Carbonic Anhydrase-Embedded Hydrogen-Bonded Organic Frameworks Coating for Facilitated Offshore CO2 Fixation.

Exhausted emission of carbon dioxide (CO2 ) from ships or offshore platforms has become one of the major contributors to global carbon emissions. Enzymes such as carbonic anhydrase (CA) have been widely used for CO2 mineralization because of their high catalytic rate. However, CA in seawater is easy to inactivate and difficult to reuse. Immobilization would be a feasible solution to address the stability issue, which, however, may cause an increase of internal diffusion resistance and reduced catalytic activity. In this regard, design of high-performance biocatalysts for acquiring high catalytic activity and stability of CA is highly desirable. Herein, a monolithic catalyst of Filler-CA@Lys-HOF-1 (FCLH) was prepared by chemical sorption of CA on the surface of the Filler followed by the coating of Lys-HOF-1. The highest catalytic activity of FCLH was obtained by regulating the amount of HOF-1 monomer added. Due to the protection of Lys-HOF-1, the FCLH showed good tolerance against acidity and salinity, which could retain about 80.2 % of the original activity after 9 h incubation in simulated seawater. The catalytic activity of FCLH could retain 85.4 % of the initial activity after 10 cycles. Hopefully, our study can provide a promising biocatalyst for CO2 mineralization, which may drive down carbon emissions when used for CO2 capture and conversion on offshore platforms.

NADH Photosynthesis System with Affordable Electron Supply and Inhibited NADH Oxidation.

Photosynthesis offers a green approach for the recycling of nicotinamide cofactors primarily NADH in bio-redox reactions. Herein, we report an NADH photosynthesis system where the oxidation of biomass derivatives is designed as an electron supply module (ESM) to afford electrons and superoxide dismutase/catalase (SOD/CAT) cascade catalysis is designed as a reactive oxygen species (ROS) elimination module (REM) to inhibit NADH degradation. Glucose as the electron donor guarantees the reaction sustainability accompanied with oxidative products of gluconic acid and formic acid. Meanwhile, enzyme cascades of SOD/CAT greatly eliminate ROS, leading to a ≈2.00-fold elevation of NADH yield (61.1 % vs. 30.7 %). The initial reaction rate and turnover frequency (TOF) increased by 2.50 times and 2.54 times, respectively, compared with those systems without REM. Our study establishes a novel and efficient platform for NADH photosynthesis coupled to biomass-to-chemical conversion.

Thylakoid Membrane-Inspired Capsules with Fortified Cofactor Shuttling for Enzyme-Photocoupled Catalysis.

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+/NADH cofactor, between active centers of enzyme and photocatalyst. However, few efforts have been devoted to NAD+/NADH shuttling. Herein, we propose a strategy of constructing a thylakoid membrane-inspired capsule (TMC) with fortified and tunable NAD+/NADH shuttling to boost the enzyme-photocoupled catalytic process. The apparent shuttling number (ASN) of NAD+/NADH for TMC could reach 17.1, ∼8 times as high as that of non-integrated EPCS. Accordingly, our TMC exhibits a turnover frequency (TOF) of 38 000 ± 365 h-1 with a solar-to-chemical efficiency (STC) of 0.69 ± 0.12%, ∼6 times higher than that of non-integrated EPCS.

Enzyme-photo-coupled catalytic systems.

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.

Hierarchically Porous Biocatalytic MOF Microreactor as a Versatile Platform towards Enhanced Multienzyme and Cofactor-Dependent Biocatalysis.

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.

Bioinspired construction of multi-enzyme catalytic systems.

Enzyme catalysis, as a green, efficient process, displays exceptional functionality, adaptivity and sustainability. Multi-enzyme catalysis, which can accomplish the tandem synthesis of valuable materials/chemicals from renewable feedstocks, establishes a bridge between single-enzyme catalysis and whole-cell catalysis. Multi-enzyme catalysis occupies a unique and indispensable position in the realm of biological reactions for energy and environmental applications. Two complementary strategies, i.e., compartmentalization and substrate channeling, have been evolved by living organisms for implementing the complex in vivo multi-enzyme reactions (MERs), which have been applied to construct multi-enzyme catalytic systems (MECSs) with superior catalytic activity and stabilities in practical biocatalysis. This tutorial review aims to present the recent advances and future prospects in this burgeoning research area, stressing the features and applications of the two strategies for constructing MECSs and implementing in vitro MERs. The concluding remarks are presented with a perspective on the construction of MECSs through rational combination of compartmentalization and substrate channeling.

Coordination polymer nanocapsules prepared using metal-organic framework templates for pH-responsive drug delivery.

