon addition of (a) 8AT; (b)drewAT;
(c)12GC;(DNA/2 ratio: 0.25, 0.50, 0.75,1.0, 1.50, 2.0, 2.5, 3.0, 4.0) (d)plotted
curve using F375/F520nm as a function of the ratio of [DNA]/[2].
3
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Fig.10 Partial HNMR spectra of 2 upon addition of 12AT (Line 1: 2 alone;
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Line 2: 2+0.25eq.DNA; Line 3: 2+0.5eqDNA; Line 4 2:+0.75eq.DNA; Line 5:
2+1.0eq.DNA)
1
In the end, HNMR spectra of 2 upon addition of AT-DNA were
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recorded to give a view of potential binding mode. The partial
spectra were listed in Fig.10 (please see full spectra in Fig. S20). Due
to the H/D exchange, unfortunately, we did not observe the
protons of both OH and NH of 2. What had been seen was that the
addition of DNA made Ha, Hb and Hc of 2 move slightly towards
upfield while the other protons of 2 barely changed. This result
indicated that 2-DNA binding probably took place in a way that the
edge of diphenylmethane unit was inserted into the minor groove
of AT-DNA due to the hydrophobic binding whereas the two
salicylaldehyde hydrazone units interacted with the un-paired
carbonyl group of thymine of AT-DNA due to hydrogen bonding.
In conclusion, a bishydrazone compound was synthesized under
physiological condition using calix[4]carbazole as a supramolecular
catalyst. This molecule adopted a folded geometry and exhibited an
intramolecular excimer emission. By engineering the switch from
the folded to the unfolded geometry, this molecule could serve as
an AT-DNA selective ratiometric sensor.
8
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The current work is not very satisfying and further work still
remains: the efficiency of supramolecular catalytic reaction needs
4 | J. Name., 2012, 00, 1-3
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