Table 1 The energy of the self-assembled nanofiber and nanosphere
Notes and references
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Relative energy/
kcal molÀ1
1aÁ2H+(open ring)
1bÁ2H+ (closed ring)
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Nanosphere
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composed predominantly of the nanofiber conformation,
while the closed-ring isomer prefers the nanosphere structure.
It was reported that histamine possesses two pKa values
(pKa1 = 5.8, pKa2 = 9.4).18 Therefore, when the pH value is
larger than pKa, the protonated histamines located on two
sides lost the protons. Concomitantly, the dipole moment of
the diarylethene decreases significantly, as is reflected in
Table 1. Therefore, the intermolecular combination strength
weakens under high pH conditions when the assembly occurs.
In other words, the degree of polymerization or aggregation
under the acidic conditions is larger than that in the basic
environment. Thus, it is reasonable that the radii of the self-
assembly nanosphere of the closed-ring isomer is larger under
low pH conditions.
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In summary, we have synthesized an amphiphilic diarylethene
derivative with histamines as side chains and investigated its
photochromic properties and light triggered self-assembling
behavior. The molecule can self-assemble into a nanostructure
at an enhanced pH value. For the open-ring isomer, a nanofiber
was obtained at a pH value larger than 6.4. After UV irradiation,
the morphology was changed from nanofiber into nanosphere.
A possible formation mechanism was presented based on theo-
retical calculations. This responsive architecture is of high
potential for smart soft material and devices.
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This work was supported by the National Natural Science
Foundation (Grant No. 20802039 and 20971077) and the Chinese
Academy of Sciences, National Program on Key Basic Research
Project of China (973 Program) (No. MOST2011CB935700).
c
6878 Chem. Commun., 2011, 47, 6876–6878
This journal is The Royal Society of Chemistry 2011