A novel layer-by-layer self-assembly approach enabled by metal-organic coordination was developed to prepare polymer-inorganic hybrid microcapsules. Alginate was first activated via N-ethyl-N'-(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) coupling chemistry, and subsequently reacted with dopamine. Afterward, the dopamine modified alginate (Alg-DA) and titanium(IV) bis(ammonium lactato) dihydroxide (Ti(IV)) were alternatively deposited onto CaCO3 templates. The coordination reaction between the catechol groups of Alg-DA and the Ti(IV) allowed the alternative assembly to form a series of multilayers. After removing the templates, the alginate-titanium hybrid microcapsules were obtained. The high mechanical stability of hybrid microcapsules was demonstrated by osmotic pressure experiment. Furthermore, the hybrid microcapsules displayed superior thermal stability due to Ti(IV) coordination. Catalase (CAT) was used as model enzyme, either encapsulated inside or covalently attached on the surface of the resultant microcapsules. No CAT leakage from the microcapsules was detected after incubation for 48 h. The encapsulated CAT, with a loading capacity of 450-500 mg g(-1) microcapsules, exhibited desirable long-term storage stability, whereas the covalently attached CAT, with a loading capacity of 100-150 mg g(-1) microcapsules, showed desirable operational stability.

An efficient, easily recyclable enzyme cascade system based on nanoparticle‐stabilized capsules (NPSCs) is constructed through a synergy of a Pickering emulsion and sol‐gel process. Specifically, oligodopa‐coated titania nanoparticles (biomimetic titania) containing the first enzyme (FateDH) are synthesized through a bioadhesion‐assisted biomimetic mineralization approach. The biomimetic titania is then spontaneously assembled at the interface between the oil phase (hexadecane/butyl titanate (BuTi) mixture) and water phase during the formation of Pickering emulsions. The sol‐gel process of BuTi can produce not only butanol for assisting the formation of Pickering emulsions but also titania gel particles (sol‐gel titania) for cross‐linking the biomimetic titania through catechol‐titanium chelating. The NPSCs obtained, which contain the first enzyme, conjugate the second enzyme (FaldDH) onto the surface for constructing the enzyme cascade system. The system exhibits high activity and stability, particularly, superior recyclability for conversion of CO2 into formaldehyde. In detail, the system shows a formaldehyde yield of 50.0%, and can quickly float onto the air/water interface soon after stopping the agitation of reaction mixtures, which ensures that the formaldehyde yield keeps almost unaltered after 10 times recycling. This study will be useful for facile construction of a wealth of catalytic systems with efficient, recyclable attributes.

A novel approach combining biomimetic mineralization and bioadhesion is proposed to prepare robust and versatile organic-inorganic hybrid microcapsules. More specifically, these microcapsules are fabricated by sequential deposition of inorganic layer and organic layer on the surface of CaCO(3) microparticles, followed by the dissolution of CaCO(3) microparticles using EDTA. During the preparation process, protamine induces the hydrolysis and condensation of titania or silica precursor to form the inorganic layer or the biomineral layer. The organic layer or bioadhesive layer was formed through the rapid, spontaneous oxidative polymerization of dopamine into polydopamine (PDA) on the surface of the biomineral layer. There exist multiple interactions between the inorganic layer and the organic layer. Thus, the as-prepared organic-inorganic hybrid microcapsules acquire much higher mechanical stability and surface reactivity than pure titania or pure silica microcapsules. Furthermore, protamine/titania/polydopamine hybrid microcapsules display superior mechanical stability to protamine/silica/polydopamine hybrid microcapsules because of the formation of Ti(IV)-catechol coordination complex between the biomineral layer and the bioadhesive layer. As an example of application, three enzymes are respectively immobilized through physical encapsulation in the lumen, in situ entrapment within the wall and chemical attachment on the out surface of the hybrid microcapsules. The as-constructed multienzyme system displays higher catalytic activity and operational stability. Hopefully, the approach developed in this study will evolve as a generic platform for facile and controllable preparation of organic-inorganic hybrid materials with different compositions and shapes for a variety of applications in catalysis, sensor, drug/gene delivery.

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