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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. 

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. 

Our understanding of the left–right (LR) asymmetry of embryonic development, in particular the contribution of intrinsic handedness of the cell or cell chirality, is limited due to the confounding systematic and environmental factors during morphogenesis and a ack of physiologically relevant in vitro 3D platforms. Here we report an efficient two-layered biomaterial platform for determining the chirality of individual cells, cell aggregates, and self-organized hollow epithelial spheroids. This bioengineered niche provides a uniform defined axis allowing for cells to rotate spontaneously with a directional bias toward either clockwise or counterclockwise directions. Mechanistic studies reveal an actin-dependent, cell-intrinsic property of 3D chirality that can be mediated by actin cross-linking via α-actinin-1. Our findings suggest that the gradient of extracellular matrix is an important biophysicochemical cue influencing cell polarity and chirality. Engineered biomaterial systems can serve as an effective platform for studying developmental asymmetry and screening for environmental factors causing birth defects.