A Highlight from Sakai Lab’s Research Last Year
The internal structure of polymer gels is generally inhomogeneous, and gel researchers have long struggled with how to quantitatively evaluate this inhomogeneity. In response to this long-standing problem, we proposed a method to quantify gel inhomogeneity using an extremely fundamental physical property: the osmotic pressure of gels.
The van ’t Hoff law is the most basic principle describing osmotic pressure, predicting that the osmotic pressure of a system is proportional to the concentration of dissolved solutes. This law is remarkably robust: at sufficiently low solute concentrations, it holds essentially independent of the chemical nature of the solute. Historically, osmotic-pressure measurements based on this solute-independent principle became an important route for estimating polymer molar masses, providing key evidence for their macromolecular nature.
Here, it is important to emphasize that osmotic pressure is determined solely by the concentration of dissolved components. Consider a simple example of dissolving sugar in water. At low sugar concentrations, the osmotic pressure increases proportionally with concentration. As the concentration increases, the strict proportionality predicted by the van ’t Hoff law eventually breaks down, yet the osmotic pressure still continues to rise as more sugar is dissolved. However, once the solution reaches its saturation limit, additional sugar no longer dissolves and instead precipitates, causing the system to become cloudy. In this regime, the amount of sugar added exceeds the amount actually dissolved, and no matter how much sugar is added, the osmotic pressure remains approximately constant.
Let us now return to my favorite subject: gels. In so-called transparent gels, where polymers are well dissolved in the solvent, there exists a strong law analogous to the van ’t Hoff law—the semidilute scaling law—which states that the osmotic pressure is determined solely by polymer concentration. For example, in hydrogels composed of polyethylene glycol (PEG) and water, once the PEG concentration is fixed, the osmotic pressure is uniquely determined, regardless of the detailed geometry of the gel network. Conversely, this means that if the osmotic pressure of a gel is known, the polymer concentration within the gel can be inferred.
As mentioned at the outset, however, most real gels are inhomogeneous and, strictly speaking, not perfectly transparent but rather turbid. Turbidity indicates that not all polymer chains are molecularly well dissolved in the solvent. If a certain fraction of polymer chains in a gel is not molecularly dispersed, such a gel is expected to exhibit a smaller osmotic pressure than would be expected from its total polymer concentration.
From this perspective, by measuring the osmotic pressure of a gel, one can back-calculate the concentration of polymer chains that effectively contribute to osmotic pressure—that is, the concentration of polymer chains that are truly dissolved. By comparing this “osmotic-pressure-effective polymer concentration” with the total polymer concentration of the gel, one can directly evaluate how homogeneous the gel is. If the two concentrations coincide, the gel is homogeneous; if they differ significantly, the gel is inhomogeneous. This approach enables the quantitative evaluation of gel inhomogeneity based on osmotic pressure, a fundamentally simple physical quantity. Despite the simplicity of this principle, surprisingly, such a method had not been proposed previously.
We will continue to tackle these “old yet new” problems, using fundamental physical principles to reveal the true nature of gels, step by step.
https://t.co/KqW2Y59s9R
Supramolecular protection of isocyanates using crystalline pillar[n]arenes has been published in Nature Communications!
Many congratulations to Yasuzawa-kun and Sutou-kun, and thanks to Nomura-sensei and Akine-sensei for collaboration!
https://t.co/BtPVvxlZp5