Mcfaddenstevenson8175
Carbon competition between cell growth and product synthesis is the bottleneck in efficient N-acetyl glucosamine (GlcNAc) production in microbial cell factories. In this study, a xylose-induced T7 RNA polymerase-PT7 promoter system was introduced in Escherichia coli W3110 to control the GlcNAc synthesis. Meanwhile, an arabinose-induced CRISPR interference (CRISPRi) system was applied to adjust cell growth by attenuating the transcription of key growth-related genes. By designing proper sgRNAs, followed by elaborate adjustment of the addition time and concentration of the two inducers, the carbon flux between cell growth and GlcNAc synthesis was precisely redistributed. Comparative metabolomics analysis results confirmed that the repression of pfkA and zwf significantly attenuated the TCA cycle and the synthesis of related amino acids, saving more carbon for the GlcNAc synthesis. Finally, the simultaneous repression of pfkA and zwf in strain GLA-14 increased the GlcNAc titer by 47.6% compared with that in E. coli without the CRISPRi system in a shake flask. GLA-14 could produce 90.9 g/L GlcNAc within 40 h in a 5 L bioreactor, with a high productivity of 2.27 g/L/h. This dynamic strategy for rebalancing cell growth and product synthesis could be applied in the fermentative production of other chemicals derived from precursors synthesized via central carbon metabolism.Molecular-level multielectron handling toward electrical storage is a worthwhile approach to solar energy harvesting. Here, a strategy which uses chemical bonds as electron reservoirs is introduced to demonstrate the new concept of "structronics" (a neologism derived from "structure" and "electronics"). Through this concept, we establish, synthesize, and thoroughly study two multicomponent "super-electrophores" 1,8-dipyridyliumnaphthalene, 2, and its N,N-bridged cyclophane-like analogue, 3. Within both of them, a covalent bond can be formed and subsequently broken electrochemically. These superelectrophores are based on two electrophoric (pyridinium) units that are, on purpose, spatially arranged by a naphthalene scaffold. A key characteristic of 2 and 3 is that they possess a LUMO that develops through space as the result of the interaction between the closely positioned electrophoric units. In the context of electron storage, this "super-LUMO" serves as an empty reservoir, which can be filled by a two-electron reduction, giving rise to an elongated C-C bond or "super-HOMO". Because of its weakened nature, this bond can undergo an electrochemically driven cleavage at a significantly more anodic-yet accessible-potential, thereby restoring the availability of the electron pair (reservoir emptying). In the representative case study of 2, an inversion of potential in both of the two-electron processes of bond formation and bond-cleavage is demonstrated. Overall, the structronic function is characterized by an electrochemical hysteresis and a chemical reversibility. This structronic superelectrophore can be viewed as the three-dimensional counterpart of benchmark methyl viologen (MV).We present a real-time time-dependent four-component Dirac-Kohn-Sham (RT-TDDKS) implementation based on the BERTHA code. This new implementation takes advantage of modern software engineering, including the prototyping techniques. The software design follows a three step approach (i) the prototype implementation of a time-propagation algorithm in nonrelativistic real-time TDDFT within the Psi4NumPy framework, which provides a suitable environment for the creation of a clear, readable, and easy to test reference code in Python, (ii) the design of an original Python application programming interface for the relativistic four-component code BERTHA (PyBERTHA), which has an efficient computational kernel for relativistic integrals written in FORTRAN, and (iii) the porting of the time-propagation scheme enveloped within the Psi4NumPy framework to PyBERTHA. The propagation scheme consequently resides in a single readable Python computer code that is easy to maintain and in which the key quantities, such as the Diracof the Dirac-Kohn-Sham Hamiltonian provides a suitable theoretical framework, with no intrinsic unfavorable features, to study molecules in the strong-field regime.Reactions of N-heterocyclic carbene boranes (NHC-boranes) with electron poor aromatic rings under photoredox conditions provide dearomatized 3-NHC-boryl-1,5-cycohexadienes, which are formally products of 1,4-hydroboration reactions. When regioisomers are possible, the more crowded (doubly ortho-substituted) product is formed preferably or exclusively. The mechanism is thought to involve oxidation of the NHC-borane to an NHC-boryl radical, reduction of the electron poor aromatic ring to a radical anion, coupling of the radical and the radical anion to give a cyclohexadienyl anion, and finally regioselective protonation.Wetlands have numerous critical ecological functions, some of which are regulated by several nitrogen (N) and carbon (C) biogeochemical processes, such as denitrification, organic matter decomposition, and methane emission. Until now, the underlying pathways of the effects of environmental and biological factors on wetland N and C cycling rates are still not fully understood. Here, we investigated soil potential/net nitrification, potential/unamended denitrification, methane production/oxidation rates in 36 riverine, lacustrine, and palustrine wetland sites on the Tibet Plateau. selleckchem The results showed that all the measured N and C cycling rates did not differ significantly among the wetland types. Stepwise multiple regression analyses revealed that soil physicochemical properties (e.g., moisture, C and N concentration) explained a large amount of the variance in most of the N and C cycling rates. Microbial abundance and diversity were also important in controlling potential and unamended denitrification rates, respectively. Path analysis further revealed that soil moisture and N and C availability could impact wetland C and N processes both directly and indirectly. For instance, the indirect effect of soil moisture on methane production rates was mainly through the regulating the soil C content and methanogenic community structure. Our findings highlight that many N and C cycling processes in high-altitude and remote Tibetan wetlands are jointly regulated by soil environments and functional microorganisms. Soil properties affecting the N and C cycling rates in wetlands through altering their microbial diversity and abundance represent an important but previously underestimated indirect pathway.