The anode oxygen evolution reaction (OER) is known to largely limit the efficiency of electrolyzers owing to its sluggish kinetics. While crystalline metal oxides are promising as OER catalysts, ...their amorphous phases also show high activities. Efforts to produce amorphous metal oxides have progressed slowly, and how an amorphous structure benefits the catalytic performances remains elusive. Now the first scalable synthesis of amorphous NiFeMo oxide (up to 515 g in one batch) is presented with homogeneous elemental distribution via a facile supersaturated co‐precipitation method. In contrast to its crystalline counterpart, amorphous NiFeMo oxide undergoes a faster surface self‐reconstruction process during OER, forming a metal oxy(hydroxide) active layer with rich oxygen vacancies, leading to superior OER activity (280 mV overpotential at 10 mA cm−2 in 0.1 m KOH). This opens up the potential of fast, facile, and scale‐up production of amorphous metal oxides for high‐performance OER catalysts.
Amorphous NiFeMo oxide (up to 515 g one batch) with homogeneous elemental distribution was synthesized through a facile supersaturated co‐precipitation method. The amorphous NiFeMo oxide undergoes rapid surface self‐reconstruction during OER that forms a metal oxy(hydroxide) active layer with oxygen vacancies, enabling efficient OER catalysis.
Peroxisomes account for ~35% of total H2O2 generation in mammalian tissues. Peroxisomal ACOX1 (acyl‐CoA oxidase 1) is the first and rate‐limiting enzyme in fatty acid β‐oxidation and a major producer ...of H2O2. ACOX1 dysfunction is linked to peroxisomal disorders and hepatocarcinogenesis. Here, we show that the deacetylase sirtuin 5 (SIRT5) is present in peroxisomes and that ACOX1 is a physiological substrate of SIRT5. Mechanistically, SIRT5‐mediated desuccinylation inhibits ACOX1 activity by suppressing its active dimer formation in both cultured cells and mouse livers. Deletion of SIRT5 increases H2O2 production and oxidative DNA damage, which can be alleviated by ACOX1 knockdown. We show that SIRT5 downregulation is associated with increased succinylation and activity of ACOX1 and oxidative DNA damage response in hepatocellular carcinoma (HCC). Our study reveals a novel role of SIRT5 in inhibiting peroxisome‐induced oxidative stress, in liver protection, and in suppressing HCC development.
Synopsis
This study reveals a role for SIRT5 in regulating peroxisomal H2O2 and ROS homeostasis and indicates its potential function in liver protection and hepatocellular carcinoma suppression.
SIRT5 is localized in peroxisomes where it controls H2O2 metabolism.
SIRT5‐mediated desuccinylation inhibits ACOX1 activity by suppressing its active dimer formation.
SIRT5 downregulation increases ACOX1 activity and oxidative DNA damage response in HCC.
This study reveals a role for SIRT5 in regulating peroxisomal H2O2 and ROS homeostasis and indicates its potential function in liver protection and hepatocellular carcinoma suppression.
Disclosed herein is a direct C−H trifluoromethylation of quinoxalin‐2(1H)‐ones with sodium trifluoromethanesulfinate. This protocol affords a series of 3‐trifluoromethylquinoxalin‐2(1H)‐one ...derivatives in moderate to excellent yields under transition‐metal‐free conditions. The present methodology features utilization of the inexpensive trifluoromethyl source without transition‐metal‐catalysts, mild reaction conditions and high functional group tolerance, which promises a convenient and efficient access to pharmaceutically interesting quinoxalinones.
Grain size is an important component trait of grain yield, which is frequently threatened by abiotic stress. However, little is known about how grain yield and abiotic stress tolerance are regulated. ...Here, we characterize GSA1, a quantitative trait locus (QTL) regulating grain size and abiotic stress tolerance associated with metabolic flux redirection. GSA1 encodes a UDP-glucosyltransferase, which exhibits glucosyltransferase activity toward flavonoids and monolignols. GSA1 regulates grain size by modulating cell proliferation and expansion, which are regulated by flavonoid-mediated auxin levels and related gene expression. GSA1 is required for the redirection of metabolic flux from lignin biosynthesis to flavonoid biosynthesis under abiotic stress and the accumulation of flavonoid glycosides, which protect rice against abiotic stress. GSA1 overexpression results in larger grains and enhanced abiotic stress tolerance. Our findings provide insights into the regulation of grain size and abiotic stress tolerance associated with metabolic flux redirection and a potential means to improve crops.
It remains highly desired but a great challenge to achieve atomically dispersed metals in high loadings for efficient catalysis. Now porphyrinic metal–organic frameworks (MOFs) have been synthesized ...based on a novel mixed‐ligand strategy to afford high‐content (1.76 wt %) single‐atom (SA) iron‐implanted N‐doped porous carbon (FeSA‐N‐C) via pyrolysis. Thanks to the single‐atom Fe sites, hierarchical pores, oriented mesochannels and high conductivity, the optimized FeSA‐N‐C exhibits excellent oxygen reduction activity and stability, surpassing almost all non‐noble‐metal catalysts and state‐of‐the‐art Pt/C, in both alkaline and more challenging acidic media. More far‐reaching, this MOF‐based mixed‐ligand strategy opens a novel avenue to the precise fabrication of efficient single‐atom catalysts.
Iron islands: Based on a mixed‐ligand strategy, a porphyrinic MOF was pyrolyzed to afford high‐content single‐atom iron‐implanted N‐doped porous carbon (FeSA‐N‐C). Thanks to the FeSA sites, hierarchical pores, oriented mesochannels, and high conductivity, FeSA‐N‐C exhibits excellent oxygen reduction activity and stability, surpassing almost all non‐noble‐metal catalysts and Pt/C, in both alkaline and the more challenging acidic media.
