For samples vitrified at 45 °C (above the LCST), cryo-EM showed significantly different structures depending on concentration. In the 1.8 wt% sample, we observed the formation of isolated spherical structures spaced about 50 nm apart (Fig. and), while the 3.6 wt% samples showed the aggregation of the spherical particles leading to a bi-continuous phase with a mesh size of about 50 nm (Fig. and). In addition, cryo-EM micrographs of 1.8 wt% samples vitrified at 45 °C also showed the presence of lamellar fringes with ~1.6 nm spacing and small particles (~5 nm) in these samples (Fig. ). These results show that although increasing the temperature caused the aggregation of the TR-CP colloids in both samples, only the 3.6 wt% samples met the criteria needed for gel formation. This observation is consistent with the visual inspection of the TR-CP and rheology, identifying 3.6 wt% as the lower limit of concentration for gel formation. To confirm our observations from microscopy, small-angle X-ray scattering (SAXS) at 20 °C and 40 °C in solution was used to study the colloidal particle self-assembly, gel structure, and gelation mechanism (Fig. , SI Section 3.5). Guinier-Porod model fitting revealed that the TR-CP colloids in solution below the LCST are disk-shaped with a radius of around 5 nm and a disk thickness of 3.3-3.6 nm, consistent with the size of the spherical/ovoid nanoparticles seen by cryo-EM (Fig. , Table ). As temperature increased above gelation, both the disk radius and thickness of these aggregates slightly increased. The intermediate q feature for single aggregate was slightly suppressed, while a strong structure factor peak S(q) appeared in low q range (centered at 0.102 nm -1 ). These features indicate that after gelation, the particles aggregated to form large, ordered structures with a center-to-center distance of ~60 nm, in line with the cryo-EM results at 45 °C.