ChemComm
Communication
three azobenzenes with tiny differences. The introduction of
azobenzenes would destroy interactions between CDP molecules
and generated new non-covalent interactions between CDP and
azobenzenes. Tiny differences among azobenzenes which
inserted into CDP molecular arrangement caused different
molecular packing, which was the key factor for the formation
of these structures. Taking CPABS as an example, assembly of
CDP could also be regulated by changing the amount of CDP or
azobenzene with the other one fixed. We hope this approach
could help to fabricate novel peptide-based functional nano-
materials by co-assembly through adjusting molecular structures.
We acknowledge the financial support of this research from
the National Nature Science Foundation of China (No. 91027045
and 20121003) and the National Basic Research Program of
Fig. 5 SEM images of co-assembly at different ratios (CDP to CPABS): (A) 0.05;
(B) 0.10; (C) 0.26; (D) 0.41; (E) 0.52; (F) 0.70.
into the arrangement of CDP molecules with different degrees.19 China (973 program, 2009CB930101).
Moreover, the relative intensity of the peaks (Ri) is also changed.
Notes and references
For the CDP powder in Fig. 4A, the Ri value is about 1.16. After co-
assembly with MO, although the peaks both shifted to smaller
angle, the ratio of their intensity is 1.12 which almost remains the
same with the CDP powder. When HPABS was used, the intensity
of the second peak decreases rapidly and the Ri value rises to 10.2.
Nevertheless, when CPABS was used, the second peak disappeared,
thus the Ri value rises up to infinity. It reveals that when the three
kinds of azobenzene molecules with tiny differences inserted into
the CDP molecular arrangement, they showed different co-assembly
behaviors, which could induce different nanostructures.
1 (a) A. Ajayaghosh and V. K. Praveen, Acc. Chem. Res., 2007, 40, 644;
(b) X. Zhang and C. Wang, Chem. Soc. Rev., 2011, 40, 94.
2 C. Brieke, F. Rohrbach, A. Gottschalk, G. Mayer and A. Heckel,
Angew. Chem., Int. Ed., 2012, 51, 8446.
3 Y. Gao, Y. Kuang, Z. F. Guo, Z. H. Guo, I. J. Krauss and B. Xu,
J. Am. Chem. Soc., 2009, 131, 13576.
4 M. T. Fenske, W. Meyer-Zaika, H.-G. Korth, H. Vieker, A. Turchanin
and C. Schmuck, J. Am. Chem. Soc., 2013, 135, 8342.
5 N. Ma, Y. Li, H. Xu, Z. Wang and X. Zhang, J. Am. Chem. Soc., 2009,
132, 442.
6 C. Wang, Y. Guo, Y. Wang, H. Xu, R. Wang and X. Zhang, Angew.
Chem., Int. Ed., 2009, 48, 8962.
We could also regulate the assembly process by increasing the
amount of one of the building blocks while keeping another one
fixed. For example, we added CPABS to a dispersed solution of CDP
nanotubes and observed morphology changes from nanotubes to
network structures and finally urchin-like microspheres (Fig. S2,
ESI†). The whole morphology change process proves that the
addition of CPABS would destroy the intrinsic interactions of
CDP in nanotubes and generate new interactions between CDP
and CPABS to form CDP-CPABS co-assembly. Then we fixed the
amount of CPABS and increased the ratio of CDP and CPABS
gradually. Morphology changes from one-dimensional (1D) to
three-dimensional (3D) ordered structures were observed when
the molar ratio (CDP to CPABS) was increased from 0.05 to 0.70
(Fig. 5). Enlarged SEM images in Fig. 5A and E indicate that the
initial formed microrods and those microrods on the surface of
urchin-like microspheres both possess polygonal shape. This result
not only reveals extremely ordered molecular arrangement in these
structures, but also sheds light on the morphology evolution from
7 (a) P. Yin, H. M. T. Choi, C. R. Calvert and N. A. Pierce, Nature, 2008,
451, 318; (b) T. Scheibel, R. Parthasarathy, G. Sawicki, X. M. Lin, H. Jaeger
and S. L. Lindquist, Proc. Natl. Acad. Sci. U. S. A., 2003, 100, 4527; (c) J. Ge,
J. D. Lei and R. N. Zare, Nat. Nanotechnol., 2012, 7, 428.
8 (a) T. Y. Cheng, M. H. Chen, W. H. Chang, M. Y. Huang and
T. W. Wang, Biomaterials, 2013, 34, 2005; (b) E. C. Wu,
S. G. Zhang and C. A. E. Hauser, Adv. Funct. Mater., 2012, 22, 456.
9 (a) H. Hosseinkhani, P.-D. Hong and D.-S. Yu, Chem. Rev., 2013,
113, 4837; (b) H. M. Wang and Z. M. Yang, Nanoscale, 2012, 4, 5259.
