To explore high-performance electrocatalysts, electronic regulation on active sites is essentially demanded. Herein, we propose controlled phosphorus doping to effectively modify the electronic ...configuration of nanostructured Mo2C, accomplishing a benchmark performance of noble-metal-free electrocatalysts in the hydrogen evolution reaction (HER). Employing MoOx–phytic acid–polyaniline hybrids with tunable composition as precursors, a series of hierarchical nanowires composed of phosphorus-doped Mo2C nanoparticles evenly integrated within conducting carbon (denoted as P-Mo2C@C) are successfully obtained via facile pyrolysis under inert flow. Remarkably, P-doping into Mo2C can increase the electron density around the Fermi level of Mo2C, leading to weakened Mo–H bonding toward promoted HER kinetics. Further density functional theory calculations show that the negative hydrogen-binding free energy (ΔGH*) on pristine Mo2C gradually increases with P-doping due to electron transfer and steric hindrance by P on the Mo2C surface, indicating the effectively weakened strength of Mo–H. With optimal doping, a ΔGH* approaching 0 eV suggests a good balance between the Volmer and Heyrovsky/Tafel steps in HER kinetics. As expected, the P-Mo2C@C nanowires with controlled P-doping (P: 2.9 wt%) deliver a low overpotential of 89 mV at a current density of −10 mA cm−2 and striking kinetic metrics (onset overpotential: 35 mV, Tafel slope: 42 mV dec−1) in acidic electrolytes, outperforming most of the current noble-metal-free electrocatalysts. Elucidating feasible electronic regulation and the remarkably enhanced catalysis associated with controlled P-doping, our work will pave the way for developing efficient noble-metal-free catalysts via rational surface engineering.
An increase in the prevalence and severity of gingival inflammation during pregnancy has been reported since the 1960s. Though the etiology is not fully known, it is believed that increasing plasma ...sex steroid hormone levels during pregnancy have a dramatic effect on the periodontium. Current works of research have shown that estrogen and progesterone increasing during pregnancy are supposed to be responsible for gingivitis progression. This review is focused not only on epidemiological studies, but also on the effects of progesterone and estrogen on the change of subgingival microbiota and immunologic physiological mediators in periodontal tissue (gingiva and periodontal ligament), which provides current information about the effects of pregnancy on gingival inflammation.
Prenylated flavonoids, a unique class of flavonoids which combine a flavonoid skeleton and a lipophilic prenyl side-chain, possess great potential biological activities including cytotoxicity, ...anti-inflammation, anti-Alzheimer, anti-microbial, anti-oxidant, anti-diabetes, estrogenic, vasorelaxant and enzyme inhibition. Recently, prenylated flavonoids have become an indispensable anchor for the development of new therapeutic agents, and have received increasing from medicinal chemists. The prenylated flavonoids have been outstanding developed through isolation, semi or fully synthesis in a very short period of time, which proves the great value in medicinal chemistry researches. In this review, research progress of prenylated flavonoids including natural prenylated flavonoids, structural modification, synthetic methodologies and pharmacological activities was summarized comprehensively. Furthermore, the structure–activity relationships (SARs) of prenylated flavonoids were summarized which provided a basis for the selective design and optimization of multifunctional prenylated flavonoid derivatives for the treatment of multi-factorial diseases in clinic.
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•This article provides over 500 natural and synthetic prenylated flavonoids from 2000 to 2021.•The diverse activities and structure–activity relationships of prenylated flavonoids are summarized.•The synthetic methodologies of prenylated flavonoids are summarized.
Abstract
We take non-Hermitian Aubry–André–Harper models and quasiperiodic Kitaev chains as examples to demonstrate the equivalence and superposition of real and imaginary quasiperiodic potentials ...(QPs) on inducing localization of single-particle states. We prove this equivalence by analytically computing Lyapunov exponents (or inverse of localization lengths) for systems with purely real and purely imaginary QPs. Moreover, when superposed and with the same frequency, real and imaginary QPs are coherent on inducing the localization, in a way which is determined by the relative phase between them. The localization induced by a coherent superposition can be simulated by the Hermitian model with an effective strength of QP, implying that models are in the same universality class. When their frequencies are different and relatively incommensurate, they are incoherent and their superposition leads to less correlation effects. Numerical results show that the localization happens earlier and there is an intermediate mixed phase lacking of mobility edge.
The development of efficient photocathodes is of critical importance for the constructions of promising tandem photo‐electrochemical cells. Most known dye‐sensitized photocathodes are prepared with ...the conventional carboxylic or phosphonic acid anchors and require the presence of other terminal linking groups to connect catalysts; they suffer from high synthetic difficulty and low adsorption stability in aqueous media. Here, a compact bilayer photocathode has been prepared by using a pyrene‐based photosensitizer with multiple terminal pyridine moieties as both the anchoring and linking groups to connect a Co hydrogen‐evolution catalyst to the NiO substrate. The catalyst and dye molecule are assembled in a layer‐by‐layer manner on NiO through the metal‐pyridine coordination. This photocathode exhibits good dye adsorption stability in aqueous media. A stable cathodic photocurrent of 70 μA cm−2 was achieved, with H2 being generated at the photocathode under the visible‐light irradiation. The Faraday efficiency of H2 evolution was estimated to be 9.1 %. Transient absorption spectral studies suggest that the interfacial hole transfer occurs within a few picoseconds. The integration of the organic photosensitizer with pyridine anchoring and linking groups is expected to provide a simple method for the fabrication of stable and efficient photocathodes.
NiO Substrate & Co. A photocathode has been prepared by using a pyrene‐based photosensitizer with multiple terminal pyridine moieties as both the anchoring and linking groups to connect a Co hydrogen‐evolution catalyst to the NiO substrate. This photocathode exhibits good dye adsorption and photochemical stability in aqueous solution and is applied in water reduction into hydrogen under irradiation in photo‐electrochemical cells.
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