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•Engineered cell experiences metabolic imbalance with reduced fitness.•Overproduction phenotype requires dynamic redistribution of cellular resource.•Metabolite-responsive TFs rewired ...to sense the fluctuating environment.•Self-adaptive and autonomous control to achieve dynamic activity compensation.•Synchronize cell activity by engineering cheater-killer and quorum-sensing circuits.
Engineered microbial cell factories are constantly experiencing metabolic imbalance due to nutrients depletion, metabolites buildup, evolutionary pressure or genetic instability. It is important to equip the engineered cell factory with sensor-regulator system to enable cell adjust metabolism and respond to the changing environment. Dynamically allocating cellular resources and optimally controlling pathway expression have proved as promising strategies to manage the tradeoff between cell growth and product formation as well as improve the cost-competitiveness of industrial fermentation. With metabolite-responsive transcriptional factors as basic tools, metabolic engineers are well positioned to engineer robust cell factories that achieve self-adaptation or autonomous control for both biotechnological and biomedical applications. In this review, we present promising dynamic control strategies that have been successfully applied to pathway optimization and chemical manufacturing.
Transition-metal-catalyzed decarbonylation via carbon-carbon bond cleavage is an essential synthetic methodology. Given the ubiquity of carbonyl compounds, the selective decarbonylative process ...offers a distinct synthetic strategy using carbonyl groups as "traceless handles". This reaction has been significantly developed in recent years in many respects, including catalytic system development, mechanistic understanding, substrate scope, and application in the synthesis of complex functional molecules. Therefore, this review aims to summarize the recent progress on transition-metal-catalyzed decarbonylative process, from the discovery of new transformations to the understanding of reaction mechanisms, to reveal the great achievements and potentials in this field. The contents of this review are categorized by the type of chemical bond cleavage in the decarbonylative process. The main challenges and opportunities of the decarbonylative process are also examined with the goal of expanding the application range of decarbonylation reactions.
This paper investigates the optimal power allocation scheme for sum throughput maximization of non-orthogonal multiple access (NOMA) system with α-fairness. In contrast to the existing fairness NOMA ...models, α-fairness can only utilize a single scalar to achieve different user fairness levels. Two different channel state information at the transmitter (CSIT) assumptions are considered, namely, statistical and perfect CSIT. For statistical CSIT, fixed target data rates are predefined, and the power allocation problem is solved for sum throughput maximization with α-fairness, through characterizing several properties of the optimal power allocation solution. For perfect CSIT, the optimal power allocation is determined to maximize the instantaneous sum rate with α-fairness, where user rates are adapted according to the instantaneous channel state information (CSI). In particular, a simple alternate optimization algorithm is proposed, which is demonstrated to yield the optimal solution. Numerical results reveal that, at the same fairness level, NOMA significantly outperforms the conventional orthogonal multiple access for both the scenarios with statistical and perfect CSIT.
With the increasing concerns about chemical pollution and sustainability of resources, among the significant challenges facing synthetic chemists are the development and application of elegant and ...efficient methods that enable the concise synthesis of natural products, drugs, and related compounds in a step-, atom- and redox-economic manner. One of the most effective ways to reach this goal is to implement reaction cascades that allow multiple bond-forming events to occur in a single vessel. This Account documents our progress on the rational design and strategic application of asymmetric catalytic cascade reactions in constructing diverse scaffolds and synthesizing complex chiral molecules. Our research is aimed at developing robust cascade reactions for the systematic synthesis of a range of interesting molecules that contain structural motifs prevalent in natural products, pharmaceuticals, and biological probes. The strategies employed to achieve this goal can be classified into three categories: bifunctional base/Brønsted acid catalysis, covalent aminocatalysis/N-heterocyclic carbene catalysis, and asymmetric organocatalytic relay cascades. By the use of rationally designed substrates with properly reactive sites, chiral oxindole, chroman, tetrahydroquinoline, tetrahydrothiophene, and cyclohexane scaffolds were successfully assembled under bifunctional base/Brønsted acid catalysis from simple and readily available substances such as imines and nitroolefins. We found that some of these reactions are highly efficient since catalyst loadings as low as 1 mol % can promote the multistep sequences affording complex architectures with high stereoselectivities and yields. Furthermore, one of the bifunctional base/Brønsted acid-catalyzed cascade reactions for the synthesis of chiral cyclohexanes has been used as a key step in the construction of the tetracyclic core of lycorine-type alkaloids and the formal synthesis of α-lycorane. Guided by the principles of covalent aminocatalysis and N-heterocyclic carbene catalysis, we synthesized chiral piperidine, indole, and cyclobutane derivatives. The synthesis of chiral cyclobutanes and pyrroloindolones showed unprecedented reactivity of substrates and catalysts. The development of the strategy of asymmetric organocatalytic relay cascades has provided a useful tool for the controlled synthesis of specific diastereomers in complex molecules. This Account gives a panoramic view and the logic of our research on the design, development, and applications of asymmetric catalytic cascade reactions that will potentially provide useful insights into exploring new reactions.
