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  • Wang Fischer posted an update 25 days ago

    Electrocatalysis enables the construction of C-C bonds under mild conditions via controlled formation of carbon-centered radicals. For sequences initiated by alkyl halide reduction, coordinatively unsaturated Ni complexes commonly serve as single-electron transfer agents, giving rise to the foundational question of whether outer- or inner-sphere electron transfer oxidative addition prevails in redox mediation. Indeed, rational design of electrochemical processes requires the discrimination of these two electron transfer pathways, as they can have outsized effects on the rate of substrate bond activation and thus impact radical generation rates and downstream product selectivities. We present results from combined synthetic, electroanalytical, and computational studies that examine the mechanistic differences of single electron transfer to alkyl halides imparted by Ni metal-ligand cooperativity. Electrogenerated reduced Ni species, stabilized by delocalized spin density onto a redox-active tpyPY2Me polypyridyl ligand, activates alkyl iodides via outer-sphere electron transfer, allowing for the selective activation of alkyl iodide substrates over halogen atom donors and the controlled generation and sequestration of electrogenerated radicals. In contrast, the Ni complex possessing a redox-innocent pentapyridine congener activates the substrates in an inner-sphere fashion owning to a purely metal-localized spin, thereby activating both substrates and halogen atom donors in an indiscriminate fashion, generating a high concentration of radicals and leading to unproductive dimerization. Our data establish that controlled electron transfer via Ni-ligand cooperativity can be used to limit undesired radical recombination products and promote selective radical processes in electrochemical environments, providing a generalizable framework for designing redox mediators with distinct rate and potential requirements.Surfactants based on fatty acids have attracted extensive attention thanks to their eco-friendly and pH-responsive features. Here, we studied two fatty acid-based surfactants that were paired with the same organic counterion but distinguished by their aliphatic chain lengths (monoethanolamine-oleic acid (MEA-OA) and monoethanolamine-lauric acid (MEA-LA)). Both surfactants exhibited the ability to lower the oil-water interfacial tension but lost their interfacial activity in a low-pH environment. We experimentally investigated their influence on the receding and spreading of oil droplets on solid surfaces. It was found that the interfacial tension reduction could decrease the static contact angle of the aqueous phase and hindered displacement dynamics during the oil droplet receding. Meanwhile, the interfacial activity was more likely to suppress the initiation of the oil droplet spreading due to the more stable thin-film forming prior to the spreading process. Nevertheless, the experimental results also exhibited that MEA-OA was more effective than MEA-LA in suppressing the receding dynamics and the spreading initiation even when they were characterized by similar interfacial tension values. Such an interesting observation could be attributed to the more considerable Marangoni flow in the solution of MEA-OA whose molecules have longer aliphatic chains. The insight from this study is expected to improve the knowledge on the molecular design for more efficient applications of fatty acid-based surfactants.The ability to dynamically control chirality remains a grand challenge in chemistry. Although many molecules possess chiral isomers, lacking their isolation, for instance during photoisomerization, results in racemic mixtures with suppressed enantiospecific chiral properties. Here, we present a nanoporous solid in which chirality and enantioselective enrichment is induced by circularly polarized light (CPL). The material is based on photoswitchable fluorinated azobenzenes attached to the scaffold of a crystalline metal-organic framework (MOF). The azobenzene undergoes trans-to-cis-photoisomerization upon irradiation with green light and reverts back to trans upon violet light. While each moiety in cis conformation is chiral, we show the trans isomer also possesses a nonplanar, chiral conformation. During photoisomerization with unpolarized light, no enantiomeric enrichment is observed and both isomers, R- and S-cis as well as R- and S-trans, respectively, are formed in identical quantities. In contrast, CPL causes chiral photoresolution, resulting in an optically active material. Right-CPL selectively excites R-cis and R-trans enantiomers, producing a MOF with enriched S-enantiomers, and vice versa. Bay117085 The induction of optical activity is reversible and only depends on the light-handedness. As shown by first-principle DFT calculations, while both, trans and cis, are stabilized in nonplanar, chiral conformations in the MOF, the trans isomer adopts a planar, achiral form in solution, as verified experimentally. This shows that the chiral photoresolution is enabled by the linker reticulation in the MOF. Our study demonstrates the induction of chirality and optical activity in solid materials by CPL and opens new opportunities for chiral resolution and information storage with CPL.Growth feedback, the inherent coupling between the synthetic gene circuit and the host cell growth, could significantly change the circuit behaviors. Previously, a diverse array of emergent behaviors, such as growth bistability, enhanced ultrasensitivity, and topology-dependent memory loss, were reported to be induced by growth feedback. However, the influence of the growth feedback on the circuit functions remains underexplored. Here, we reported an unexpected damped oscillatory behavior of a self-activation gene circuit induced by nutrient-modulating growth feedback. Specifically, after dilution of the activated self-activation switch into the fresh medium with moderate nutrients, its gene expression first decreases as the cell grows and then shows a significant overshoot before it reaches the steady state, leading to damped oscillation dynamics. Fitting the data with a coarse-grained model suggests a nonmonotonic growth-rate regulation on gene production rate. The underlying mechanism of the oscillation was demonstrated by a molecular mathematical model, which includes the ribosome allocation toward gene production, cell growth, and cell maintenance.

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