Fine-tuning single-atom catalysts (SACs) to surpass their activity limit remains challenging at their atomic scale. Herein, we exploit p -type semiconducting character of SACs having a metal center coordinated to nitr...
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Fine-tuning single-atom catalysts (SACs) to surpass their activity limit remains challenging at their atomic scale. Herein, we exploit p -type semiconducting character of SACs having a metal center coordinated to nitrogen donors (MeN x ) and rectify their local charge density by an n -type semiconductor support. With iron phthalocyanine (FePc) as a model SAC, introducing an n -type gallium monosulfide that features a low work function generates a space-charged region across the junction interface, and causes distortion of the FeN 4 moiety and spin-state transition in the Fe II center. This catalyst shows an over two-fold higher specific oxygen-reduction activity than that of pristine FePc. We further employ three other n -type metal chalcogenides of varying work function as supports, and discover a linear correlation between the activities of the supported FeN 4 and the rectification degrees, which clearly indicates that SACs can be continuously tuned by this rectification strategy.
The control of endogenous protein activity with light inside live cells is helpful for the high spatiotemporal probing of their dynamic roles. Herein, we report the first small-molecule-ligand-directed caging approach...
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The control of endogenous protein activity with light inside live cells is helpful for the high spatiotemporal probing of their dynamic roles. Herein, we report the first small-molecule-ligand-directed caging approach to control the endogenous human O 6 -alkylguanine-DNA alkyltransferase (AGT) activity with light, and the caged AGT is constructed from the native intracellular AGT. The photo-responsive O 6 -benzylguanine derivative O 6 -NBG3 is developed to site-specifically cage the AGT′s catalytic cysteine residue, and the light irradiation on-demand restores AGT′s activity in vitro, in bacteria, and in mammalian cells. With O 6 -NBG3, the alkylated AGT is dealkylated for the first time to recover the DNA repair activity in breast cancer MCF-7 cells by the dose-dependent light irradiation. This decaging strategy enables the localized modulation of endogenous AGT activity with high temporal precision without genetic engineering, which holds great potential for therapeutic applications.
Routine electrolyte additives are not effective enough for uniform zinc (Zn) deposition, because they are hard to proactively guide atomic-level Zn deposition. Here, based on underpotential deposition (UPD), we propos...
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Routine electrolyte additives are not effective enough for uniform zinc (Zn) deposition, because they are hard to proactively guide atomic-level Zn deposition. Here, based on underpotential deposition (UPD), we propose an “escort effect” of electrolyte additives for uniform Zn deposition at the atomic level. With nickel ion (Ni 2+ ) additives, we found that metallic Ni deposits preferentially and triggers the UPD of Zn on Ni. This facilitates firm nucleation and uniform growth of Zn while suppressing side reactions. Besides, Ni dissolves back into the electrolyte after Zn stripping with no influence on interfacial charge transfer resistance. Consequently, the optimized cell operates for over 900 h at 1 mA cm −2 (more than 4 times longer than the blank one). Moreover, the universality of “escort effect” is identified by using Cr 3+ and Co 2+ additives. This work would inspire a wide range of atomic-level principles by controlling interfacial electrochemistry for various metal batteries.
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