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The utilization of biocatalytic oxidations has evolved from the niche applications of the early 21st century to a widely recognized tool for general chemical synthesis. One of the major drawbacks that hinders commercialization is the dependence on expensive nicotinamide adenine dinucleotide (NAD(P)+) cofactors, and so, their regeneration is essential. Here, we report the design of carbon-supported Pt catalysts that can regenerate NAD(P)+ by proton-driven NAD(P)H oxidation with concurrent hydrogen formation. The carbon support was modified to tune the electronic nature of the Pt nanoparticles, and it was found that the best catalyst for NAD(P) regeneration (TOF = 581 h-1) was electron-rich Pt on carbon. Finally, the heterogeneous Pt catalyst was applied in the biocatalytic oxidation of a variety of alcohols catalyzed by different alcohol dehydrogenases. The Pt catalyst exhibited good compatibility with the biocatalytic system. Its NAD(P)+ regeneration function successfully supported biocatalytic conversion from alcohols to corresponding ketone or lactone products. This work provides a promising strategy for chemical synthesis NAD(P)+-dependent pathways utilizing a cooperative inorganic-enzymatic catalytic system.

High emission of carbon dioxide (CO2) has aroused global concern due to the 'greenhouse effect'. The conversion of CO2 to valuable chemicals/materials is an indispensable route toward 'carbon neutrality'. Enzyme-photo-coupled catalytic systems (EPCCSs), integrating synthetic library of semiconductor photocatalyst and natural database of enzyme, have emerged as a green and powerful platform toward CO2 conversion. Herein, we discuss the recent progress in design and application of EPCCSs for CO2 conversion from the perspective of pathway engineering, reaction engineering and system engineering. We firstly summarize the explored pathways of EPCCSs for converting CO2 to C1 and C2+ products. Secondly, we discuss the matching of kinetics between photocatalytic and enzymatic reactions in EPCCSs. Thirdly, we unveil the complex interplay between photocatalytic and enzymatic modules, and further demonstrate the strategy of compartmentalization to eliminate the negative interactions. Lastly, we conclude with the perspective on the opportunities and challenges of EPCCSs for CO2 conversion.

Immobilization is an effective method to promote the application of enzyme industry for improving the stability and realizing recovery of enzyme. To some extent, the performance of immobilized enzyme depends on the choice of carrier material. Therefore, the development of new carrier materials has been one of the key issues concerned by enzyme immobilization researchers. In this work, a novel organic–inorganic hybrid material, nickel-carnosine complex (NiCar), was synthesized for the first time by solvothermal method. The obtained NiCar exhibits spherical morphology, hierarchical porosity and abundant unsaturated coordination nickel ions, which provide excellent anchoring sites for the immobilization of proteins. His-tagged organophosphate-degrading enzyme (OpdA) and ω-transaminase (ω-TA) were used as model enzymes to evaluate the performance of NiCar as a carrier. By a simple adsorption process, the enzyme molecules can be fixed on the particles of NiCar, and the stability and reusability are significantly improved. The analysis of protein adsorption on NiCar verified that the affinity adsorption between the imidazole functional group on the protein and the unsaturated coordination nickel ions on NiCar was the main force in the immobilization process, which provided an idea way for the development of new enzyme immobilization carriers.

Carbonic anhydrase (CA) is a powerful biocatalyst for carbon dioxide (CO

Efficient chemical transformation in a green, low-carbon way is crucial for the sustainable development of modern society. Enzyme-photo-coupled catalytic systems (EPCS) that integrate the exceptional selectivity of enzyme catalysis and the unique reactivity of photocatalysis hold great promise in solar-driven 'molecular editing'. However, the involvement of multiple components and catalytic processes challenged the design of efficient and stable EPCS. To show a clear picture of the complex catalytic system, in this review, we analyze EPCS from the perspective of system engineering. First, we disintegrate the complex system into four elementary components, and reorganize these components into biocatalytic and photocatalytic ensembles (BE and PE). By resolving current accessible systems, we identify that connectivity and compatibility between BE and PE are two crucial factors that govern the performance of EPCS. Then, we discuss the origin of undesirable connectivity and low compatibility, and deduce the possible solutions. Based on these understandings, we propose the designing principles of EPCS. Lastly, we provide a future perspective of EPCS.

