Quantification of functional crosslinker reaction kinetics via super-resolution microscopy of swollen microgels.

Super resolution microscopy (SRM) brings the advantages of optical microscopy to the imaging of nanostructured soft matter, and in colloidal microgels, promises to quantify variations of crosslink densities at unprecedented length scales. However, the distribution of all crosslinks does not coincide with that of dye-tagged crosslinks, and density quantification in SRM is not guaranteed due to over/under-counting dye molecules. Here we demonstrate that SRM images of microgels encode reaction rate constants of functional cross linkers, which hold the key to correlating these distributions. Combined with evolution of microgel particle radii, the functional cross linker distributions predict consumption versus time with high fidelity. Using a Bayesian regression approach, we extract reaction rate constants for homo and cross propagation of the functional crosslinker, which should be widely useful for predicting spatial variations in crosslink density of gels.

One-pot surfactant-free modulation of size and functional group distribution in thermoresponsive microgels.

Control over the size and functional group distribution of soft responsive hydrogel particles is essential for applications such as drug delivery, catalysis and chemical sensing. Traditionally, targeted functional group distributions are achieved with semi-batch techniques which require specialized equipment, while the preparation of size-tailored particles typically involves the use of surfactants. Herein, we present a simple and robust surfactant-free method for the modulation of size and carboxylic acid functional group distribution in poly(N-isopropylacrylamide) thermoresponsive microgels, employing reaction pH as the single experimental parameter. The varying distributions of carboxylic acid residues arise due to differences in kinetic reactivity, which are a function of the degree of dissociation of methacrylic acid, and thus of reaction pH. Incorporated charged residues induce a surfactant-like action during the particle nucleation stage, and impact the final particle size. Characterization with dynamic light scattering, and electron microscopy consistently supports the pH-tailored morphology of the microgels. A mathematical model which accounts for particle deformation on the imaging substrate also shows excellent agreement with the experimental results.

Super-resolution interference lithography enabled by non-equilibrium kinetics of photochromic monolayers.

Highly parallelized optical super-resolution lithography techniques are key for realizing bulk volume nanopatterning in materials. The majority of demonstrated STED-inspired lithography schemes are serial writing techniques. Here we use a recently developed model spirothiopyran monolayer photoresist to study the non-equilibrium kinetics of STED-inspired lithography systems to achieve large area interference lithography with super-resolved feature dimensions. The linewidth is predicted to increase with exposure time and the contrast is predicted to go through a maximum, resulting in a narrow window of optimum exposure. Experimental results are found to match with high quantitative accuracy. The low photoinhibition saturation threshold of the spirothiopyran renders it especially conducive for parallelized large area nanopatterning. Lines with 56 and 92 nm FWHM were obtained using serial and parallel patterning, respectively. Functionalization of surfaces with heterobifunctional PEGs enables diverse patterning of any desired chemical functionality on these monolayers. These results provide important insight prior to realizing a highly parallelized volume nanofabrication technique.

3D mapping of nanoscale crosslink heterogeneities in microgels.

The majority of swollen polymer networks exhibit spatial variations in crosslink density. These spatial heterogeneities are particularly important in colloidal gel particles, or microgels, where they manifest themselves on the nanoscale and impact mechanical and transport properties. Despite their importance, the real space nanostructure of these heterogeneities at the individual particle level has remained elusive. Using state of the art super-resolution microscopy known as Whole cell 4Pi Single Molecule Switching Nanoscopy (W-4PiSMSN) we demonstrate 3D nanoscale mapping of spatial crosslink heterogeneities in a model system of poly(N-isopropylacrylamide) colloidal gel particles containing a novel fluorophore tagged crosslinker. We reveal the presence of higher crosslink density clusters embedded in a lower crosslink density matrix within the core of individual microgel particles, a phenomenon that has been predicted, but never been observed before in real space. The morphology of the clusters provides insight into the kinetics of microgel formation. This study also provides proof-of-concept 3D super-resolution imaging of spatial heterogeneities in bulk hydrogels.