Guest release and solution behavior of a hydrogen-bonding physical micelle during chemoresponsive shell disruption

The guest release and solution behavior during shell disruption of a polymeric nanocapsule are described. Hyperbranched polyethylenimine (PEI, M_n = 10?000) is chemically functionalized with multiple DAD hydrogen-bonding motifs (D and A: hydrogen-bonding donor and acceptor), leading to PEI₂₃₂-(DAD)_x (3) (x = 93 (3a), x = 46 (3b), x = 23 (3c), x = 12 (3d)). Meanwhile, polyethylene oxide (M_n = 2 200) is end-capped with thymine moieties (PEO-ADA) (4). Mixing of the hydrogen-bonding complementary 3 and 4 (DAD/ADA = 1) leads to a physical micelle (3·4) in apolar media, and the resulting micelle can completely and irreversibly transfer the ionic and water-soluble Congo red (CR) into chloroform phase by encapsulation. Experiment proves that the micelle can exist as a pseudo-unimolecular micelle (p-UIM, meaning one PEI in one micelle) or as aggregate, depending on the shell density. As a result, 3b·4 generally exists as a p-UIM while 3d·4 can exist as p-UIM only in a very narrow range of concentrations. The critical aggregation concentration (CAC) is also dependent on the core structure of the micelle, thus when the residual amines in the core of 3b are transformed into amide, the resulting 5b·4 shows a very low CAC. Small chemicals bearing DAD hydrogen-bonding motif can compete to bind with the PEO-ADA shell and destruct the p-UIM, leading to aggregation and precipitation of the p-UIM along with the CRs. Experiment proves that the CR has strong acid-base interaction with the PEI core of the p-UIM, but when the basicity of the PEI core is reduced by amidation, partial CRs can be released into the water phase.     

Self-association of double-hydrophilic copolymers of acrylic acid and poly(ethylene oxide) macromonomer

Poly(ethylene oxide) (PEO) end-capped by a methacrylate unsaturation was copolymerized with acrylic acid by RAFT with dibenzyltrithiocarbonate as a chain transfer agent. Tapered triblock copolymers consisting of a poly(acrylic acid) (PAA) inner block and comb-like outer blocks of PEO macromomers were formed as result of the comonomers reactivity ratios. Composition of these copolymers and length of the PEO branches were varied. Dynamic light scattering (DLS) was used to characterize the aggregates formed in water and to investigate their response to stimuli, such as pH, temperature and ionic strength. In parallel, the morphology of the aggregates was directly observed by transmission electron microscopy (TEM). Well-defined aggregates were formed in the 5<pH<8 range, with a morphology strongly depending on the copolymer composition. At pH<5, the copolymers were poorly soluble and no well-defined structure was observed, whereas free chains were formed at pH>8 as consequence of the complete ionization of the PAA block.     

Three component terpolymer and IPN hydrogels with response to stimuli

Two different types of multi-stimuli-shrinking hydrogels were synthesized (IPNs and terpolymeric hydrogels) by properly polymerizing N-isopropylacrylamide, 2-hydroxyethyl methacrylate and 2-acrylamido-2-methylpropanesulfonic acid in various mutual ratios and different synthetic orders. Both classical (CP) and frontal (FP) polymerizations were used and the resulting material properties compared. The best compositions and synthetic routes were found and the swelling, morphological and thermal material properties were studied. The results show that some IPNs exhibit marked stimuli-shrinking properties while some terpolymers present an opposite behavior. IPNs swell more than terpolymers and show a sharper stimuli-response, with a larger swelling ratio variation. In addition, FP allowed obtaining samples with the same characteristic of CP materials, but with significant preparation advantages. It has been demonstrated that by varying monomer mutual ratio, synthetic technique (FP or CP) and structural architecture (terpolymers or IPNs), different materials having peculiar properties and characteristics can be obtained.     

Preparation of polymer latex particles carrying salt-responsive fluorescent graft chains

We prepared the novel fluorescent polymer latex particles which can change their fluorescence intensity in response to the increasing NaCl concentration in water. Core polymer latex particles were synthesized by emulsifier-free emulsion polymerization of styrene and 2-(2-chloroisobutyroyloxy)ethyl methacrylate. Hydrophilic polymer chains containing epoxy groups were grafted from the core particles by surface-initiated atom transfer radical copolymerization of methoxy polyethyleneglycol methacrylate (MEO_xMA, x = 4 or 9) and glycidyl methacrylate in aqueous media. After azidation of epoxy groups in graft chains, a water-soluble fluorescent dansyl derivative was successfully coupled with the graft chains by copper-catalyzed azide-alkyne cycloaddition in aqueous media. The wavelength of maximum fluorescence intensity of polymer particles carrying graft chains with longer PEG side chains (x = 9) was slightly blue-shifted (7 nm) and the fluorescence intensity increased (1.35 times) with an increase in NaCl concentration as opposed to polymer particles with shorter PEG chains (x = 4).