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As electrochemical water splitting is an extremely promising direction for solving future energy problems and the oxygen evolution reaction (OER) is the key half-reaction in water splitting, it is necessary to develop a new type of highly active and stable non-noble metal catalyst. Herein, we construct a series of hierarchical structure by modifying ZIF-67 on clustered-MnO 2 nanotubes which are used as precursor. The fruit@branch-shaped compounds, marked as X@MnO 2 (X = CoS x , Co 3 O 4 and CoP). Compared with pure MnO 2 nanotubes, the obtained derivatives imaginably result in the unique hierarchical structure and introduce synergistic effect between MnO 2 and Co-based species that result in higher performance. In Particular, owing to the abundant active sites, a facil mass transfer pathway and improved electrical conductivity in amorphous/crystallize hierarchical structure, CoS x @MnO 2 possesses the highest electrocatalytic activity with a lower overpotential of 329 mV at the current density of 10 mA cm−2, which is superior to most MnO 2 -based catalyst previously reported. Most importantly, to expand this strategy is an effective way to synthesize more high-activity catalysts. [Display omitted] • Fruit-shaped Co-based species surrounding branch-shaped MnO 2 and Co-based species include oxides, sulfides and phosphates. • Rapid process with a general facility and the strategy is simple and low cost. • CoS x @MnO 2 shows an overpotential of 329 mV to achieve a current density of 10 mA cm−2 even better than commercial RuO 2. [ABSTRACT FROM AUTHOR]

• Aimed to identify biomarkers for predicting the efficacy of triple therapy to RA. • iTRAQ identified 51 DEPs between responders and non-responders to triple therapy. • Targeted mass spectrometry by PRM identified 10 candidate biomarkers. • 3 of 10 candidates were confirmed as predictive biomarkers. Patients with rheumatoid arthritis (RA) usually receive triple therapy with methotrexate (MTX), leflunomide (LEF) and infliximab (IFX), but nearly one-third of them do not respond to triple therapy. This study aimed to identify biomarkers for predicting the efficacy of triple therapy to optimize personalized treatment of RA. All 20 enrolled patients met 2010 ACR/EULAR criteria for RA and were classified into good, moderate and non-responders (GR, MR, NR) for triple therapy. The Responders (R) were defined as the sum of GR and MR. Protein profiles of 4 responders and 4 non-responders were investigated via isobaric tags for relative and absolute quantification (iTRAQ), and differentially expressed proteins (DEPs) with high-confidence peptides were validated in 15 responders and 5 non-responders by parallel response monitoring (PRM). iTRAQ identified 51 DEPs between responders and non-responders (p < 0.05, fold change >±1.2). The top five up-regulated DEPs were B7Z7M2, A0A087WZR4, Q53FL1, P08254 and G3V2V8, while the top five down-regulated proteins were Q6MZX9, B3KP77, P0DJI9, P0DJI8 and P02787. Targeted mass spectrometry by PRM identified 10 candidate biomarkers, and 3 DEPs including fibrinogen beta chain, epididymal secretory protein Li 282 and testicular tissue protein Li 70 were confirmed as predictive biomarkers. This study demonstrated the feasibility of exploring biomarkers by applying iTRAQ and PRM mass spectrometry techniques, and a panel of biomarkers were identified to predict clinical response of IFX + MTX + LEF treatment in active RA patients. [ABSTRACT FROM AUTHOR]