Protein tyrosine phosphatases (PTP) are exciting and novel targets for cancer drug discovery that work in concert with protein tyrosine kinases (PTK) in controlling cellular homeostasis. Given the ...activating role that some PTKs play in initiating growth factor-mediated cellular processes, PTPs are usually perceived as the negative regulators of these events and therefore tumor suppressive in nature. However, mounting evidence indicate that PTPs do not always antagonize the activity of PTKs in regulating tyrosine phosphorylation, but can also play dominant roles in the initiation and progression of signaling cascades that regulate cell functions. It follows, therefore, that PTP malfunction can actively contribute to a host of human disorders, in particular, cancer, metabolic syndromes, and autoimmune diseases. The Src homology domain containing phosphatase 2 (SHP2) and the three-membered family of phosphatases of regenerating liver (PRL) are infamously oncogenic members of the PTP superfamily. Both are established regulators of major cancer pathways such as Ras/ERK1/2, Src, JAK/STAT, JNK, NF-κB, and PTEN/PI3K/AKT. Furthermore, upregulation, mutation, or other dysregulation of these PTPs has been positively correlated with cancer initiation and progression. This review will provide topical coverage of target validation and drug discovery efforts made in targeting these oncogenic PTPs as compelling candidates for cancer therapy.
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•Corrosion behavior of laser powder bed fusion produced Ti–6Al–4V samples was investigated.•Static and dynamic Hank’s solutions were selected as the corrosion environments.•Flow ...solution degrades passive film of sample and thereby the corrosion resistance.•Flow solution promotes the deposition of calcium phosphate and hydroxyapatite.
The corrosion behavior of laser powder bed fusion produced (L-PBF-produced) titanium alloys involving flowing body fluid is still unclear. Therefore, this work investigates in vitro corrosion behavior and the characteristics of passive films formed on L-PBF-produced Ti–6Al–4V in both static and dynamic Hank’s solutions. Electrochemical measurements, immersion tests, X-ray photoelectron spectroscopy and scanning electron microscopy were conducted. In comparison to the L-PBF-produced Ti–6Al–4V in static Hank’s solution, the samples showed lower charge transfer resistance and higher passivation current density (anodic current density as well) in dynamic Hank’s solution. Meanwhile, a more apparent deposition of apatite and hydroxyapatite is found on the L-PBF-produced Ti–6Al–4V in dynamic Hank’s solution. Such outcomes mainly result from the enhancement of film/solution interfacial transportation in dynamic Hank’s solution. The dynamic Hank’s solution provides more calcium and phosphate ions to the surface of the passive film and also takes away the dissolved metal ions. Therefore, more salt deposition and a lower-quality passive film are found.
A copper‐catalyzed direct C−H difluoroacetylation of quinoxalinones at the C‐3 position with ethyl bromodifluoroacetate has been developed. In this reaction, diverse difluoroacetylated ...quinoxalin‐2(1H)‐ones with a wide range of functional groups could be obtained in moderate to good yields, using cheap, commercially available reagents. This protocol would offer a meaningfully synthetic method for pharmacologically interesting difluoroacetylated quinoxalin‐2(1H)‐one derivatives.
Ultrathick electrode design is a promising strategy to enhance the specific energy of Li‐ion batteries (LIBs) without changing the underlying materials chemistry. However, the low Li‐ion conductivity ...caused by ultralong Li‐ion transport pathway in traditional random microstructured electrode heavily deteriorates the rate performance of ultrathick electrodes. Herein, inspired by the vertical microchannels in natural wood as the highway for water transport, the microstructures of wood are successfully duplicated into ultrathick bulk LiCoO2 (LCO) cathode via a sol–gel process to achieve the high areal capacity and excellent rate capability. The X‐ray‐based microtomography demonstrates that the uniform microchannels are built up throughout the whole wood‐templated LCO cathode bringing in 1.5 times lower of tortuosity and ≈2 times higher of Li‐ion conductivity compared to that of random structured LCO cathode. The fabricated wood‐inspired LCO cathode delivers high areal capacity up to 22.7 mAh cm−2 (five times of the existing electrode) and achieves the dynamic stress test at such high areal capacity for the first time. The reported wood‐inspired design will open a new avenue to adopt natural hierarchical structures to improve the performance of LIBs.
Inspired by the vertical microchannels in natural wood as the highway for water transport, an ultra‐thick bulk LiCoO2 (LCO) cathode with vertical channels is fabricated to enhance the transport of Li+. Remarkably, the fabricated LCO cathode shows low tortuosity and high Li‐ion conductivity, and can deliver high areal capacity up to 22.7 mAh cm−2.
Covalent organic frameworks (COFs) are an emerging type of crystalline and porous photocatalysts for hydrogen evolution, however, the overall water splitting activity of COFs is rarely known. In this ...work, we firstly realized overall water splitting activity of β-ketoamine COFs by systematically engineering N-sites, architecture, and morphology. By in situ incorporating sub-nanometer platinum (Pt) nanoparticles co-catalyst into the pores of COFs nanosheets, both Pt@TpBpy-NS and Pt@TpBpy-2-NS show visible-light-driven overall water splitting activity, with the optimal H
and O
evolution activities of 9.9 and 4.8 μmol in 5 h for Pt@TpBpy-NS, respectively, and a maximum solar-to-hydrogen efficiency of 0.23%. The crucial factors affecting the activity including N-sites position, nano morphology, and co-catalyst distribution were systematically explored. Further mechanism investigation reveals the tiny diversity of N sites in COFs that induces great differences in electron transfer as well as reaction potential barriers.
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