Exploring systems with distinct stimuli-response properties is vital for controlled release. In our study, a reaction-triggered system based on enzyme-encased capsules is constructed through mussel-inspired chemistry for controlled release of insulin (INS, a kind of protein hormone for diabetes mellitus treatment). In detail, glucose oxidase (GOD) and INS were first entrapped in CaCO3 particles through a co-precipitation method. Tannic acid (TA, a natural polyphenol) was adhered on the particle surface and conjugated with polyethyleneimine (PEI) through a Schiff base reaction and electrostatic interactions, thus acquiring TA–PEI (TP) capsules encasing GOD and INS. The GOD inside the capsules catalysed the oxidation of glucose to form gluconic acid, which caused the enrichment of protons (H+) around the capsules. The decrease of the pH value further broke the CN bond in the capsule wall, which led to the disassembly of the capsules and the release of INS. The capsular system could continuously release 73.1% of the INS in 3 h, and exhibited a specific response to glucose. Combined with the facile and mild preparation of the enzyme-encased capsules, it was expected that the as-constructed capsular system could be applied for the delivery and controlled release of a broad range of cargoes.

Albeit that photo-enzymatic catalysis has sparked more and more attention, its efficiency is restricted by lower electron transfer and poor compatibility between the natural enzyme and synthetic ph...

Carbonic anhydrase (CA) is an important carbon fixation enzyme. Immobilization of CA can expand its application in the realm of adsorption, catalysis, and so on. As a typical metal-free framework, hydrogen-bonded organic frameworks (HOFs) featuring mild synthesis process, exquisite framework structure and good enzyme compatibility have been used for enzyme embedding. However, the catalytic performance of CA-embedded HOFs (CA@HOFs) is limited by the micropore size of HOFs and the slow adsorption of CO2. Herein, CA@Lys-HOF-1 was synthesized by introducing lysine (Lys), a basic amino acid, during the coprecipitation of CA and HOFs for CO2 fixation. The addition of Lys enlarged the average pore size of HOF-1 from 1.8 to 3.2 nm, whereas the introduced -NH2 groups increased the initial adsorption of CO2 from 0.55 to 1.21 cm3 g-1. Compared to CA@HOF-1, the activity of CA@Lys-HOF-1 was enhanced by 71.25%, and the corresponding production of CaCO3 was enhanced by 12.7%. After eight reaction cycles, CA@Lys-HOF-1 still maintained an output of 9.97 mg of CaCO3 every 5 min, 83.7% of the initial production. It is hoped that the CA@Lys-HOF-1 reported offers a platform for efficient and continuous fixation of CO2.

A new integrated catalyst, Fe3O4@Cu/GMP–GOx, was successfully constructed by assembling Cu2+ and guanosine 5-monophosphate (GMP) on magnetic nanoparticles and in situ encapsulating glucose oxidase ...

Carbonic anhydrase (CA) as a typical metalloenzyme in biological system can accelerate the hydration/dehydration of carbon dioxide (CO2, the major components of greenhouse gases), which performer with high selectivity, environmental friendliness and superior efficiency. However, the free form of CA is quite expensive (~ RMB 3000/100 mg), unstable, and non-reusable as the free form of CA is not easy for recovery from the reaction environment, which severely limits its large-scale industrial applications. The immobilization may solve these problems at the same time. In this context, many efforts have been devoted to improving the chemical and thermal stabilities of CA through immobilization strategy. Very recently, a wide range of available inorganic, organic and hybrid compounds have been explored as carrier materials for CA immobilization, which could not only improve the tolerance of CA in hazardous environments, but also improve the efficiency and recovery to reduce the cost of large-scale application of CA. Several excellent reviews about immobilization methods and application potential of CA have been published. By contrast, in our review, we stressed on the way to better retain the biocatalytic activity of immobilized CA system based on different carrier materials and to solve the problems facing in practical operations well. The concluding remarks are presented with a perspective on constructing efficient CO2 conversion systems through rational combining CA and advanced carrier materials.

