Академический Документы
Профессиональный Документы
Культура Документы
1 Introduction
2 Supramolecular Gels
3 Supramolecular Liquid Crystals
4 Supramolecular Polymers
5 Vesicles
6 Nanotubes, -Pores, -Ribbons, -Rods, and -Spheres
7 Supramolecular Chirality
8 Conclusion
References
1
2
5
6
7
8
11
12
13
INTRODUCTION
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc044
Techniques
SUPRAMOLECULAR GELS
OH
1
10 m
(a)
200 m
(d)
2 m
(b)
20 m
(e)
20 m
(c)
10 m
(f)
Figure 1 SEM images of fractured xerogels of 1 in cyclohexane: (a) random repartition of very long and rigid fibers;
(b) detail showing the presence of thinner and more flexible
fibrils; (c) collapsed network of the phase-separated solid of
1/heptane gel, showing fibers emanating from a central point;
(d) thick bundles of fibers; (e and f) high orientation degree of
fibers. (Reproduced from Ref. 8. American Chemical Society,
1998.)
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc044
Et
O
Et
N
N
N
O
17
Et
O
Et
0.5 m
(a)
5 m
(c)
OCH3
17
CH3O
O
Et
O
Et
200 nm
(b)
2 m
(d)
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc044
Techniques
O
S
N
H
N
H
100nm
1 m
NONE
SEI
(a)
NONE
(b)
Figure 3 SEM image of (a) the cyclohexane gel of 3 and (b) that of the charge-transfer complex of 3 with TCNQ. The inset clearly
shows the tube-like superfine structures of the complex gel. (Reproduced from Ref. 10. American Chemical Society, 2005.)
O
O
OH HO
O
O
O
O
4
(c)
1 m
(a)
Intensity (a.u.)
3.01 nm
3.01 nm
(d)
1.49 nm
2
(b)
Cu-KR (2q /)
8
(e)
Figure 4 (a) SEM image and (b) SAXD pattern of xerogel 4 obtained from cyclohexane. (c) Molecular structure of 4. (d) Unimolecular
stacking with a length of 3.01 nm in the gel. (e) Proposed molecular packing model along the growing direction of the gel fiber.
(Reproduced from Ref. 11. American Chemical Society, 2009.)
xerogels revealed that both samples formed fibrous structures (Figure 5) and the addition of the second component dramatically changed the nanoscale morphology of
the assembled superstructure. On the basis of the observations, they proposed that the formation of the complex made
the network more interpenetrate and the nanoscale fibers
narrower because of the presence of more connecting
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc044
O
N
H
C11H23
N
H
O
C11H23
N
5 H
OH NH(CH2)12NH2
HO
(a)
C11H23
O
C11H23
N
H 5
(b)
3
H O
N
8
100 m
(a)
a'
8
N
OH
100 m
Crystal
Fiber
50 m
(b)
(c)
50 m
b'
100 m
c'
SUPRAMOLECULAR LIQUID
CRYSTALS
OH
O
O
O
O
H
100 m
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc044
Techniques
O
HN
NR2
NH
RO
H
N
(CH2)n
H
N
N N N
N N
H
H
9
10a: n = 5 10b: n = 7 NR2
R2N
R = n -C12H25
n N
R2N N N
N NR2
H
H
O
N N
N N
H
H
N N
N
N
H
H
O
O
RO
OR
9
10
(i) Hamilton-type complexes
NR2
OR
Ar
N NR2
N
H
H
9
O
N
N
N
N
O
O
H
H
N
N
H
H
N
N
N
N
H
N
H
10
HN
H
O
10
O
N N
N N
O
H
H
R2N N N
N N NR2
9
R2N
Ar
Ar
8
R2N
R2N
Ar
N
100 m
100 mm
(a)
(b)
A
P
(c)
100 m
(d)
5 m
(e)
4
P
100 m
1 m
(f)
SUPRAMOLECULAR POLYMERS
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc044
O
11a: X =
O
11b: X =
N
H
N
H
O
11c: X =
N
H
OC12H25
O
OC12H25
11d: X =
O
OC12H25
OC12H25
OC12H25
7 kV
(a)
15 kV
6,000 2 m
10 kV
5,000
2670 RRLSEM
(b)
10 kV
5,000
5 m 2680 RRLSEM
(c)
5 m 2683 RRLSEM
(d)
Figure 8 Scanning electron micrograph (SEM) images of self-assembled (a) 11a, (b) 11b, (c) 11c, and (d) 11d drop-cast from toluene.
(Reproduced from Ref. 17. American Chemical Society, 2008.)
5 VESICLES
The formation of vesicles in solution can be characterized
by DLS. To get more insight into their structures and assembling mechanisms, their surface morphology is usually also
studied by using a combination of microscopic methods.
Zhao et al. have reported that compound 16a and b formed
supramolecular polymers that were stabilized by hydrazidebased quadruple hydrogen bonding motifs.21 In decalin, the
supramolecular polymers further self-assembled into vesicular structures. SEM images clearly showed the formation
of spherical entities of average diameters of about 0.6 and
1.0 m, as shown in Figure 11(a) and (b), respectively. The
vesicles may exhibit defects, which may be regarded as an
evidence for their hollowness.22 For 16a and b, the fluorescence and TEM micrographs (Figure 11c and d) further
supported their hollow feature, because obvious luminance
differences and membranes were observed.
