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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. 

The majority of gels exhibit nanoscale spatial variations in crosslink density. We present the first 3D super-resolution microscopy images of dye tagged cross-link distributions in microgels and hydrogels. The morphology of nanoscale features never imaged previously in microgels, are revealed.