A facile, efficient, and versatile approach is presented to synthesize pH-responsive nanocapsules (∼120 nm) by combining the advantages of metal-organic frameworks (MOFs) and metal-organic thin films. ZIF-8 nanoparticles are used as templates on which a thin film coating of iron(III)-catechol complexes is derived from the coordination between dopamine-modified alginate (AlgDA) and iron(III) ions. After the template removal, nanocapsules with a pH-responsive wall are obtained. Doxorubicin (Dox), a typical anticancer drug, is first immobilized in ZIF-8 frameworks through coprecipitation and then encapsulated in nanocapsules after the removal of ZIF-8. The structure of the iron(III)-catechol complex varies with pH value, thus conferring the Dox@Nanocapsules with tailored release behavior in vitro. Cytotoxicity tests illustrate the highly effective cytotoxicity of Dox@Nanocapsules towards cancer cells. This study provides a new method for preparing smart nanocapsules and offers more opportunities for the controlled delivery of drugs.

In situ biosynthesis of ultrafine metal nanoparticles within a metal-organic framework for efficient heterogeneous catalysis.

The synthesis of ultrafine, uniform, well-dispersed functional nanoparticles (NPs) under mild conditions in a controlled manner remains a great challenge. In biological systems, a well-defined biomineralization process is exploited, in which the control over NPs' size, shape and distribution is temporally and spatially regulated by a variety of biomolecules in a confined space. Inspired by this, we embedded proteins into metal-organic frameworks (MOFs) and explored a novel approach to synthesize metallic NPs by taking the synergy of protein-induced biomineralization process and space-confined effect of MOFs. The generation and growth of ultrafine metal NPs (Ag or Au) was induced by the entrapped lysozyme molecules and confined by the ZIF-8 pores. Due to the narrow size distribution and homogeneous spatial distribution of metal NPs, the as-synthesized NPs exhibit remarkably elevated catalytic activity. These findings demonstrate that MOFs can be loaded with specific proteins to selectively deposit inorganic NPs via biomimetic mineralization and these novel kinds of nanohybrid materials may find applications in catalysis, sensing and optics.

Enzymatic conversion of carbon dioxide.

With the continuous increase in fossil fuels consumption and the rapid growth of atmospheric CO2 concentration, the harmonious state between human and nature faces severe challenges. Exploring green and sustainable energy resources and devising efficient methods for CO2 capture, sequestration and utilization are urgently required. Converting CO2 into fuels/chemicals/materials as an indispensable element for CO2 capture, sequestration and utilization may offer a win-win strategy to both decrease the CO2 concentration and achieve the efficient exploitation of carbon resources. Among the current major methods (including chemical, photochemical, electrochemical and enzymatic methods), the enzymatic method, which is inspired by the CO2 metabolic process in cells, offers a green and potent alternative for efficient CO2 conversion due to its superior stereo-specificity and region/chemo-selectivity. Thus, in this tutorial review, we firstly provide a brief background about enzymatic conversion for CO2 capture, sequestration and utilization. Next, we depict six major routes of the CO2 metabolic process in cells, which are taken as the inspiration source for the construction of enzymatic systems in vitro. Next, we focus on the state-of-the-art routes for the catalytic conversion of CO2 by a single enzyme system and by a multienzyme system. Some emerging approaches and materials utilized for constructing single-enzyme/multienzyme systems to enhance the catalytic activity/stability will be highlighted. Finally, a summary about the current advances and the future perspectives of the enzymatic conversion of CO2 will be presented.

Mask-Like Symmetrical Microclusters through a Diffusion-Limited Assembly Approach.

A diffusion-limited assembly approach was explored to fabricate symmetrical [Cu(Succinate)]n microclusters with a different shape and size for the first time. The molecular structure of succinate and its coordination reaction capability towards copper(II) ions governed the one-dimensional growth of the nanofibers and the concomitant formation of the microclusters. In detail, a symmetrical concentration gradient was formed around the endpoints of the nanofibers caused by the diffusion-limited process at high reactant concentrations. The concentration gradient forced the nanofibers to grow divergently and further aggregate into open microcluster structure. The shape and size of the microclusters could be tuned by altering the concentration of the reactants. Particularly, mask-like double-hole symmetrical microclusters (MDHSMs) were obtained when the concentration of both reactants was as high as 140 mM. The resultant MDHSMs showed high selectivity in adsorption of dyes and proteins, and may find potential applications in water treatment, bioseparation, and immobilization of biomacromolecules.

Design and synthesis of organic-inorganic hybrid capsules for biotechnological applications.