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc044
Techniques
NR2
OC12H25
H
N
O
N
H
12
O
C12H25O
RHN
O
O
13
NH
X
CH3
X=
OH HO
OH
OH
H
N
O
C12H25
O
N
C12H25
O
(a)
000045
10 kV 500.000
0.5 m
N
H
H
N
N
N
H
NR
N
NR2
000063
(b)
Supramolecular polymer
500 m
10 kV 500
NHR
NR2
O
N
O
N
H
NH
N
H
NR2
O
RN
H
OH
C12H25
15
N
C12H25O
CH3
CH3
CH3
H
N
OC12H25
N
C12H25O
Bu
R = C8H17
O
OC12H25
Et
14: R =
N
H
O
O
X
N
N
10 m
(a)
1 m
(b)
1 m
(c)
example, Bo et al. have reported that compound 20 selfassembled into nanotubes and layered sheets, which were
driven by stacking and hydrogen bonding between
the amide units.24 The materials were prepared by heating its suspension in THF to reflux until all the solids
were completely dissolved and then allowing it to cool
gradually to room temperature. SEM study of its air-dried
suspension showed the formation of fibril assemblies with
a high aspect ratio (Figure 13a). Their open-ended feature
clearly revealed the tubular structure (Figure 13b). TEM
images were also utilized to support the presence of the
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc044
OR
H
N
HN
RO
H
N
NH
O
HN
NH
C11H23
HN
N
H
OR
C11H23
20
O
O
NH
N
H
RO
O
16a: R = CH2CH(CH3)2
16b: R = n -C8H17
10 m
(a)
5 kV 7,000 2 m
02/ MAR/09
(a)
100 nm
(b)
10 kV 16,000 1 m
(b)
500 nm
(c)
200 nm
(d)
2.6 nm
10 m
50 nm
(c)
(d)
Figure 11 SEM images of the vesicles of (a) 16a (1.0 mM) and
(b) 16b (1.0 mM); (c) fluorescence micrograph of the vesicle of
16b (20 mM); and (d) TEM image of the vesicle of 16b (0.4 mM)
in decalin. (Reproduced from Ref. 21. Elsevier, 2010.)
+
C16H33 N
+
N C16H33
+
HO
18
O
CB[8] =
N CH2
H
N
N
H
N
C16H33
+
N
+
N
(f)
OH
17
100 nm
100 nm
(e)
C16H33
O
HO
=
500 nm
(a)
OH
19
(Ternary complex)
1 m
2 m
(b)
nanotubes (Figure 13c and d). Magnified SEM images further revealed the rolled-up style of the nanotubes with a
scrolling structure (Figure 13e), which was further confirmed by the terminal types of tubes (Figure 13f). SEM
images were also obtained for samples at different concentrations, which revealed that nanotubes were formed when
the concentration was low and transformed to layered sheets
at high concentrations. On the basis of the observations, the
authors proposed a hierarchical self-assembling mechanism;
that is, the one-layer nanosheets were first formed, which
might further roll up to generate the nanotubes or stack to
give layered sheets.
Jiang et al. have utilized SEM to study the morphology of the aggregates of porphyrin 21.25 The samples were
prepared by drop-casting a 6 mg ml1 chloroform solution
onto the surface of SiO2 substrate or quartz. It is worthy to note that the obtained films were annealed in a
chloroform-vapor-saturated desiccator. Only after annealing, the molecules self-assemble into long microtubes. The
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc044
10
Techniques
C10H21
N
NH
CH3COS(CH2)5O
C10H21
C10H21
N
N
O(CH2)5SCOCH3
M
N
22a: M = 2H
22b: M = Zn
HN
(A)
21
(B)
C10H21
a
50 nm
1 m
1 m
(C)
(D)
50 nm
50 nm
1 m
e
100 nm
(E)
18 nm
(F)
10 nm
100 nm
100 nm
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc044
Zn
23
24a: R = H
24b: R = t -Bu
300 nm
1 m
2.5 m
300 nm
(a)
(b)
3 m
300 nm
500 nm
2 m
Number
7.82 2.07 m
(e)
SUPRAMOLECULAR CHIRALITY
(d)
60
500 nm
(c)
11
5 m
40
20
0
(f)
6 8 10 12 14
Length (m)
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc044
12
Techniques
O
RO
N
N
O
O
H
N
NH
25a: R = (CH2)2CH3
H
N
HN
H
N
NH
H
N
HN
(R,R )-26
(S,S )-26
25b: R = (CH2)4N(CH3)3+ Br
500 nm
(a)
250 nm
3 m
2 m
(b)
(a)
(b)
CONCLUSION
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc044
13
REFERENCES
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Berlin, 2009, p. 330.
5. V. Seydewitz, Scanning electron microscopy (SEM), in Electron Microscopy of Polymers, ed. G. H. Michler, Springer,
Berlin, 2008, pp. 87120.
6. G. D. Danilatos, Microsc. Res. Tech., 1993, 25, 529.
7. R. P. Apkarian, Cryo-temperature stages in nanostructural
research, in Scanning Microscopy for Nanotechnology,
eds. W. Zhou and Z. L. Wang, Springer, Berlin, 2007,
pp. 467490.
8. P. Terech, J. J. Allegraud, and C. M. Garner, Langmuir,
1998, 14, 3991.
9. E. Krieg, E. Shirman, H. Weissman, et al., J. Am. Chem.
Soc., 2009, 131, 14365.
10. C. Wang, D. Zhang, and D. Zhu, J. Am. Chem. Soc., 2005,
127, 16372.
and
T. Hasobe,
12. W. Cai, G.-T. Wang, P. Du, et al., J. Am. Chem. Soc., 2008,
130, 13450.
Supramolecular Chemistry: From Molecules to Nanomaterials, Online 2012 John Wiley & Sons, Ltd.
This article is 2012 John Wiley & Sons, Ltd.
This article was published in the Supramolecular Chemistry: From Molecules to Nanomaterials in 2012 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470661345.smc044