Soft
nanoparticles are interesting materials due to their size,
deformability, and ability to host guest molecules. Surface properties
play an essential role in determining the fate of the particles in
biological medium, and coating of the nanoparticles (and polymers)
with carbohydrates has been found to be an efficient strategy for
increasing their biocompatibility and fine-tuning other important
properties such as aqueous solubility. In this work, soft nanogels
of poly(
N
-vinylcaprolactam), PNVCL, were surface-functionalized
with different glucose and maltose ligands, and the colloidal properties
of the gels were analyzed. The PNVCL nanogels were first prepared
via semibatch precipitation polymerization, where a comonomer, propargyl
acrylate (PA), was added after preparticle formation. The aim was
to synthesize “clickable” nanogels with alkyne groups
on their surfaces. The nanogels were then functionalized with two
separate azido-glucosides and azido-maltosides (containing different
linkers) through a copper-catalyzed azide–alkyne cycloaddition
(CuAAc) click reaction. The glucose and maltose bearing nanogels were
thermoresponsive and shrank upon heating. Compared to the PNVCL–PA
nanogel, the carbohydrate bearing ones were larger, more hydrophilic,
had volume phase transitions at higher temperatures, and were more
stable against salt-induced precipitation. In addition to investigating
the colloidal properties of the nanogels, the carbohydrate recognition
was addressed by studying the interactions with a model lectin, concanavalin
A (Con A). The binding efficiency was not affected by the temperature,
which indicates that the carbohydrate moieties are located on the
gel surfaces, and are capable of interacting with other biomolecules
independent of temperature. Thus, the synthesis produces nanogels,
which have surface functions capable of biorelevant interactions and
a thermoresponsive structure. These types of particles can be used
for drug delivery.
Soft poly(N-vinylcaprolactam) (PNVCL) based nanogels were prepared and surface-decorated with gold nanoparticles (AuNPs). The applicability of the hybrid nanogels (PNVCL-AuNPs) as carriers for low molar mass substances was of special interest. AuNPs protected with a mixture of 11azidoundecanothiol and 11-mercaptoundecanoic acid were bound to propargyl functionalized PNVCL based nanogels. Acidic groups on the surfaces of AuNPs and PNVCL based nanogels stabilize the particle dispersions against precipitation above the phase transition temperature of PNVCL. Both the neat PNVCL nanogels and the PVCL-AuNPs shrink upon heating the dispersions. Even though the AuNPs are mainly located in the soft surface layer of the nanogels, the PNVCL-AuNPs respond to visible light as well as to radio-frequency (RF) irradiation by shrinking due to the AuNPs acting as nanoheaters. Interactions of linear PNVCL, PNVCL nanogels and PNVCL-AuNPs with two fluorescent probes were studied as function of increasing temperature. Once bound to the polymer the fluorescent probe may or may not be released from it, depending on its polarity and water solubility. Presence of AuNPs changed the release behavior of the water soluble charged fluorescent probe from the nanogels.
A thermoresponsive polymer, poly(N-vinylcaprolactam) (PNVCL), was synthesized in an emulsion above its thermal transition temperature to produce particles via polymerization induced self-assembly (PISA).
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