Nitrogen is the main limiting nutrient after carbon, hydrogen and oxygen for photosynthetic process, phyto-hormonal, proteomic changes and growth-development of plants to complete its lifecycle. ...Excessive and inefficient use of N fertilizer results in enhanced crop production costs and atmospheric pollution. Atmospheric nitrogen (71%) in the molecular form is not available for the plants. For world's sustainable food production and atmospheric benefits, there is an urgent need to up-grade nitrogen use efficiency in agricultural farming system. The nitrogen use efficiency is the product of nitrogen uptake efficiency and nitrogen utilization efficiency, it varies from 30.2 to 53.2%. Nitrogen losses are too high, due to excess amount, low plant population, poor application methods etc., which can go up to 70% of total available nitrogen. These losses can be minimized up to 15-30% by adopting improved agronomic approaches such as optimal dosage of nitrogen, application of N by using canopy sensors, maintaining plant population, drip fertigation and legume based intercropping. A few transgenic studies have shown improvement in nitrogen uptake and even increase in biomass. Nitrate reductase, nitrite reductase, glutamine synthetase, glutamine oxoglutarate aminotransferase and asparagine synthetase enzyme have a great role in nitrogen metabolism. However, further studies on carbon-nitrogen metabolism and molecular changes at omic levels are required by using "whole genome sequencing technology" to improve nitrogen use efficiency. This review focus on nitrogen use efficiency that is the major concern of modern days to save economic resources without sacrificing farm yield as well as safety of global environment, i.e. greenhouse gas emissions, ammonium volatilization and nitrate leaching.
Quick capacity loss due to the polysulfide shuttle effects and poor rate performance caused by low conductivity of sulfur have always been obstacles to the commercial application of lithium sulfur ...batteries. Herein, an in‐situ doped hierarchical porous biochar materials with high electron‐ion conductivity and adjustable three‐dimensional (3D) macro‐meso‐micropore is prepared successfully. Due to its unique physical structure, the resulting material has a specific surface area of 2124.9 m2 g−1 and a cumulative pore volume of 1.19 cm3 g−1. The presence of micropores can effectively physically adsorb polysulfides and mesopores ensure the accessibility of lithium ions and active sites and give the porous carbon material a high specific surface area. The large pores provide channels for the storage of electrolyte and the transmission of ions on the surface of the substrate. The combined effect of these three kinds of pores and the N doping formed in‐situ can effectively promote the cycle and rate performance of the battery. Therefore, prepared cathode can still reach a reversible discharge capacity of 616 mAh g−1 at a rate of 5 C. After 400 charge–discharge cycles at 1 C, the reversible capacity is maintained at 510.0 mAh g−1. This new strategy has provided a new approach to the research and industrial‐scale production of adjustable hierarchical porous biochar materials.