Wilm Jones received his PhD from Cardiff University; his research concerned photocatalytic hydrogen production using supported gold and gold alloy nanoparticles. He then worked at the UK Catalysis Hub on CO2 hydrogenation, followed by a research fellowship at the University of Aberdeen, working on photocatalytic NADH regeneration. Currently Wilm works as a research associate for UCL at the Research Complex at Harwell on a project developing photocatalytic materials for the depollution of air. Joseph Burnett is a final year PhD student at the University of Aberdeen, where his research is focused on heterogeneous systems, utilizing both supported metal catalysts and photocatalysts for the regeneration of the biocofactor NADH. He obtained his BS in chemistry from Manchester Metropolitan University, where his initial curiosity for catalysis was sparked, and later went on to study an MS in catalysis at Cardiff University. Jiafu Shi is an associate professor at School of Environmental Science and Engineering of Tianjin University. He obtained his PhD in chemical technology from Tianjin University. After graduation, he joined the faculty of Tianjin University and started working at the School of Environmental Science and Engineering. He was a visiting scholar at the University of California at Berkeley from 2016 to 2017. His research interests include biocatalysis, photo-biocatalysis, and hierarchically structured materials, which are related to energy and the environment. Russell Howe is a professor in materials chemistry at the University of Aberdeen. His research focuses on the use of spectroscopic methods to investigate catalysts and catalytic reaction mechanisms. Xiaodong Wang is a senior lecturer in chemical engineering at Lancaster University. Prior to this, he was a lecturer in chemical engineering at the University of Aberdeen. He obtained his PhD at Heriot-Watt University and completed both MS and BE studies at Tianjin University. Xiaodong’s research interests are heterogeneous catalysis and reaction engineering; his recent work focuses on the innovative use of heterogeneous catalysts (e.g., supported metals) in enzymatic transformations via cofactor regeneration.

Enzyme-photocoupled catalytic systems (EPCSs), combining the natural enzyme with a library of semiconductor photocatalysts, may break the constraint of natural evolution, realizing sustainable solar-to-chemical conversion and non-natural reactivity of the enzyme. The overall efficiency of EPCSs strongly relies on the shuttling of energy-carrying molecules, e.g., NAD

Chemoenzymatic catalysis inherits the attributes of enzymatic catalysis and chemical catalysis, where the efficiency is usually governed by the synergy of the two catalytic modules, particularly, t...

Porous carbon materials are highly attractive in the research field of adsorption, particularly, for treating organic pollutants in wastewater, of which the facile yet generic methods is highly pur...

Solar energy conversion by photocatalysis holds promise in energy supply, but its efficiency is hindered by the mismatch in charge generation, transfer, and utilization. In natural photosynthesis, ...

Metal–organic frameworks (MOFs) with tailored chemical compositions and topological structures have exhibited good application potential in the fields of adsorption, catalysis, and so on. In our st...

In-depth understanding and rational manipulation of the electron transfer process and molecule diffusion process are critical to promote the overall photocatalytic efficiency. In our study, core@shell photocatalysts that embody graphitic carbon nitride (GCN) core and amorphous titania (a-TiO 2) nanoshell are prepared to elucidate and coordinate the electron transfer and molecule diffusion for the regeneration of nicotinamide adenine dinucleotide (NADH) with [Cp*Rh(bpy)H 2O] 2+ as the redox mediator. The GCN core absorbs visible light to generate electron-hole pairs, whereas the a-TiO 2 nanoshell facilitates the transfer of photogenerated electrons from GCN to the a-TiO 2 surface for NADH regeneration, which also enables the diffusion of electron donor molecules (triethanolamine, TEOA) from the a-TiO 2 surface to GCN for consuming the holes left on GCN. The transfer of photogenerated electrons and the diffusion of electron donor molecules are coordinated by finely tuning the thickness of the a-TiO 2 nanoshell. Under the optimized nanoshell thickness of â¼2.1 nm, the GCN@a-TiO 2 photocatalyst exhibits the highest NADH regeneration yield of 82.1% after a 10 min reaction under LED light (405 nm), over 200% higher than that of the GCN photocatalyst. Combined with the highly controllable and mild features of the bioinspired mineralization method, our study may offer a facile and generic strategy to design high performance photocatalysts through rational coordination of different substances/species transport processes.

Microplastics (MPs), tiny particles broken down from larger pieces of plastics, have accumulated everywhere on the earth. As an inert carbon stream in aquatic environment, they have been reported as carriers for heavy metals and exhibit diverse interactive effects. However, these interactions are still poorly understood, especially mechanisms driving these interactions and how they pose risks on living organisms. In this mini review, a bibliometric analysis in this field was conducted and then the mechanisms driving these interactions were examined, especially emphasizing the important roles of microorganisms on the interactions. Their combined toxic effects and the potential hazards to human health were also discussed. Finally, the future research directions in this field were suggested. This review summarized the recent research progress in this field and highlighted the essential roles of the microbes on the interactions between MPs and heavy metals with the hope to promote more studies to unveil action mechanisms and reduce/eliminate the risks associated with MP presence.

