Temperature- and pH-responsive poly(N-isopropylacrylamide-co-methacrylic acid) microgels as a carrier for controlled protein adsorption and release.

Herein, we report controlled protein adsorption and delivery of thermo- and pH-responsive poly(N-isopropylacrylamide-co-methacrylic acid) (PNIPAM-co-MAA) microgels at different temperatures, pH values and ionic strengths by employing bovine serum albumin (BSA) as a model protein. For these dual-responsive microgels, we found that the BSA adsorption was driven by several of six competing contributions, viz., physical diffusion (PD), hydrophobic interactions (HI), electrostatic attraction (EA), hydrogen bonding (HB) and temperature or pH-induced seizing action (SAT or SApH), depending on the temperature and pH of the solution. Compared to the pure PNIPAM microgels, the higher swelling degree of the PNIPAM-co-MAA microgels allowed a large amount of BSA loading under any experimental conditions. A largest BSA adsorption of 45.1 µg mg-1 was achieved at 40 °C and pH 4 due to the presence of all six contributions. The BSA adsorption and delivery could be further tuned by changing the crosslinking density within the microgels. The BSA binding onto the microgels was found to be ionic strength dependent, which could be attributed to the charge shielding of Na+ ions, salting out of BSA and aggregate formation of the microgels. The adsorbed BSA could be controllably released by adjusting the temperature and pH of the experiment, and with the help of sodium dodecyl sulphate (SDS) addition so as to eliminate each interaction between BSA and the microgels. Thus, this study can be useful to design a stimuli-responsive microgel-based carrier for controlled release of proteins.

Adsorption dynamics of thermoresponsive microgels with incorporated short oligo(ethylene glycol) chains at the oil-water interface.

Herein, we report a systematic study of the adsorption behaviour of short oligo(ethylene glycol) (OEG) chains incorporated into poly(N-isopropylaccrylamide) (PNIPAM) microgels at the dodecane-water interface as a function of the microgel concentration at two different temperatures: 298 and 313 K. The dynamic interfacial tension of the interface for the adsorption of these functional microgels is measured by means of a pendent drop method. We find that similar to pure PNIPAM microgels, the functionalized microgels initially get transported from the bulk to the interface, where they undergo the deformability dependent spreading process, and thus leading to a reduction of interfacial tension. However, the OEG chains significantly influence the dynamic processes of the microgels at the interface, enabling precise control over the interfacial activity. A tuneability of adsorption behaviour that is interpreted in terms of the diversity of structural and morphological features of the microgels, can be achieved by changing the temperature and/or the OEG chain length of the comonomer. While the temperature induced phase transition generally slows down the adsorption kinetics of the microgels, increasing the temperature from 298 to 313 K allows faster reduction of interfacial tension for the adsorption of the microgels with long OEG chains among the studied comonomers, making them a unique interfacially active functional material. Overall, incorporation of OEG chains allows tailoring the interfacial activity of microgels, thereby paving the way for the use of these microgels to act as effective Pickering emulsion stabilizers in a range of applications.

Short oligo(ethylene glycol) chain incorporated thermoresponsive microgels: from structural analysis to modulation of solution properties.

Herein, we report synthesis of thermoresponsive poly(N-isopropylaccrylamide) (PNIPAM) microgels with short oligo(ethylene glycol) (OEG) chain comonomers (1 to 4/5 repeating unit) by surfactant-free precipitation copolymerization. The efficient incorporation of the comonomers was confirmed by a complete set of characterization methods viz., FTIR, 1H NMR, TEM, DLS, and viscometry. The structural heterogeneity and the distribution of the comonomers within the microgels were determined by means of 1H high-resolution transverse relaxation magnetization measurements. Interestingly, the incorporation of these short OEG chain comonomers led to the formation of a core-corona structure, in which the comonomers were mainly located in the core of the polymeric network with PNIPAM dangling chains at the microgel periphery. The experimental investigations of deswelling behaviours revealed that the OEG chains allowed precise control over the colloidal properties, including phase transition, particles size, swelling degree and polydispersity of the microgels. The tuneability of these properties that was interpreted in terms of polymeric hydrophobic/hydrophilic balance as well as structural diversity, could be achieved by changing the OEG chain length, comonomer feed and crosslinking density. Further, we found that the microgels with more hydrophilic OEG chains were able to show a higher relative swelling, and the same solid content thus led to a higher viscosity at all temperatures. The OEG chains remarkably improved the colloidal stability of the microgels in electrolyte solutions even at higher temperatures, thereby paving the way for the use of these microgels in a range of applications.

Microgel-stabilized liquid crystal emulsions enable an analyte-induced ordering transition.

We develop a new strategy that involves the formation of microgel (MG) decorated liquid crystal (LC) droplets, which show remarkable stability. This system facilitates the analysis of the LC droplets that undergo an analyte-triggered conformational transition, thus optimizing the quantitation of aqueous analytes.