Star block-copolymers: enzyme-inspired catalysts for oxidation of alcohols in water

Abstract

A number of fluorous amphiphilic star block-copolymers containing a tris(benzyltriazolylmethyl)amine motif have been prepared. These polymers assembled into well-defined nanostructures in water, and their mode of assembly could be controlled by changing the composition of the polymer. The polymers were used for enzyme-inspired catalysis of alcohol oxidation.

Hollow Nanospheres with Fluorous Interiors for Transport of Molecular Oxygen in Water

“…Although the ultra‐hydrophobic nature of SFCs often benefits their application, it also makes direct incorporation of fluorous compounds into water‐based systems impossible. A wide range of compatibilizing agents/systems have been proposed for suspending SFCs in water, including lipids, block copolymers, and proteins. The oleophobicity of fluorous compounds tends to destabilize SFC emulsions, thus rendering common dispersion approaches only a temporary success.…”

“…Deionized water and the dispersions were stirred vigorously in vials filled with pure O 2 . The vials were then opened to air, and the evolution of dissolved oxygen concentration was followed using an Inlab 605 immersion probe (Mettler Toledo) (Figure ) …”

“…Liquid SFCs exhibit an impressive ability to dissolve significant amounts of gases, including xenon, nitrogen, carbon dioxide, and oxygen, [1][2][3][4] and impressively have been found to dissolve and transport higher concentrations of respiratory gases than blood. [5] SFC liquids, polymers, and emulsions have found applications in catalysis of aerobic oxidations, [6][7] in oxygenation of submerged aerobic cultures, [8] as blood substitutes [3,9] and as media for liquid ventilation [3,10] and oxygenation in lung injury treatment [11] .Although the ultra-hydrophobic nature of SFCs often benefits their application, [3,[12][13] it also makes direct incorporation of fluorous compounds into water-based systems impossible. A wide range of compatibilizing agents/systems have been proposed for suspending SFCs in water, including lipids, [14] block copolymers, [7,15] and proteins [16] .…”

“…[5] SFC liquids, polymers, and emulsions have found applications in catalysis of aerobic oxidations, [6][7] in oxygenation of submerged aerobic cultures, [8] as blood substitutes [3,9] and as media for liquid ventilation [3,10] and oxygenation in lung injury treatment [11] .Although the ultra-hydrophobic nature of SFCs often benefits their application, [3,[12][13] it also makes direct incorporation of fluorous compounds into water-based systems impossible. A wide range of compatibilizing agents/systems have been proposed for suspending SFCs in water, including lipids, [14] block copolymers, [7,15] and proteins [16] . The oleophobicity of fluorous compounds tends to destabilize SFC emulsions, [17][18][19] thus rendering common dispersion approaches only a temporary success.…”

“…The vials were then opened to air, and the evolution of dissolved oxygen concentration was followed using an Inlab 605 immersion probe (Mettler Toledo) (Figure 4). [6][7] The addition of a small droplet of perfluorodecalin to water did not improve the O 2 transport behavior, as the SFC droplet has a small surface area and both gas uptake and release from these droplets are slow processes. Addition of the hollow nanospheres, either fluorocarbon-or hydrocarbon-lined, also did not produce any significant change in gas sorption properties.…”