Microfluidic emulsification has been exploited for the segmentation of complex fluids and biological suspensions into monodisperse microscale droplets. As the emulsion is conveyed through downstream microfluidics networks, optical tracking techniques allow the determination of mechanical fluid properties, such as viscosity, from discrete droplets. The application of this combined emulsification and optical monitoring technique to bulk biofluids, including whole blood or blood fractions, enables the design of highly multiplexed diagnostic approaches. We have demonstrated the ability of this integrated technique to monitor dynamic processes in droplets that are representative of bulk solution behavior. Using whole blood, plasma and a panel of synthetic and natural hydrogels that mimic coagulation behavior, we have focused upon the evolution of these materials during polymerization and gelation. The results of these studies have borne not only a methodology by which bulk properties may be monitored in femtoliter volumes, but also a technique appropriate for the controlled fabrication of monodisperse microscale hydrogel constructs. Fundamental building blocks in this size regime with unique materials composition are essential for the evolution of designer vehicles for cell-based therapies and regenerative medicine approaches.