Thermo‐Osmotic Energy Conversion Enabled by Covalent‐Organic‐Framework Membranes with Record Output Power DensityZuo, Xiuhui; Zhu, Changjia; Xian, Weipeng; Meng, Qing‐Wei; Guo, Qing; Zhu, Xincheng; Wang, Sai; Wang, Yeqing; Ma, Shengqian; Sun, Qi
doi: 10.1002/anie.202116910pmid: 35179288
A vast amount of energy can be extracted from the untapped low‐grade heat from sources below 100 °C and the Gibbs free energy from salinity gradients. Therefore, a process for simultaneous and direct conversion of these energies into electricity using permselective membranes was developed in this study. These membranes screen charges of ion flux driven by the combined salinity and temperature gradients to achieve thermo‐osmotic energy conversion. Increasing the charge density in the pore channels enhanced the permselectivity and ion conductance, leading to a larger osmotic voltage and current. A 14‐fold increase in power density was achieved by adjusting the ionic site population of covalent organic framework (COF) membranes. The optimal COF membrane was operated under simulated estuary conditions at a temperature difference of 60 K, which yielded a power density of ≈231 W m−2, placing it among the best performing upscaled membranes. The developed system can pave the way to the utilization of the enormous supply of untapped osmotic power and low‐grade heat energy, indicating the tremendous potential of using COF membranes for energy conversion applications.
Selectively Regulating Lewis Acid–Base Sites in Metal–Organic Frameworks for Achieving Turn‐On/Off of the Catalytic Activity in Different CO2 ReactionsTian, Xue‐Rui; Jiang, Xiao‐Lei; Hou, Sheng‐Li; Jiao, Zhuo‐Hao; Han, Jie; Zhao, Bin
doi: 10.1002/anie.202200123pmid: 35199447
Regulating Lewis acid–base sites in catalysts to investigate their influence in the chemical fixation of CO2 is significant but challenging. A metal–organic framework (MOF) with open metal Co sites, {(NH2Me2)[Co3(μ3‐OH)(BTB)2(H2O)]⋅9 H2O⋅5 DMF}n (1), was obtained and the results of the catalytic investigation show that 1 can catalyze cycloaddition of CO2 and aziridines to give 99 % yield. The efficiency of the cyclization of CO2 with propargyl amines is only 32 %. To improve the catalytic ability of 1, ligand XN with Lewis base sites was introduced into 1 and coordinated with the open Co sites, resulting in a decrease of the Lewis acid sites and an increase in the Lewis base sites in a related MOF 2 ({(NH2Me2)[Co3(μ3‐OH)(NHMe2)(BTB)2(XN)]⋅8 H2O⋅4 DMF}n). Selective regulation of the type of active centers causes the yield of oxazolidinones to be enhanced by about 2.4 times, suggesting that this strategy can turn on/off the catalytic activity for different reactions. The catalytic results from 2 treated with acid solution support this conclusion. This work illuminates a MOF‐construction strategy that produces efficient catalysts for CO2 conversion.
Out‐of‐Equilibrium Self‐Replication Allows Selection for Dynamic Kinetic Stability in a System of Competing ReplicatorsLiu, Bin; Wu, Juntian; Geerts, Marc; Markovitch, Omer; Pappas, Charalampos G.; Liu, Kai; Otto, Sijbren
doi: 10.1002/anie.202117605pmid: 35179808
Among the key characteristics of living systems are their ability to self‐replicate and the fact that they exist in an open system away from equilibrium. Herein, we show how the outcome of the competition between two self‐replicators, differing in size and building block composition, is different depending on whether the experiments are conducted in a closed vial or in an open and out‐of‐equilibrium replication–destruction regime. In the closed system, the slower replicator eventually prevails over the faster competitor. In a replication‐destruction regime, implemented through a flow system, the outcome of the competition is reversed and the faster replicator dominates. The interpretation of the experimental observations is supported by a mass‐action‐kinetics model. These results represent one of the few experimental manifestations of selection among competing self‐replicators based on dynamic kinetic stability and pave the way towards Darwinian evolution of abiotic systems.
