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We did not synthesize tri- or tetramethylated azobenzenes because of the following reasons: Synthesis of tri- or tetraalkylated azobenzenes at ortho positions is rather difficult due to the steric hindrance between the methyl groups on both sides of the benzene rings note
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We did not synthesize tri- or tetramethylated azobenzenes because of the following reasons: Synthesis of tri- or tetraalkylated azobenzenes at ortho positions is rather difficult due to the steric hindrance between the methyl groups on both sides of the benzene rings (C. J. Byrne, D. A. R. Happer, M. P. Hartshorn, H. K. J. Powell, J. Chem. Soc, Perkin Trans. 1 1987, 1649-1653). According to the literature (ref. [9b]), tri- or tetraalkylation at the ortho positions makes the trans-to-cis photoisomerization slower, and accordingly the cis content after UV light irradiation becomes much less, which is unfavorable for the efficient photoregulation. In addition, we think that fur- ther methylation might not improve the photoregulatory efficiency based on our present finding; modification of the distal benzene ring, but not the proximal one was effective for the significant improvement of photoregulatory efficiency.
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m curves were depicted in Figure S1 in the Supporting Information
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m curves were depicted in Figure S1 in the Supporting Information.
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Our group previously also investigated the sequence dependency of non-modified Azo to obtain the nearest-neighbor parameter note
-
m on the adjacent base pair as that of 2′,6′-Me-Azo in both the trans and cis forms. In addition, although the length of the present sequence involving 2′,6′-MeAzo was four bases longer than that of Azo, which our group previously used, the ΔTm of 2′,6′-Me-Azo was higher than that of Azo in all the sequences, demonstrating the superiority of 2′,6′-Me-Azo (see the Supporting Information, Figure S2 and Table Sl).
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9). Other terminal imino proton signals might be overlapped with the signal at δ = 12.8 ppm
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9). Other terminal imino proton signals might be overlapped with the signal at δ = 12.8 ppm.
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34
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76449119160
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As described above, the DNA duplex that contain cis-2′,6′-Me- Azo was much more unstable than that of trans form.
-
As described above, the DNA duplex that contain cis-2′,6′-Me- Azo was much more unstable than that of trans form.
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35
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31444454427
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76449110165
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Typical UV/Vis spectra of the thermal cis-to-trans isomerization are depicted in Figure S3 in the Supporting Information.
-
Typical UV/Vis spectra of the thermal cis-to-trans isomerization are depicted in Figure S3 in the Supporting Information.
-
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76449116667
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a of benzoic acid. But neither 2′,6′-Me-Azo nor 2,6-Me-Azo would dissolve at all under stronger acidic conditions.
-
a of benzoic acid. But neither 2′,6′-Me-Azo nor 2,6-Me-Azo would dissolve at all under stronger acidic conditions.
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