Enclosed films, also called capsules, bearing an ultrathin and robust nanoshell have sparked much interest for use in many applications, for which facile preparation methods are urgently pursued. Inspired by the pH-programmed adhesion/cohesion of mussel-secreted foot proteins, polyphenol/polyamine capsules with an ultrathin and robust nanoshell are fabricated through a pH-switched assembly on sacrificial calcium carbonate (CaCO

Metal–organic frameworks (MOFs) for in situ enzyme encapsulation commonly possess weak metal–ligand coordination bonds and rather small pores, which are instable in aqueous solution and present rat...

Artificial photosynthesis holds promise in producing solar fuels and chemicals. Although encouraging achievements have been made in the development of catalysts for reaction/process modules in arti...

BACKGROUND: The enzymatic process in continuous flow reactors has become attractive owing to the merits of in‐line purification, improved mixing and mass transfer, etc. However, the construction of continuous flow reactors requires stable and surface‐active monolithic scaffolds for enzyme immobilization. RESULTS: In this study, nanofibers of linear polyethyleneimine (LPEI) are formed on the surface of poly(sodium 4‐styrenesulfonate) (PSS)‐treated cordierite honeycomb (named LPEI/PSS cordierite‐H) as monolithic scaffold for enzyme immobilization. The controlled self‐assembly of LPEI ensures the formation of nanofibers (diameters of 20–80 nm) on the surface of cordierite‐H, which roughens the surface and offers many active sites for enzyme loading. The electrostatic interaction between negatively charged enzyme and positively charged LPEI helps the enzyme firmly attach on the surface. The loading capacity of LPEI/PSS cordierite‐H was 1.24 mg g⁻¹. Horseradish peroxidase (HRP)‐loaded LPEI/PSS cordierite‐H (HRP@LPEI/PSS cordierite‐H) exhibited activity recovery of 55.33%, 2‐fold higher than that of HRP‐loaded branched polyethyleneimine (BPEI)/PSS cordierite‐H (HRP@BPEI/PSS cordierite‐H) (23.72%). Furthermore, a silica layer was formed on the surface of HRP@LPEI/PSS cordierite‐H through LPEI‐induced silicification, which could prevent the enzyme from deactivation under extreme conditions. CONCLUSION: These monolithic biocatalysts have great potential for applications in wastewater treatment and even in other fields such as pharmaceutical synthesis. © 2019 Society of Chemical Industry

Physical/chemical adsorption is well-known as a facile and effective method for enzyme immobilization, while ideal adsorbents with a high structural stability, high loading capacity, and low leaching ratio are still under exploration. In this study, nanoporous assemblies of two-dimensional (2D) copper phyllosilicate (L-CuSiO3) are prepared as an adsorbent to immobilize horseradish peroxidase (HRP) for phenol-containing wastewater treatment. Specifically, the robust chemical bonds of Si–O–Si and Si–O–Cu in L-CuSiO3 ensure its superior structural stability; the well-developed porous structure endows L-CuSiO3 assemblies with a high specific surface area of 611.7 cm3 g–1, which enables a fast and high enzyme loading of 140 mg g–1 within 4 h, and the well-distributed Cu(II) ions ensure the stable attachment of enzyme through Cu(II)-arginine (in HRP) coordination with a leaching ratio less than 10%. Meanwhile, the scaling assembly of L-CuSiO3 renders the resultant biocatalyst (HRP-loaded L-CuSiO3 assemblies) ea...

Herein, the first example of crackled organosilica nanocapsules (CONs) is reported to directly immobilize enzymes without any further chemical modification. Enzymes are adsorbed on both the exterior and interior surfaces of CONs, integrating the merits of adsorption and encapsulation. When used for Candida rugosa lipase (CRL) immobilization, the CONs displayed higher enzyme loading, lower enzyme leaching, and elevated enzyme activity, compared to the conventional non-crackled nanocapsules/particles.

