Interfacial Behaviors of Giant Amphiphilic Molecules Composed of Hydrophobic Isobutyl POSS and Hydrophilic POSS Bearing Carboxylic Acid Groups at the Air-Water Interface.

The behavior of giant amphiphilic molecules at the air-water interface has become a subject of concern to researchers. Small changes in the molecular structure can cause obvious differences in the molecular arrangement and interfacial properties of the monolayer. In this study, we have systematically investigated the interfacial behaviors of the giant amphiphilic molecules with different number of hydrophobic BPOSS blocks and one hydrophilic ACPOSS block ((BPOSS)n-ACPOSS (n = 1-5)) at the air-water interface by the surface pressure-area (π-A) isotherm, Brewster angle microscopy (BAM), compression modulus measurement, and hysteresis measurement. We found that both the number of BPOSS blocks and the compression rate can significantly influence the interfacial behaviors of giant molecules. The π-A isotherms of giant molecules (BPOSS)n-ACPOSS (n = 2-5) exhibit a "cusp" phenomenon which can be attributed to the transition from monolayer to multilayer. However, the cusp is dramatically different from the "collapse" of the monolayer studied in other molecular systems, which is highly dependent on the compression rate of the monolayer. In addition, the compression modulus and hysteresis measurements reveal that the number of BPOSS blocks of (BPOSS)n-ACPOSS plays an important role in the static elasticity, stability, and reversibility of the Langmuir films.

Leveraging Macromolecular Isomerism for Phase Complexity in Janus Nanograins.

It remains intriguing whether macromolecular isomerism, along with competing molecular interactions, could be leveraged to create unconventional phase structures and generate considerable phase complexity in soft matter. Herein, we report the synthesis, assembly, and phase behaviors of a series of precisely defined regioisomeric Janus nanograins with distinct core symmetry. They are named B2DB2 where B stands for iso-butyl-functionalized polyhedral oligomeric silsesquioxanes (POSS) and D stands for dihydroxyl-functionalized POSS. While BPOSS prefers crystallization with a flat interface, DPOSS prefers to phase-separate from BPOSS. In solution, they form 2D crystals owing to strong BPOSS crystallization. In bulk, the subtle competition between crystallization and phase separation is strongly influenced by the core symmetry, leading to distinct phase structures and transition behaviors. The phase complexity was understood based on their symmetry, molecular packing, and free energy profiles. The results demonstrate that regioisomerism could indeed generate profound phase complexity.

Corner-opening and corner-capping of mono-substituted T8 POSS: product distribution and isomerization.

We applied chromatographic and spectroscopic techniques to revisit the product distribution of the corner-opening and corner-capping reactions of monosubstituted T8 POSS. The monosubstituted Si is more likely to be removed than the remaining seven Si atoms during the corner-opening. After the corner-capping, the yield of monosubstituted T8 POSS is much higher than the yields of the ortho- and meta-isomers of disubstituted T8 POSS, and the para-isomer is negligible.

Thickness control of 2D nanosheets assembled from precise side-chain giant molecules.

The performance of 2D nanomaterials hinges on both the chemical compositions and the morphological structures across different length scales. Among all the three dimensions, thickness is the only one that falls into the nanometer scale and, to some extent, determines the intrinsic properties of 2D nanomaterials. In this study, we report the preparation and precise thickness control of 2D nanosheets assembled from a library of monodispersed amphiphilic giant molecules composed of functional polyhedral oligomeric silsesquioxanes (POSSs) as the side groups. Solution self-assembly of such giant molecules resulted in 2D nanosheets with similar structural configurations, where a bilayer of hydrophobic isobutyl POSS (BPOSS) is sandwiched by two monolayers of hydrophilic POSS bearing carboxylic acid groups (APOSS). The thickness of the obtained nanosheets could be tuned through adjusting the chemical compositions of the pendant POSS cages. Intriguingly, we found that the thickness of the 2D nanosheets was not necessarily proportional to the contour length of the giant molecule nor the total number of POSS cages tethered to the main chain. Indeed, the number ratio of BPOSS to APOSS, rather than the exact number, played a deterministic role in the thickness control. To explain the unusual thickness dependence, we built up a structure model with an in-plane orientation of the giant molecules in the nanosheets, from which a formula was further deduced to semi-quantitatively describe the inverse relationship between the overall thickness and the number ratio of BPOSS to APOSS.