Visulization of peroxynitrite variation for accurate diagnosis and assessing treatment response of hepatic fibrosis using a Golgi-targetable ratiometric fluorescent probe.

Hepatic fibrosis (HF) is caused by persistent inflammation, which is closely associated with hepatic oxidative stress. Peroxynitrite (ONOO-) is significantly elevated in HF, which would be regarded as a potential biomarker for the diagnosis of HF. Research has shown that ONOO- in the Golgi apparatus can be overproduced in HF, and it can induce hepatocyte injury by triggering Golgi oxidative stress. Meanwhile, the ONOO- inhibitors could effectively relieve HF by inhibiting Golgi ONOO-, but as yet, no Golgi-targetable fluorescent probe available for diagnosis and assessing treatment response of HF through sensing Golgi ONOO-. To this end, we reported a ratiometric fluorescent probe, Golgi-PER, for diagnosis and assessing treatment response of HF through monitoring the Golgi ONOO-. Golgi-PER displayed satisfactory sensitivity, low detection limit, and exceptional selectivity to ONOO-. Combined with excellent biocompatibility and good Golgi-targeting ability, Golgi-PER was further used for ratiometric monitoring the Golgi ONOO- fluctuations and screening of ONOO- inhibitors from polyphenols in living cells. Meanwhile, using Golgi-PER as a probe, the overexpression of Golgi ONOO- in HF and the treatment response of HF to the screened rosmarinic acid were precisely visualized for the first time. Furthermore, the screened RosA has a remarkable therapeutic effect on HF, which may be a new strategy for HF treatment. These results demonstrated the practicability of Golgi-PER for monitoring the occurrence, development, and personalized treatment response of HF.

Electrocatalytic reduction of furfural to furfuryl alcohol using carbon nanofibers supported zinc cobalt bimetallic oxide with surface-derived zinc vacancies in alkaline medium.

Electrocatalytic hydrogenation (ECH) reduction provides an environment-friendly alternative to conventional method for the upgrade of furfural to furfuryl alcohol. At present, exploring superior catalysts with high activity and selectivity, figuring out the reduction mechanism in aqueous alkaline environment are urgent. In this work, zinc cobalt bimetallic oxide (ZnMn2O4) with surface-derived Zn2+ vacancies supported by carbon nanofibers (d-ZnMn2O4-C) was fabricated. The d-ZnMn2O4-C exhibited excellent performance in electrocatalytic reduction of furfural, high furfuryl alcohol yield (49461.1 ± 228 µmol g-1) and Faradaic efficiency (95.5 ± 0.5 %) was obtained. In-depth research suggested that carbon nanofiber may strongly promoted the production of adsorbed hydrogen (Hads), and Zn2+ vacancies may significantly lowered the energy barrier of furfural reduction to furfuryl alcohol, the synergistic effect between carbon nanofiber and d-ZnMn2O4 probably facilitated the reaction between Hads and furfuryl alcohol radical, thereby promoting the formation of furfuryl alcohol. Furthermore, the reaction mechanism was clarified by inhibitor coating and isotope experiments, the results of which revealed that the conversion of furfural to furfuryl alcohol on d-ZnMn2O4-C followed both ECH and direct electroreduction mechanism.

Waste to treasure: Electrocatalytic upcycling of n-valeraldehyde to octane by Zn-Co bimetallic oxide with atomic level cation defect.

n-Valeraldehyde is widely used in organic synthesis field as an important intermediate and feedstock, which makes it a significant class of environmental pollutants. In view of the high poisonous and harmful of n-valeraldehyde to human health and ecological environment, it is important to develop green and sustainable technology to reduce the pollution of n-valeraldehyde. In this work, electrocatalytic n-valeraldehyde oxidation using Zn-Co bimetallic oxides was applied to control n-valeraldehyde contamination and highly valuable octane production. To further improve the performance of Zn-Co bimetallic oxides, atomic level Zn vacancies were created across the Zn-Co bimetallic oxides (dx-ZnCo2O4) by post-etching and oxygen vacancy filling methods. Electrochemical experiments results showed that dx-ZnCo2O4 owned a much higher octane yield (1193.4 µmol g-1 h-1) and octane selectivity (octane/butene ≈10). Theoretical calculations demonstrated that the introduction of atomic level Zn vacancies in Zn-Co bimetallic oxide changed the electronic distribution around O, Co and Zn atoms, resulted in an alteration in n-valeraldehyde adsorption sites from Co to Zn, reduced the formation barrier of key intermediate *C4H9 and facilitated the transfer of n-valeraldehyde to octane. This study provides a new idea for the development of high-performance electrocatalysts for controlling n-valeraldehyde pollution.