Heterogeneous catalyst plays a dual role in the transesterification reaction owing to the advantages of separation and reusability. Recently, heterogeneous catalysts derived from renewable sources have gotten more attention. The renewable resources described include shells, bones, ashes from plant/tree, natural sources, large-scale industrial wastes, etc. Advantageously, catalysts prepared from these materials could make the biodiesel product more sustainable, environmentally friendly and cost-effective. The purpose of this work is to review some recent developments on the heterogeneous catalyst derived from renewable resource for the transesterification reaction. Furthermore, the current advances and the future perspectives of catalysts from renewable resources will be presented. Hopefully, this review will offer some perspective and guidelines of the future research and development for renewable resources derived catalysts.

Engineering MOFs nanocrystals into hierarchical/macroscopic structures is critical for many applications. However, defects between MOFs nanocrystals often exist due to the uncontrollable nucleation and growth in MOFs crystallization. In our study, inspired by biomineralization processes in nature, we report a facile and generic method to prepare polymer@MOFs capsules with defect-free MOFs layer through controlled interfacial mineralization. Specifically, zeolitic imidazolate framework-8 (ZIF-8) and polydopamine (PDA) capsules are used to prepare the polymer@MOFs capsules. The PDA capsules are exploited to confine Zn2+ ions within the capsule lumen and on the capsule wall. When incubated into a solution of 2-methylimidazole (2-MeIm), Zn2+ ions on the capsule wall will trigger the interfacial nucleation of ZIF-8, while Zn2+ ions in the capsule lumen will diffuse into the capsule wall and react with 2-MeIm, enabling the growth and formation of defect-free ZIF-8 nanolayer. The molecule-sieving property of polymer@MOFs capsules is tested by the controlled permeation of small molecules (methylene blue, 6.0 × 13.8 A2) through the capsule wall, conferring the enzyme-embedded polymer@MOFs capsules with the unique features of on/off control of enzymatic reactions over multiple reaction cycles, and high stability of entrapped enzymes against long-term storage. Through changing the species of polymer capsules, shapes of polymer capsules and species of MOFs, a series of polymer@MOFs capsules are prepared, highlighting the versatility and functionality extension of this interfacial mineralization method.

Nicotinamide cofactors (e.g., NADH) are essential hydrogen sources for the majority of enzyme reduction reactions. Currently, highly efficient and in situ cofactor regeneration is urgently required but remains challenging. In this study, red phosphorus quantum dots were decorated onto graphitic carbon nitride hollow tubes to prepare high-performance heterojunction photocatalyst (g-C3N4-HTs@rP-QDs) for visible-light-driven NADH regeneration. Energy band analysis combined with photoelectrochemical measurements demonstrates rP-QDs not only act as additional photosensitizers for charge generation but also constitute a type II heterojunction with g-C3N4-HTs for charge transfer, facilitating enrichment of electrons on the g-C3N4-HTs surface. Such enrichment of electrons for g-C3N4-HTs@rP-QDs offers ∼5 times higher reducing active sites than bulk g-C3N4 to trigger the NADH regeneration reaction under visible-light (LED, 405 nm) illumination, thus acquiring superior NADH regeneration efficiency with an initial re...

Inspired by the structure and function of chloroplast, an artificial photosynthetic alginate (ALG) capsule bearing carboxymethylcellulose (CMC) matric, red phosphorus quantum dots@g-C3N4 (P/CN) tubular photocatalysts, and alcohol dehydrogenase (ADH) is prepared for efficient and sustainable synthesis of methanol from formaldehyde. CMC liquid core resembles grana in the chloroplast to afford a favorable microenvironment for stabilizing ADH, whereas P/CN photocatalysts mimic thylakoid in chloroplast to supply nicotinamide adenine dinucleotide (NADH, the hydride donor) for triggering enzymatic hydrogenation. Moreover, P/CN photocatalysts reinforce the mechanical stability and thereby inhibit the swelling of ALG capsules, thus suppressing the leaching of P/CN photocatalysts and enzymes. The kinetic processes of photocatalytic regeneration and enzyme hydrogenation are investigated, respectively. The optimal coupling of photoenzyme reactions enabled by the capsules achieves the efficient and sustainable product...