Diversifying Nanoparticle Superstructures and Functions Enabled by Translative Templating from Supramolecular PolymerizationLiu, Jiaming; Liu, Rongjuan; Li, Hui; Zhang, Fenghua; Yao, Qingyuan; Wei, Jingjing; Yang, Zhijie
doi: 10.1002/anie.202201426pmid: 35179293
Biology exploits a transcription–translation approach to deliver structural information from DNA to the protein‐building machines with high precision. Here, we show how the structural information of small synthetic molecules could be used to guide the assembly of inorganic nanoparticles into diversified yet long‐range ordered superstructures, enabling the information transfer across four or five orders of magnitude in length scale. We designed three perylene diimide (PDI) based isomers differing by their site‐specific substitutions of the methyl group, which were able to supramolecularly polymerize into diverse structures. Importantly, coassembly of these PDI isomers with nanoparticles (NPs) could produce diverse long‐range ordered nanoparticle superstructures, including one‐dimensional NPs chains, double helical NPs assemblies and two‐dimensional NPs superlattices. Equally important, we demonstrate that the information originated from small molecules could diversify the functions of the self‐assembled nanocomposites.
Azulene‐Embedded [n]Helicenes (n=5, 6 and 7)Duan, Chao; Zhang, Jianwei; Xiang, Junjun; Yang, Xiaodi; Gao, Xike
doi: 10.1002/anie.202201494pmid: 35191154
Azulene is a non‐benzenoid aromatic building block with unique chemical structure and physicochemical properties. By using the “bottom‐up” synthetic strategy, we synthesized three azulene‐embedded [n]helicenes ([n]AzHs, n=5, 6 and 7), in which one terminal azulene subunit was fused with n‐2 benzene rings. P‐ and M‐enantiomers were observed in the packing diagrams of [5]‐, and [6]AzHs. However, P‐ and M‐[7]AzHs could be isolated by recrystallization of the racemic mixture. These [n]AzHs were endowed with new properties through the azulene moiety such as low‐lying first electric state (S1), small optical energy gap and anti‐Kasha emission. [6]‐, and [7]AzHs exhibit strong chiroptical responses with high absorption dissymmetry factor (gabs) maxima of about 0.02, which is among the highest |gabs| values of helicenes in the visible range. These azulene‐embedded [n]helicenes contribute to the non‐benzenoid helicene library and allow the structure–property relationships to be better understood.
Profiling of the ADP‐Ribosylome in Living CellsLehner, Maike; Rieth, Sonja; Höllmüller, Eva; Spliesgar, Daniel; Mertes, Bastian; Stengel, Florian; Marx, Andreas
doi: 10.1002/anie.202200977pmid: 35188710
Post‐translational modification (PTM) with ADP‐ribose and poly(ADP‐ribose) using nicotinamide adenine dinucleotide (NAD+) as substrate is involved in the regulation of numerous cellular pathways in eukaryotes, notably the response to DNA damage caused by cellular stress. Nevertheless, due to intrinsic properties of NAD+ e.g., high polarity and associated poor cell passage, these PTMs are difficult to characterize in cells. Here, two new NAD+ derivatives are presented, which carry either a fluorophore or an affinity tag and, in combination with developed methods for mild cell delivery, allow studies in living human cells. We show that this approach allows not only the imaging of ADP‐ribosylation in living cells but also the proteome‐wide analysis of cellular adaptation by protein ADP‐ribosylation as a consequence of environmental changes such as H2O2‐induced oxidative stress or the effect of the approved anti‐cancer drug olaparib. Our results therefore pave the way for further functional and clinical studies of the ADP‐ribosylated proteome in living cells in health and disease.
Real‐Time Monitoring of Dynamic Microbial Fe(III) Respiration Metabolism with a Living Cell‐Compatible Electron‐Sensing ProbeChen, Na; Du, Na; Wang, Wenjie; Liu, Tiangang; Yuan, Quan; Yang, Yanbing
doi: 10.1002/anie.202115572pmid: 35212095
Monitoring microbial metabolism is vital for biomanufacturing processes optimization. However, it remains a grand challenge to offer insight into microbial metabolism due to particularly complex and dynamic processes. Here, we report an electron‐sensing probe Zn2GeO4:Mn@Fe3+ for real‐time and dynamic monitoring of Fe(III) respiration metabolism. The quenched persistent luminescence of Zn2GeO4:Mn@Fe3+ is recovered when Fe3+ accepted electrons from the dynamic Fe(III) respiration metabolism, enabling the real‐time monitoring of microbial metabolism. The probe shows the capability to verify the role of related biomolecules in microbial Fe(III) respiration metabolism, to track the dynamic Fe(III) respiration metabolic response to environmental stress and microbial co‐culture interactions. Furthermore, the Zn2GeO4:Mn@Fe3+ probe provides guidance for improving biosynthesis efficiency by monitoring Fe redox recycling in microbial co‐culture.