Confinement on Soft Materials: Systems Synthesis and Application

Abstract

Isolating chemically-reactive sites into nanosized compartments is an important mode of control used by Nature to perform chemical transformations with extremely high yields and selectivity. Biological systems are fundamentally organized as bounded and isolated nano- and micro-sized environments featuring distinct localized properties, such as steric crowding, polarity, hydrophobicity, potential for molecular recognition, or pH. Through this compartmentalization, reaction substrates are sequestered away from interfering factors and competing substrates, or are physically prevented from forming alternative products or favoring specific pathways. Inspired by Nature, chemists have explored the rational design and application of various nanocompartments. This work explores three types of nanoconfinement systems capable of catalysis and specific transport: surfactant micelles, block-copolymer micelles, and hollow inorganic nanoparticles.

The surfactant micelles are designed as part of a system of self-replicating micelles and are used to show how the chirality of the confinement system effects reaction kinetics. Simple click chemistry between a hydrophilic chiral head and a hydrophobic tail is used to produce an amphiphile under biphasic conditions. Once the product achieves critical micelle concentration, stable micelles can form. These micelles subsequently compartmentalize and pre-concentrate hydrophobic substrates, increasing the reaction rate and resulting in the self-propagation of the micellar structures and their chiralities.

The next system explores block-copolymer micelles that are made up of a hydrophobic saturated fluorocarbon block and a hydrophilic block. The amphiphilic copolymers can form aggregates in water and, because of properties unique to the hydrophobic block, this system also increases oxygen solubility in water. Different fluorocarbon monomers are discussed and it was found that the structure of the fluorinated monomer, temperature, and pH effect aggregation behavior and the concentration of dissolved oxygen. Additionally, varying the pH of the system could be used to trigger oxygen release.

Similar to the block-copolymer micelles, the hollow inorganic nanoparticles were designed to transport oxygen. Here, hollow silica nanoparticles were designed with a fluorinated interior surface and a hydrophilic exterior. This design allows for highly dispersible nanoparticles in water and facilitates the uptake of saturated fluorocarbon liquids into their cores. Once the saturated fluorocarbon is incorporated, the system can les to increases in oxygen solubility.