Organic-inorganic hybrid capsules, which typically possess a hollow lumen and a hybrid wall, have emerged as a novel and promising class of hybrid materials and have attracted enormous attention. In comparison to polymeric capsules or inorganic capsules, the hybrid capsules combine the intrinsic physical/chemical properties of the organic and inorganic moieties, acquire more degrees of freedom to manipulate multiple interactions, create hierarchical structures and integrate multiple functionalities. Thus, the hybrid capsules exhibit superior mechanical strength (vs. polymeric capsules) and diverse functionalities (vs. inorganic capsules), which may give new opportunities to produce high-performance materials. Much effort has been devoted to exploring innovative and effective methods for the synthesis of hybrid capsules that exhibit desirable performance in target applications. This tutorial review firstly presents a brief description of the capsular structure and hybrid materials in nature, then classifies the hybrid capsules into molecule-hybrid capsules and nano-hybrid capsules based upon the size of the organic and inorganic moieties in the capsule wall, followed by a detailed discussion of the design and synthesis of the hybrid capsules. For each kind of hybrid capsule, the state-of-the-art synthesis methods are described in detail and a critical comment is embedded. The applications of these hybrid capsules in biotechnological areas (biocatalysis, drug delivery, etc.) have also been summarized. Hopefully, this review will offer a perspective and guidelines for the future research and development of hybrid capsules.

Preparation of ultrathin, robust protein microcapsules through template-mediated interfacial reaction between amine and catechol groups.

A novel approach to the synthesis of protein microcapsules is developed through template-mediated interfacial reaction. Protein-doped CaCO3 templates are first synthetized via coprecipitation and then coated with a catechol-containing alginate (AlgDA) layer. Afterward, the templates are exposed to ethylenediamine tetraacetic acid disodium (EDTA) solution to dissolve CaCO3. During CaCO3 dissolution, the generated CO2 gas pushes protein molecules moving to the AlgDA layer, and thereby Michael addition and Schiff base reactions proceed, forming the shell of protein microcapsules. Three kinds of proteins, namely, bovine serum albumin, catalase, and protamine sulfate, are utilized. The shell thickness of microcapsule varies from 25 to 82 nm as the doping amount of protein increased from 2 to 6 mg per 66 mg CaCO3. The protein microcapsules have a robust but flexible shell and can be reversibly deformed upon exposure to osmotic pressure. The bioactivity of protein microcapsules is demonstrated through enzymatic catalysis experiments. The protein microcapsules remain about 80% enzymatic activity of the equivalent free protein. Hopefully, our approach could be extended to many other applications such as drug/gene delivery, tissue scaffolds, and catalysis due to the universality of Michael reaction and Schiff base reactions.

Synthesis of a Healthy Sweetener d-Tagatose from Starch Catalyzed by Semiartificial Cell Factories.

d-Tagatose is one of the several healthy sweeteners that can be a substitute for sucrose and fructose in our daily life. Whole cell-catalyzed phosphorylation and dephosphorylation previously reported by our group afford a thermodynamic-driven strategy to achieve tagatose production directly from starch with high product yields. Nonetheless, the poor structural stability of cells and difficulty in biocatalyst recycling restrict its practical application. Herein, an efficient and stable semiartificial cell factory (SACF) was developed by constructing an organosilica network (OSN) artificial shell on the cells bearing five thermophilic enzymes to produce tagatose. The OSN artificial shell, the thickness of which can be regulated by changing the tetraethyl silicate concentration, exhibited tunable permeability and superior mechanical strength. In contrast with cells, SACFs showed a relative activity of 99.5% and an extended half-life from 33.3 to 57.8 h. Over 50% of initial activity was retained after 20 reuses. The SACFs can catalyze seven consecutive reactions with tagatose yields of over 40.7% in field applications.

Hierarchically Structured CA@ZIF-8 Biohybrids for Carbon Dioxide Mineralization.

Carbonic anhydrase (CA) is a powerful biocatalyst for carbon dioxide (CO2) mineralization, of which immobilization is usually used for maintaining its catalytic activity against harsh external stimuli. However, the incorporated materials for CA immobilization would commonly increase the internal diffusion resistance during the catalytic process, thereby decreasing the catalytic efficiency. In our study, poly-L-glutamic acid (PLGA) as the structure regulator was used to induce the synthesis of CA@zeolitic imidazolate framework-8 (CA@ZIF-8) biohybrids. The introduction of PLGA that could coordinate with Zn2+ interfered the crystallization of ZIF-8, thereby changing the morphological structure of CA@ZIF-8 biohybrids. With the increase of PLGA amount from 0 to 60 mg, PLGA(x)-CA@ZIF-8 biohybrids were gradually transformed from a dodecahedron structure to a 3D lamellar nano-flower structure, which caused elevated exposed surface area. Accordingly, the loading ratio was increased from 34.6 to 49.8 mg gcat-1, while the catalytic activity was elevated from 20.6 to 23.4%. The CO2 conversion rate was enhanced by nearly two folds compared to PLGA(0)-CA@ZIF-8 under the optimized condition. The final CaCO3 yield could reach 5.6 mg mgcat-1, whereas the reaction system could remain above 80% of the initial reaction activity after 8 cycles.