Solar-driven photocatalytic regeneration of cofactors, including reduced nicotinamide adenine dinucleotide (NADH), reduced nicotinamide adenine dinucleotide phosphate (NADPH), and reduced flavin adenine dinucleotide (FADH 2 ), could ensure the sustainable energy supply of enzymatic reactions catalyzed by oxidoreductases for the efficient synthesis of chemicals. However, the elevation of cofactor regeneration efficiency is severely hindered by the inefficient utilization of electrons transferred on the surface of photocatalysts. Inspired by the phenomenon of ferredoxin-NADP + reductase (FNR) anchoring on thylakoid membrane, herein, a homogeneous catalyst of rhodium (Rh) complex, [Cp ∗ Rh(bpy)H 2 O] 2+ , was anchored on polymeric carbon nitride (PCN) mediated by a tannic acid/polyethyleneimine (TA/PEI) adhesive layer, acquiring PCN@TA/PEI-Rh core@shell photocatalyst. Illuminated by visible light, electrons were excited from the PCN core, then transferred through the TA/PEI shell, and finally captured by the surface-anchored Rh for instant utilization during the regeneration of NADH. The TA/PEI-Rh shell could facilitate the electron transfer from the PCN core and, more importantly, achieved ~1.3-fold elevation of electron utilization efficiency compared with PCN. Accordingly, the PCN@TA/PEI-Rh afforded the NADH regeneration efficiency of 37.8% after 20 min reaction under LED light (405 nm) illumination, over 1.5 times higher than PCN with free Rh. Coupling of the NADH regeneration system with formate dehydrogenase achieved continuous production of formate from carbon dioxide (CO 2 ). Our study may provide a generic and effective strategy to elevate the catalytic efficiency of a photocatalyst through intensifying the electron utilization.

Metal-organic frameworks (MOFs) have recently emerged as excellent hosting matrices for enzyme immobilization, offering superior physical and chemical protection for biocatalytic reactions. However, for multienzyme and cofactor-dependent biocatalysis, the subtle orchestration of enzymes and cofactors is largely disrupted upon immobilizing in the rigid crystalline MOF network, which leads to a much reduced biocatalytic efficiency. Herein, we constructed hierarchically porous MOFs by controlled structural etching to enhance multienzyme and cofactor-dependent enzyme biocatalysis. The expanded size of the pores can provide sufficient space for accommodated enzymes to reorientate and spread within MOFs in their lower surface energy state as well as to decrease the inherent barriers to accelerate the diffusion rate of reactants and intermediates. Moreover, the developed hierarchically porous MOFs demonstrated outstanding tolerance to inhospitable surroundings and recyclability.

Photoenzymatic coupled catalysis, integrating semiconductor photocatalysis and enzymatic catalysis, exhibits great potential for light-driven synthesis. To make photocatalyst and enzyme at play concertedly, nicotinamide-based cofactors have been widely used as electron carrier. However, these cofactors are easily oxidized into enzymatically inactive form by photo-generated holes. Herein, oxidation mechanism of NADH, one typical nicotinamide-based cofactor, by photo-generated holes was reported. With CdS, g-C3N4 and BiVO4 as hole generators, NADH is oxidized into NAD+ or fragmented into ADP-ribose derivatives through multi-step electron transfer. Importantly, fragmentation reaction is inhibited with dopamine and neutral red to coordinate electron transfer between NADH and photo-generated holes.

A mild and efficient method for the construction of robust organic–inorganic hybrid microcapsules was developed by merging of covalent cross-linking and biomimetic mineralization into a layer-by-layer (LBL) self-assembly process. The diatom cell-inspired microcapsule structure had a biocompatible inner organic layer which could create a suitable microenvironment for biologically active substances inside the microcapsules and an inorganic layer which could function as a supporting membrane to maintain the intact morphology of the microcapsules. When in 40% PSS solution, only 5% of the hybrid microcapsules were deformed indicating that the hybrid microcapsule had a higher mechanical stability. The combination of the advantages of both the organic layer and the inorganic layer was applied for the immobilization of catalase (CAT). After being reused 7 times, the CAT in the hybrid microcapsules retained 78% of its initial activity. A buffering effect was created by the capsule wall and the immobilized CAT had a higher pH stability than the free CAT. After storing for 45 days, the CAT in the hybrid microcapsules retained 78% of its initial activity. It is envisaged that the as-prepared hybrid microcapsules can be extended to many applications such as biocatalysis, drug/gene delivery and biosensor fields.