Oxygen-vacancy-rich MnO_(x)supported RuO_(x)for efficient base-free oxidation of 5-hydroxymethylfurfural and 5-methoxymethylfurfural to 2,5-furandicarboxylic acid

2,5-Furandicarboxylic acid(FDCA)is a promising biomass-derived polymeric monomer that serves as an attractive alternative to terephthalic acid derived from fossil resources.However,the green and efficient production of FDCA through the oxidation of 5-hydroxymethylfurfural(HMF)and its derivatives is still rudimentary under base-free conditions.In this work,oxygen-vacancy-rich Mn Oxwas prepared and displayed a strong adsorption and anchoring ability to Ru species that mainly exposed the(210)plane of RuO_(2),bringing about highly dispersed and active interfacial Ru-O-Mn structures.Experimental results and density functional theory calculations confirm that these above features greatly facilitate the adsorption/activation of oxygen and the dehydrogenation-oxidation of HMF/5-methoxymethylfurfural(MMF),which enables an efficient FDCA production under base-free and mild conditions.Notably,a desirable FDCA yield of 86.56%was still obtained from concentrated HMF(10 wt%)under base-free conditions over oxygen-vacancy-rich Mn Oxsupported Ru Ox(1.0 MPaO_(2),120℃,6 h).This work delineates a facile catalyst preparation strategy for HMF/MMF oxidation,and might open a new avenue for the green synthesis of FDCA under base-free conditions.

Base-free oxidative esterification of 5-hydroxymethylfurfural to furan-2,5-dimethylcarboxylate over n-doped carbon-supported Co/Fe bimetallic catalyst under batch-operation or continuous-flow conditions

Developing an efficient and easily available catalyst for the selective conversion of biomass-derived 5-hydroxymethylfurfural(HMF)into furan-2,5-dimethylcarboxylate(FDMC),a valuable biomass-based monomer,remains a high demand but formidable challenge.Herein,a facile strategy for the synthesis of N-doped carbon-supported Co/Fe bimetallic catalyst(CoFe-NC)was developed,which provided an outstanding FDMC yield of 93%in a batch reactor(base-free,80℃,2 bar O_(2),4 h).Interestingly,CoFe-NC also gave a high FDMC yield of 91%under continuous-flow conditions for 80 h(5 bar O_(2),80℃,GHSV 1320 h^(-1),LHSV 0.6 h^(-1),base-free).Notably,it is the first time that a non-noble catalyst gave such a high FDMC yield under continuous-flow conditions.The introduction of Fe could greatly improve both the electron intensity of Co-N_(x)species and basicity of the catalyst,which endowed CoFe-NC with improved O_(2)activation capacity and enhanced dehydrogenation activity for the oxidation-esterification of HMF.This work delineates the efficient strategy on the construction of N-doped carbon-supported non-noble catalyst,which might open a new avenue for developing highly efficient catalyst for FDMC production.

Catalyst design strategy toward the efficient heterogeneously-catalyzed selective oxidation of 5-hydroxymethylfurfural

The selective oxidation of 5-hydroxymethylfurfural(HMF),a versatile bio-based platform molecule,leads to the formation of several intriguing and useful downstream chemicals,such as 2,5-diformylfuran(DFF),5-hydroxymethyl-2-furancarboxylic acid(HMFCA),formyl 2-furancarboxylic acid(FFCA),2,5-furandicarboxylic acid(FDCA) and furan-2,5-dimethylcarboxylate(FDMC).These products have been extensively employed to fabricate novel polymers,pharmaceuticals,sustainable dyes and many other value-added fine chemicals.The heart of the developed HMF oxidation processes is always the catalyst.In this regard,this review comprehensively summarized the established heterogeneous catalyst design strategy for the selective oxidation of HMF via thermo-catalysis.Particular attention has been focused on the reaction mechanism of HMF oxidation over different catalysts as well as enhancing the catalytic performance of the catalyst through manipulating the properties of the support and fabricating of multi-component metal nano-particles and oxides.The current challenges and possible research directions for the catalytic oxidation of HMF in the future are also discussed.

miR-410 induces both epithelial–mesenchymal transition and radioresistance through activation of the PI3K/mTOR pathway in non-small cell lung cancer

Radiotherapy remains one of the major treatments for non-small cell lung cancer(NSCLC)patients;whereas intrinsic or acquired radioresistance limits its efficacy.Nevertheless,most studies so far have only focused on acquired resistance.The exact mechanisms of intrinsic radioresistance in NSCLC are still unclear.A few studies have suggested that epithelial–mesenchymal transition(EMT)is associated with radioresistance in NSCLC.However,little is known about whether the abnormal expression of specific microRNAs induces both EMT and radioresistance.We previously found that miR-410 has multiple roles as an oncomiRNA in NSCLC.In this study,we revealed that miR-410 overexpression promoted EMT and radioresistance,accompanied by enhanced DNA damage repair both in vitro and in vivo.Conversely,knockdown of miR-410 showed the opposite effects.We further demonstrated that PTEN was a direct target of miR-410 by using bioinformatic tools and dual-luciferase reporter assays,and the miR-410-induced EMT and radioresistance were reversed by PI3K,Akt,and mTOR inhibitors or by restoring the expression of PTEN in NSCLC cells.In addition,we preliminarily found that the expression of miR-410 was positively correlated with EMT and negatively associated with the expression of PTEN in NSCLC specimens.In summary,these results demonstrated that miR-410 is an important regulator on enhancing both NSCLC EMT and radioresistance by targeting the PTEN/PI3K/mTOR axis.The findings suggest that miR-410-induced EMT might significantly contribute to the enhanced radioresistance.Therefore,miR-410 may serve as a potential biomarker or therapeutic target for NSCLC radiotherapy.