10 (a) F. Boato, R. M. Thomas, A. Ghasparian, A. Freund-Renard,
K. Moehle and J. A. Robinson, Angew. Chem., Int. Ed., 2007,
46, 9015; (b) J. S. Rudra, Y. F. Tian, J. P. Jung and J. H. Collier, Proc.
Natl. Acad. Sci. U. S. A., 2010, 107, 622.
11 (a) M. Reches and E. Gazit, Science, 2003, 300, 625; (b) M. Reches and
E. Gazit, Nano Lett., 2004, 4, 581; (c) Z. M. Yang, P. L. Ho, G. L. Liang,
K. H. Chow, Q. G. Wang, Y. Cao, Z. H. Guo and B. Xu, J. Am. Chem.
Soc., 2007, 129, 266; (d) A. R. Hirst, S. Roy, M. Arora, A. K. Das,
N. Hodson, P. Murray, S. Marshall, N. Javid, J. Sefcik, J. Boekhoven,
J. H. van Esch, S. Santabarbara, N. T. Hunt and R. V. Ulijn, Nat.
Chem., 2010, 2, 1089; (e) Y. Su, X. H. Yan, A. H. Wang, J. B. Fei,
Y. Cui, Q. He and J. B. Li, J. Mater. Chem., 2010, 20, 6734;
( f ) P. L. Zhu, X. H. Yan, Y. Su, Y. Yang and J. B. Li, Chem.–Eur. J.,
2010, 16, 3176; (g) X. H. Yan, Y. Su, J. B. Li, J. Fruh and H. Mohwald,
Angew. Chem., Int. Ed., 2011, 50, 11186.
1D to 3D structures. Furthermore, in the case of CPABS, confocal 12 (a) X. H. Yan, P. L. Zhu and J. B. Li, Chem. Soc. Rev., 2010, 39, 1877;
(b) Y. Gao, F. Zhao, Q. G. Wang, Y. Zhang and B. Xu, Chem. Soc. Rev.,
2010, 39, 3425; (c) M. Reches and E. Gazit, Nat. Nanotechnol., 2006, 1, 195.
13 S. Yuran, Y. Razvag and M. Reches, ACS Nano, 2012, 6, 9559.
laser scanning microscopy (CLSM) and photoluminescence (PL)
were employed to investigate optical properties. Red emission was
observed when the urchin-like microspheres were irradiated by 14 X. H. Yan, Q. He, K. W. Wang, L. Duan, Y. Cui and J. B. Li, Angew.
Chem., Int. Ed., 2007, 46, 2431.
15 X. H. Yan, P. L. Zhu, J. B. Fei and J. B. Li, Adv. Mater., 2010, 22, 1283.
16 (a) C. I. Stains, K. Mondal and I. Ghosh, ChemMedChem, 2007,
laser light. The fluorescence spectrum of the microspheres with the
peak located at 590 nm is shown in Fig. S3 (ESI†). However,
fluorescence spectra of pure CPABS molecules did not show any
peak at the same region, neither did CDP.15 The new optical
characteristics of co-assembly indicates that there may exist p–p
interaction between CDP and CPABS molecules in the assembly
structures, which is in accordance with the FTIR result (Fig. 3A).
In conclusion, the assembly of CDP could be manipulated
2, 1674; (b) C. X. Wang, A. H. Yang, X. Li, D. H. Li, M. Zhang,
H. W. Du, C. Li, Y. Y. Guo, X. B. Mao, M. D. Dong, F. Besenbacher,
Y. L. Yang and C. Wang, Nanoscale, 2012, 4, 1895.
17 (a) J. T. Feng, W. Yan and L. Z. Zhang, Microchim. Acta, 2009,
166, 261; (b) M. Vlassa, G. Borodi, A. Biris, G. Blanita, M. Vlassa
and C. Silvestru, Rev. Roum. Chim., 2011, 56, 857.
18 M. T. Gulluoglu, Y. Erdogdu, J. Karpagam, N. Sundaraganesan and
S. Yurdakul, J. Mol. Struct., 2011, 990, 14.
into urchin-like, flower-like and plate-like nanostructures by 19 A. Nisar, J. Zhuang and X. Wang, Adv. Mater., 2011, 23, 1130.
c
9958 Chem. Commun., 2013, 49, 9956--9958
This journal is The Royal Society of Chemistry 2013