Modulating Catalytic Activity and Stability of Atomically Precise Gold Nanoclusters as Peroxidase Mimics via Ligand Engineering.

Metal nanoclusters (NCs), composed of a metal core and protecting ligands, show promising potentials as enzyme mimics for producing fuels, pharmaceuticals, and valuable chemicals, etc. Herein, we explore the critical role of ligands in modulating the peroxidase mimic activity and stability of Au NCs. A series of Au15(SR)13 NCs with various thiolate ligands [SR = N-acetyl-l-cysteine (NAC), 3-mercaptopropionic acid (MPA), or 3-mercapto-2-methylpropanoic acid (MMPA)] are utilized as model catalysts. It is found that Au15(NAC)13 shows higher structural stability than Au15(MMPA)13 and Au15(MPA)13 against external stimuli (e.g., pH, oxidants, and temperature) because of the intramolecular hydrogen bonds. More importantly, detailed enzymatic kinetics data show that the catalytic activity of Au15(NAC)13 is about 4.3 and 2.7 times higher than the catalytic activity of Au15(MMPA)13 and Au15(MPA)13, respectively. Density functional theory (DFT) calculations reveal that the Au atoms on the motif of Au NCs should be the active centers, whereas the superior peroxidase mimic activity of Au15(NAC)13 should originate from the emptier orbitals of Au atoms because of the electron-withdrawing effect of acetyl amino group in NAC. This work demonstrates the ligand-engineered electronic structure and functionality of atomically precise metal NCs, which afford molecular and atomic level insights for artificial enzyme design.

The influence of the discharging sewage on microbial diversity in sludge from Dongting Lake.

Human activities have a tremendous impact not only on the macroscopic world, but also on the micro-organisms. Here, Amplified Ribosomal DNA Restriction Analysis (ARDRA) was used for assessing the effect of the industrial sewage on the microbial community in sludge of Dongting Lake, the second-largest freshwater lake in China. The sludge samples from the outfall of the representative nitrogenous fertilizer plant near the lake were collected in March, 2010, and the sludge samples from the surrounding waters were treated as the control. The multi-element analysis results showed that the content of nitrogen, phosphorus in Sample SY were 1.9 and 1.47 times of the control group respectively. Based on restriction patterns derived from ARDRA, 26 representative clones (15 clones in the SY group and 11 clones in the DZ group) were sequenced. The sequence data and phylogenetic analysis of 16S rRNA gene presented that microorganism diversity of two sludge samples were abundant. Bacterial diversity presented among the outfall samples was dominated by Aeromonas sp. (5.8%), Acidimicrobidae sp. (5.8%) and Gemmatimonas sp. (5.0%). In contrast, bacterial diversity presented among the control group was dominated by Xanthomonas sp. (8.0%), Lautropia sp. (5.8%) and Duganella sp. (5.1%). The results indicated that due to the excessive of nitrogen and phosphorus discharged by the nitrogen fertilizer plant, the eutrophication in Dongting Lake has great influence on the microbial community structure.

General framework for enzyme-photo-coupled catalytic system toward carbon dioxide conversion.

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.

Supported Pt Enabled Proton-Driven NAD(P)+ Regeneration for Biocatalytic Oxidation.

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 via NAD(P)+-dependent pathways utilizing a cooperative inorganic-enzymatic catalytic system.

Interactions Between Microplastics and Heavy Metals in Aquatic Environments: A Review.

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.

Intensifying Electron Utilization by Surface-Anchored Rh Complex for Enhanced Nicotinamide Cofactor Regeneration and Photoenzymatic CO2 Reduction.

Solar-driven photocatalytic regeneration of cofactors, including reduced nicotinamide adenine dinucleotide (NADH), reduced nicotinamide adenine dinucleotide phosphate (NADPH), and reduced flavin adenine dinucleotide (FADH2), 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)H2O]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 (CO2). Our study may provide a generic and effective strategy to elevate the catalytic efficiency of a photocatalyst through intensifying the electron utilization.