Tremella is utilized as the precursor, a new process method (high‐shear, freeze‐drying and chemical activation are used in turn) is proposed, and an in‐situ doped hierarchical porous biochar materials with adjustable 3D macro‐meso‐micropore is prepared successfully. Due to its unique physical structure, prepared cathode can still reach a reversible discharge capacity of 616 mAh g−1 at a rate of 5 C. After 400 charge‐discharge cycles at 1 C, the reversible capacity is maintained at 510.0 mAh g−1.
In December 2019, an outbreak of severe acute respiratory syndrome coronavirus 2 infection occurred in Wuhan, Hubei Province, China, and spread across China and beyond. On February 12, 2020, the ...World Health Organization officially named the disease caused by the novel coronavirus as coronavirus disease 2019 (COVID-19). Because most patients infected with COVID-19 had pneumonia and characteristic CT imaging patterns, radiologic examinations have become vital in early diagnosis and the assessment of disease course. To date, CT findings have been recommended as major evidence for clinical diagnosis of COVID-19 in Hubei, China. This review focuses on the etiology, epidemiology, and clinical symptoms of COVID-19 while highlighting the role of chest CT in prevention and disease control.
Herein we describe a mild method for the dual C(sp3)−H bond functionalization of saturated nitrogen‐containing heterocycles through a sequential visible‐light photocatalyzed dehydrogenation/2+2 ...cycloaddition procedure. As a complementary approach to the well‐established use of iminium ion and α‐amino radical intermediates, the elusive cyclic enamine intermediates were effectively generated by photoredox catalysis under mild conditions and efficiently captured by acetylene esters to form a wide array of bicyclic amino acid derivatives, thus enabling the simultaneous functionalization of two vicinal C(sp3)−H bonds.
A great team: A dual C(sp3)−H bond functionalization strategy was developed by merging dehydrogenation under visible‐light photocatalysis with a 2+2 cycloaddition reaction in a sequential process. This method enabled cyclobutene rings to be fused to various saturated nitrogen‐containing heterocycles to produce a series of cyclic amino acid derivatives.
Designing highly efficient electrocatalysts for oxygen evolution reaction (OER) plays a key role in the development of various renewable energy storage and conversion devices. In this work, we ...developed metallic Co4N porous nanowire arrays directly grown on flexible substrates as highly active OER electrocatalysts for the first time. Benefiting from the collaborative advantages of metallic character, 1D porous nanowire arrays, and unique 3D electrode configuration, surface oxidation activated Co4N porous nanowire arrays/carbon cloth achieved an extremely small overpotential of 257 mV at a current density of 10 mA cm−2, and a low Tafel slope of 44 mV dec−1 in an alkaline medium, which is the best OER performance among reported Co‐based electrocatalysts to date. Moreover, in‐depth mechanistic investigations demonstrate the active phases are the metallic Co4N core inside with a thin cobalt oxides/hydroxides shell during the OER process. Our finding introduces a new concept to explore the design of high‐efficiency OER electrocatalysts.
Metallic Co4N porous nanowire arrays activated by surface oxidation are shown to be highly efficient OER electrocatalysts. Benefiting from multiple synergistic effects of metallic character, 1D porous nanowire structure, and unique 3D electrode configuration, Co4N NW/CC achieves the best OER performance among well‐developed Co‐based electrocatalysts to date.
A synergistic catalytic method combining photoredox catalysis, hydrogen‐atom transfer, and proton‐reduction catalysis for the dehydrogenative silylation of alkenes was developed. With this approach, ...a highly concise route to substituted allylsilanes has been achieved under very mild reaction conditions without using oxidants. This transformation features good to excellent yields, operational simplicity, and high atom economy. Based on control experiments, a possible reaction mechanism is proposed.
A synergistic catalytic method of combining photoredox catalysis, hydrogen‐atom transfer, and proton‐reduction catalysis for the dehydrogenative silylation of alkenes was developed. The reaction features high regioselectivity, excellent tolerance of functional groups, wide substrate scope, and mild reaction conditions. Moreover, this oxidant‐free system offers a cleaner and more efficient method beyond traditional catalysis, which requires either stoichiometric or excess amounts of oxidants.
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