Evaluation Only. Created with Aspose.PDF. Copyright 2002-2021 Aspose Pty Ltd.
Page 3 of 3
ChemComm
DOI: 10.1039/C3CC45752D
inside the illuminated quadrangle area (Fig. 3b, bottom row),
which can be attributed to the photogenerated, weakly fluorescent
nitrile imine intermediates.7a To verify that the fluorescence is
derived from microtubuleꢀbound pyrazoline, inꢀcell fluorescence
spectrumꢀscan was performed, revealing a maximum cytosolic
emission at 548 nm (Fig. S13). Separately, we also measured the
fluoresnce spectrum of the preformed pyrazoline and founf that it
shows solventꢀdependent fluorescence: it is nonꢀfluorescent in
PBS/acetonitrile (4:1), but strongly fluorescent in organic
10 solvents along with a hypsochromic shift in emission maxima
from 585 nm to 560 nm (Fig. S14). The blueꢀshifted inꢀcell
fluorescence matches closely to that observed in organic solvents,
suggesting that the generally formed pyrazolineꢀdocetaxel likely
graduate student from Lanzhou University sponsored by China
Scholarship Council.
Notes and references
5
a Department of Chemistry, State University of New York at Buffalo,
50 Buffalo, NY 14260 (USA); E-mail: qinglin@buffalo.edu
† Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/b000000x/
‡ Footnotes should appear here. These might include comments relevant
55 to but not central to the matter under discussion, limited experimental and
spectral data, and crystallographic data.
1
a) S. Kawata, Y. Kawata, Chem. Rev., 2000, 100, 1777; b) J. Delaire,
K. Nakatani, Chem. Rev., 2000, 100, 1817.
binds to the microtubule surface with a low dielectric constant.
a)
2
a) N. Ruangsupipachat, M. Pollard, S. Harutyunran, B. Feringa, Nat.
Chem., 2011, 3, 53; b) J. Wang, B. Feringa, Science, 2011, 331,
1429.
60
65
70
75
80
85
90
3
4
P. Gorostiza, E. Y. Isacoff, Science, 2008, 322, 395.
M. A. Tasdelen, Y. Yagci, Angew. Chem. Int. Ed., 2013, 52, 23 and
references therein.
5
6
A. Sesto, M. Navarro, F. Burslem, J. L. Jorcano, Proc. Natl. Acad.
Sci. USA, 2002, 99, 2965.
a) W. Song, Y. Wang, J. Qu, M. M. Madden, Q. Lin, Angew. Chem.
Int. Ed., 2008, 47, 2832; b) W. Song, Y. Wang, J. Qu, Q. Lin, J. Am.
Chem. Soc., 2008, 130, 9654; c) R. K. Lim, Q. Lin, Acc. Chem. Res,.
2011, 44, 828.
DIC
Fluorescence
Fluorescence
Overlay
b)
+ IPFA-Doc
7
8
9
a) W. Song, Y. Wang, Z. Yu, C. I. Vera, J. Qu, Q. Lin, ACS Chem.
Biol., 2010, 5, 875; b) Z. Yu, Y. Pan, Z. Wang, J. Wang, Q. Lin,
Angew. Chem. Int. Ed., 2012, 51, 10600.
a) S. L. Zheng, Y. Wang, Z. Yu, Q. Lin, P. Coppens, J. Am. Chem.
Soc., 2009, 131, 18036; b) D. Bégué, G. G. Qiao, C. Wentrup, J. Am.
Chem. Soc., 2012, 134, 5339.
a) Y. Wang, W. Hu, W. Song, R. K. V. Lim, Q. Lin, Org. Lett., 2008,
10, 3725; b) Z. Yu, L. Y. Ho, Z. Wang, Q. Lin, Bioorg. Med. Chem.
Lett., 2011, 21, 5033; c) Z. Yu, L. Y. Ho, Q. Lin, J. Am. Chem. Soc.,
2011, 133, 11912.
0 s
48 s
48 s
− IPFA-Doc
0 s
48 s
48 s
15
Fig. 3 Spatiotemporally controlled imaging of microtubules via laserꢀ
triggered docetaxelꢀdirected photoclick chemistry with terthiopheneꢀ
tetrazole 6. (a) Reaction scheme. (b) Confocal micrographs of CHO cells
treated with 40 ꢂM tetrazole 6 in the presence of (top row) or absence
20 (bottom row) of 30 ꢂM IPFAꢀdocetaxel. The cells in the quadrangle areas
were exposed to 405 nm laser irradiation (0.15 mW) at 1.27 ꢂs/pixel
illumination dwell followed by scanning entire viewing areas with 458
nm laser at 6.30 ꢂs/pixel illumination dwell; the scanning sequence was
intermittently repeated for a duration of 125 sec. Scale bar = 50 ꢂm.
