The mean size of the hybrid nanoparticles was measured by dynamic light scatter (DLS).
As aforementioned, with the increase of silica substitutions, the more bulky groups exist in
the hybrids, which may hinder the self-assemble behavior, resulting in higher CAC values and
larger nanoparticle size, shown in Table 3.3. The zeta potential of CHC and the hybrids
nanoparticles was also shown in Table3.3.
The swelling ratio was primarily estimated by comparing the size under SEM image with
the size measured by dynamic light scatter (DLS). The self-assembly silica-CHC
nanoparticles show a spherical appearance with an average size around 65 nm in diameter in
SEM images. Besides, from the dynamic light scattering (DLS) measurement (Table 3.3), the
mean size of the hybrid nanoparticles was around 133 nm in diameter, which is greater by
about 2 times in volume than that of SEM measurement. This is mainly due to swelling effect
in water medium. In comparison with neat CHC, where a swelling of nearly 8 times was
observed in an earlier study [8], indicating a considerable reduction in the swelling behavior, to
nearly 4 times, when an equivalent amount of the -NH2 groups from the APTES was
chemically modified with the –COOH groups of the CHC macromolecule. Such a silica
substitution should enhance the rigidity of the resulting hybrid entity, thus, reduce
considerably its swelling.
10 20 30 40 50 60 70 0
1000 2000 3000 4000 5000 6000
Intensity
2 theda
Figure 3.13 X-ray diffraction pattern of silica-CHC.
Table 3.3 The mean size and zeta potential of the different ratio of (COOH of
CHC): (NH
2of APTES) hybrids.
sample mean size Zeta potential(mV)
CHC 122 -33.47
CA 133 17.59
C2A 302 34.78
C5A 500 45.26
C10A 600 --
Figure 3.14 (a) TEM image of the silica-CHC nanoparticle (b) The
interior TEM image of silica-CHC nanoparticle, showing a layer-like
nanoarchitecture where a highly- ordered silica phase of ~6 nm in width
surrounding the nanoparticle.
Conclusions
A novel hybrid macromolecule based on a chemical modification along the –COOH groups
of amphiphilic chitosan (CHC) with (3-aminopropyl) triethoxysilane molecules was
successfully designed and synthesized. This hybrid macromolecule showed a
concentration-dependent self-assembly behavior making a final hybrid nanoparticle tunable in
size, drug encapsulation efficiency and release profile. Formation of a highly-ordered
crystalline silica layer of ~6 nm in thickness, upon self-assembly of the hybrid molecule
rendered a prolonged, sustained release of a model drug, CPT, compared with the neat CHC
molecules. Such an continuous highly-ordered silica nanoarchitecture evolved surrounding
the hybrid nanopartciles provided not only a well-stabilized nanostructure without using
crosslinker to prevent undesirable diluting disassembly, but proved to be a result of highly
self-organization rather than random arrangement of the hybrid macromolecule upon the
natural assembly operation.
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計畫名稱：以無機分子改質雙性機丁聚糖之自組裝混成複合材料及其生醫特性之研究