Hollow polymeric spheres have been attracting increasing
interest because of their potential applications, which range
from targeted drug delivery to advanced functional materi-
als.[1,2] Because of their hollow core structure, such polymeric
spheres can encapsulate large quantities of guest moleculesÐ
especially those spheres with functionalities within the empty
coreÐand release them at a later stage in a controlled man-
ner. Although hollow polymeric spheres with dimensions in
the micrometer and submicrometer regions are readily con-
structedÐby layer-by-layer deposition of polyelectrolytes
onto a template core,[3±6] polymerizing monomers in lipid vesi-
cles,[7,8] emulsion polymerization,[9,10] pH-induced micelliza-
tion of a grafted copolymer,[11] and by the assembly of posi-
tively charged polyelectrolytes and negatively charged
nanoparticles[12]Ðthe synthesis of hollow spheres 100 nm or
less in size has only recently become the subject of research
activity. Several different routes, such as the self-assembly of
block copolymers in a selective solvent,[13,14] the deposition of
polyelectrolytes on a decomplexable or soluble core,[15,16] and
microemulsion (as well as miniemulsion) polymerization,[17,18]
have been developed to form hollow polymeric nanospheres.
Although some of these methods have been quite successful,
these strategies require the core templates to be removed in
order to create a hollow interior, or need large quantities of
surfactants to form nanosized micelles. Furthermore, although
the majority of the proposed applications of hollow nano-
spheres or nanocapsules are concentrated in the biomedical
field, most of the hollow polymeric spheres described to date
are ill-suited for such purposes. Therefore, materials (in par-
ticular for the surfaces of the hollow nanospheres) that are
biocompatible, non-toxic, and sometimes also biodegradable,
are highly desirable. Herein, we demonstrate a simple and di-
rect method for fabricating hollow polymeric nanospheres
with biocompatible and biodegradable macromolecules. In
this approach, hollow polymeric nanospheres were formed in
a completely aqueous system without the aid of surfactants,
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