10 G. M. Halliday, S. N. Byrne, D. L. Damian, Semin. Cutan. Med.
Surg., 2011, 30, 214.
11 a) R. S. Becker, J. S. Melo, A. L. Macanita, F. Elisei, J. Phys. Chem.,
1996, 100, 18683; b) A. Adronov, P. R. L. Malenfant, J. M. Fréchet,
J. Chem. Mater., 2000, 12, 1463.
12 a) J. Gierschner, J. Cornil, H. –J. Egelhaaf, Adv. Mater., 2007, 19,
173; b) D. Fichou, J. Chem. Mater., 2000, 10, 571.
13 A. Mishra, C.–Q. Ma, P. Bäuerle, Chem. Rev., 2009, 109, 1141.
14 J. Garfunkle, C. Ezzili, T. J. Rayl, D. J. Hochstatter, I. Hwang, D. L.
Boger, J. Med. Chem., 2008, 51, 4392.
25
In summary, we have synthesized a panel of oligothiopheneꢀ
based tetrazoles and found that a terthiopheneꢀtetrazole gave
excellent photoreactivity under 405 nm laser irradiation with ring
rupture quantum yield of 0.16. A waterꢀsoluble terthiopheneꢀ
tetrazole was then prepared that showed a faster reaction kinetics
15 a) L. Antolini, G. Horowitz, F. Kouki, F. Garnier, Adv. Mater., 1998,
10, 382; b) T. Siegrist, C. Kloc, R. A. Laudise, H. E. Katz, R. C.
Haddon, Adv. Mater., 1998, 10, 379; c) R. Azumi, M. Goto, K.
Honda, M. Matsumoto, Bull. Chem. Soc. Jpn., 2003, 76, 1561.
95 16 Light intensity value was recorded by placing a FieldMaster GS
energy analyzer equipped with LMꢀ10 HTD power meter sensor in
the light path of the laser beam.
17 The quantum yield for ring rupture of tetrazole 6 was determined to be
0.15; see Fig. S5 in ESI for details.
100 18 a) K. C. Nicolaou, W. M. Dai, R. K. Guy, Angew. Chem., Int. Ed.,
1994, 33, 15; b) A. Desai, T. J. Mitchison, Annu. Rev. Cell Dev. Biol.,
1997, 13, 83.
30 with with a fumarate dipolarophile (k2 = 1299 ± 110 M−1 s−1) and
capability for realꢀtime spatiotemporally controlled imaging of
microtubules via laserꢀtriggered photoclick chemistry in live
mammalian cells. Given that 405 nm laser is widely available on
fluorescent microscope for exciting tcommon fluorophores, we
35 expect that this class of 405 nm laserꢀactivatable thiopheneꢀ
tetrazoles should facilitate a wider adoption of photoclick
chemistry in cell biologcal studies.
19 Z. Yu, T. Y. Ohulchanskyy, P. An, P. N. Prasad, Q. Lin, manuscrpt
submitted.
This research was financially supported by the National
Institutes of Health (GM 085092). We thank William Brennessel
40 at the University of Rochester for solving Xꢀray structures of
tetrazoles 2 and 4 (Cambridge Structural Database accession no.
CCDC 931877 and 931876), and Alan Siegel at SUNY Buffalo
Biological Sciences Imaging Facility (supported by the National
Science Foundation Major Research Instrumentation grant DBIꢀ
45 0923133) for assistance with microscopy. P.A. is a visiting
105 20 a) Y. W. Yang, J. S. Lee, I. Kim, Y. J. Jung, Y. M. Kim, Eur. J.
Pharm. Biopharm., 2007, 66, 260; b) In our in vitro analysis, IPFA
was stable in the presence of 10 mM glutathione in deuterated
DMSO/PBS buffer (7:3); see Fig. S10 in ESI for details.
21 a) R. Matesanz, J. RodríguezꢀSalarichs, B. Pera, A. Canales, J. M.
110
Andreu, J. JiménezꢀBarbero, W. Bras, A. Nogales, W. –S. Fang, J. F.
Díaz, Biophy. J., 2011, 101, 2970; b) M. L. Miller, E. E. Roller, R. Y.
Zhao, B. A. Leece, O. Ab, E. Baloglu, V. S. Goldmacher, V. J. Chari,
J. Med. Chem., 2004, 47, 4802.
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 3