Polymersome Colloidosomes for Enzyme Catalysis in a Biphasic System

Abstract

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Enzyme–Polymer Conjugates as Robust Pickering Interfacial Biocatalysts for Efficient Biotransformations and One‐Pot Cascade Reactions

“…[2] To address this limitation, Pickering interfacial catalysis (PIC) has been developed. [1b] Fore xample,l ipases were attached into/onto metal-organic frameworks (MOFs), [8] polymersomes, [9] and Janus silica [10] for both esterification and hydrolysis reactions at the water-oil interface.P IB promotes not only reaction efficiency but also biocatalyst recyclability and usability after operation. [1b] Fore xample,l ipases were attached into/onto metal-organic frameworks (MOFs), [8] polymersomes, [9] and Janus silica [10] for both esterification and hydrolysis reactions at the water-oil interface.P IB promotes not only reaction efficiency but also biocatalyst recyclability and usability after operation.…”

“…[1b, 3] PIC is typically enabled by the use of catalytically active micro-/nanoparticles to stabilize emulsions,t hat is,P ickering emulsions (PEs), for interfacial reactions.I np ioneering studies,t he research groups of Resasco and Qiu prepared these active particles by loading transition metals onto carbon nanotubes,which formed waterin-oil emulsions for efficient biofuel upgrading [4] and alcohol oxidation, [5] respectively.L ater, av ariety of interface-active chemocatalysts were developed for PIC,r anging from acid/ base [3,6] to oxidation/epoxidationc atalysts, [7] as nicely reviewed by Pera-Titus et al [1b] Recently,t he PIC concept was evolved into Pickering interfacial biocatalysis (PIB), in which biocatalysts and solid carriers are integrated into biohybrid catalyst particles amenable to emulsion reactions. [1b] Fore xample,l ipases were attached into/onto metal-organic frameworks (MOFs), [8] polymersomes, [9] and Janus silica [10] for both esterification and hydrolysis reactions at the water-oil interface.P IB promotes not only reaction efficiency but also biocatalyst recyclability and usability after operation. However,f rom ap ractical point of view,t he current PIB preparation method requires external particles as stabilizers (also as enzyme carriers), which inevitably increases the diffusional resistance to catalysts.T om inimize such resistance,acarrier-free biocatalyst-stabilized PIB would be preferable because it would allow direct biocatalyst exposure to the reaction interface.H owever,t his direct exposure is often accompanied by reduced stability of the biocatalysts.…”

Fibrous Networks with Incorporated Macrocycles: A Chiral Stimuli‐Responsive Supramolecular Supergelator and Its Application to Biocatalysis in Organic Media

“…This increased specific activity can be attributed to the considerably larger interfacial area of the SiO 2 -nanoparticle-stabilized microparticles, which improves the mass transfer between the two phases and the accessibility to the enzyme catalyst. [12,26] Interestingly, different amounts of lipase in the gel particles yield almost the same specific activity (Figure 5g). Also, the initial reaction rates of the esterification reaction increase with enzyme concentration.…”

“…[10] As most enzymes operate best in water or polar solvents, their use in organic reactions is often limited unless the phase incompatibility is appropriately dealt with. This can be achieved either in emulsions that are stabilized by amphiphilic surfactants or in Pickering emulsions [11,12] in which the enzyme-containing polar-phase droplets are stabilized by surrounding SiO 2 nanoparticles. Gelling of the polar phase inside these nanoparticle-surrounded droplets stabilizes them with the synthetic advantage that the droplets containing the enzyme can easily be reused by separating them from the reaction mixture by centrifugation.…”

Stimuli-responsive polymersomes and nanoreactors

“…52,53 Polymersomes composed of PAA-b-P(S-co-4vinyl benzyl azide) were stabilized by a Cu-assisted azide alkyne conjugation reaction with a bis-alkyne reagent. The polymersomes were able to form and stabilize water/oil Pickering emulsions and disassemble to the dispersed state in aqueous solution under acidic and neutral pH, respectively.…”