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.

Covalent organic framework membranes for efficient separation of monovalent cations.

Covalent organic frameworks (COF), with rigid, highly ordered and tunable structures, can actively manipulate the synergy of entropic selectivity and enthalpic selectivity, holding great potential as next-generation membrane materials for ion separations. Here, we demonstrated the efficient separation of monovalent cations by COF membrane. The channels of COF membrane are decorated with three different kinds of acid groups. A concept of confined cascade separation was proposed to elucidate the separation process. The channels of COF membrane comprised two kinds of domains, acid-domains and acid-free-domains. The acid-domains serve as confined stages, rendering high selectivity, while the acid-free-domains preserve the pristine channel size, rendering high permeation flux. A set of descriptors of stage properties were designed to elucidate their effect on selective ion transport behavior. The resulting COF membrane acquired high ion separation performances, with an actual selectivity of 4.2-4.7 for K+/Li+ binary mixtures and an ideal selectivity of ~13.7 for K+/Li+.

Missing-linker Defects in Covalent Organic Framework Membranes for Efficient CO2 Separation.

Covalent organic framework (COF) membranes with tunable ordered channels and free organic groups hold great promise in molecular separations owing to the synergy of physical and chemical microenvironments. Herein, we develop a defect engineering strategy to fabricate COF membranes for efficient CO2 separation. Abundant amino groups are in situ generated on the COF nanosheets arising from the missing-linker defects during the reactive assembly of amine monomer and mixed aldehyde monomers. The COF nanosheets are assembled to fabricate COF membranes. Amino groups, as the CO2 facilitated transport carriers, along with ordered channels endow COF membrane with high CO2 permeances exceeding 300 GPU and excellent separation selectivity of 80 for CO2 /N2 , and 54 for CO2 /CH4 mixed gas under humidified state. Our defect engineering strategy offers a facile approach to generating free organic functional groups in COF membranes and other organic framework membranes for diverse chemical separations.

MOF-COF "Alloy" Membranes for Efficient Propylene/Propane Separation.

Molecular-sieving membranes from metal-organic frameworks (MOFs) are promising candidates for separating olefin/paraffin mixtures, a critical demand in sustainable chemical processes and a grand challenge in molecular separation. Currently, the inherent lattice flexibility of MOFs severely compromises their precise sieving ability. Here, a proof-of-concept of "alloy" membranes (AMs), which are fabricated by incorporating quaternary ammonium (QA)-functionalized covalent organic frameworks (COFs) into a zeolitic imidazolate framework-8 (ZIF-8) matrix is demonstrated. The Coulomb force between the COFs and the ZIF-8 restricts the linker rotation of the ZIF-8, generating a distinct alloying effect, by which the lattice rigidity of ZIF-8 can be conveniently tuned through varying the content of the COFs, similar to the flexible-to-rigid transition in aluminum alloy manufacturing. Such an alloying effect confers the AM's superior propylene/propane separation performance, with a propylene/propane separation factor surpassing 200 and a propylene permeance of 168 GPU. Hopefully, the AMs concept and the concomitant alloying effect can update the connotation of mixed matrix membranes and stimulate the re-envisioning about the design paradigm and development of advanced membranes for energy-efficient separations.

Oil-Water-Oil Triphase Synthesis of Ionic Covalent Organic Framework Nanosheets.

Ionic covalent organic framework nanosheets (iCOFNs) with long-range ordered and mono-dispersed ionic groups hold great potential in many advanced applications. Considering the inherent drawbacks of oil-water biphase method, herein, we explore an oil-water-oil triphase method based on phase engineering strategy for the bottom-up synthesis of iCOFNs. The middle water phase serves as a confined reaction region, and the two oil phases are reservoirs for storing and supplying monomers to the water phase. A large aqueous space and low monomer concentration lead to the anisotropic gradual growth of iCOFNs into few-layer thickness, large lateral size, and high crystallinity. Notably, the resulting three cationic and anionic iCOFNs exhibit ultra-high aspect ratios of up to 20,000. We further demonstrate their application potential by processing into ultrathin defect-free COF membranes for efficient biogas separation. Our triphase method may offer an alternative platform technology for the synthesis and innovative applications of iCOFNs.

Membrane-Based Olefin/Paraffin Separations.

Efficient olefin/paraffin separation is a grand challenge because of their similar molecular sizes and physical properties, and is also a priority in the modern chemical industry. Membrane separation technology has been demonstrated as a promising technology owing to its low energy consumption, mild operation conditions, tunability of membrane materials, as well as the integration of physical and chemical mechanisms. In this work, inspired by the physical mechanism of mass transport in channel proteins and the chemical mechanism of mass transport in carrier proteins, recent progress in channel-based and carrier-based membranes toward olefin/paraffin separations is summarized. Further, channel-based membranes are categorized into membranes with network structures and with framework structures according to the morphology of channels. The separation mechanisms, separation performance, and membrane stability in channel-based and carrier-based membranes are elaborated. Future perspectives toward membrane-based olefin/paraffin separation are proposed.

Total synthesis of a functional designer eukaryotic chromosome.

Rapid advances in DNA synthesis techniques have made it possible to engineer viruses, biochemical pathways and assemble bacterial genomes. Here, we report the synthesis of a functional 272,871-base pair designer eukaryotic chromosome, synIII, which is based on the 316,617-base pair native Saccharomyces cerevisiae chromosome III. Changes to synIII include TAG/TAA stop-codon replacements, deletion of subtelomeric regions, introns, transfer RNAs, transposons, and silent mating loci as well as insertion of loxPsym sites to enable genome scrambling. SynIII is functional in S. cerevisiae. Scrambling of the chromosome in a heterozygous diploid reveals a large increase in a-mater derivatives resulting from loss of the MATα allele on synIII. The complete design and synthesis of synIII establishes S. cerevisiae as the basis for designer eukaryotic genome biology.