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.

The Enhancement of Soil Fertility,Dry Matter Transport and Accumulation,Nitrogen Uptake and Yield in Rice via Green Manuring

Readily available chemical fertilizers have resulted in a decline in the use of organic manure(e.g.,green manures),a traditionally sustainable source of nutrients.Based on this,we applied urea at the rate of 270 kg ha−1 with and without green manure in order to assess nitrogen(N)productivity in a double rice cropping system in 2017.In particular,treatment combinations were as follows:winter fallow rice-rice(WF-R-R),milk vetch rice-rice(MV-R-R),oil-seed rape rice-rice(R-R-R)and potato crop rice-rice(P-R-R).Results revealed that green manure significantly(p≤0.05)improved the soil chemical properties and net soil organic carbon content increased by an average 117.47%,total nitrogen(N)by 28.41%,available N by 26.64%,total phosphorus(P)by 37.77%,available P by 20.48%and available potassium(K)by 33.10%than WF-R-R,however pH was reduced by 3.30%across the seasons.Similarly,net dry matter accumulation rate enhanced in green manure applied treatments and ranked in order:P-R-R>R-R-R>MV-R-R>WF-R-R.Furthermore,the total leaf dry matter transport(t ha−1)for the P-R-R in both seasons was significantly higher by an average 11.2%,7.2%and 36%than MV-R-R,R-R-R,and WF-R-R,respectively.In addition,net total nitrogen accumulation(kg ha−1)was found higher in green manure applied plots compared to the control.Yield and yield attributed traits were observed maximum in green manure applied plots,with treatments ranking as follows:P-R-R>R-R-R>MV-R-R>WF-R-R.Thus,results obtained highlight ability of green manure to sustainably improve soil quality and rice yield.

阿帕替尼治疗耐药的复发胶质母细胞瘤的临床研究

目的:探讨阿帕替尼治疗替莫唑胺(temozolomide,TMZ)耐药的复发胶质母细胞瘤(glioblastoma,GBM)的疗效和不良反应,并观察治疗过程中免疫因子的变化。方法:选取2018年7月至2020年10月郑州大学附属肿瘤医院标准方案治疗失败的GBM患者51例,给予阿帕替尼和TMZ治疗。阿帕替尼500 mg/d口服,第1~14天;休息7天,开始口服TMZ 150 mg/(m^(2)·d),连续口服5天,28天为1个周期。连续服用直至疾病进展或不可耐受。治疗前及治疗后每周采集外周血,采用ELISA法检测外周血中可溶性PD-1(soluble programmed death-1,sPD-1)、可溶性PD-L1(soluble programmed death-ligand 1,sPD-L1)、白介素-6(interleukin-6,IL-6)和白介素-10(interleukin-10,IL-10)的表达。每4周行MRI增强扫描,测量肿瘤体积。结果:客观缓解率(objective response rate,ORR)为33.33%(17/51),疾病控制率(disease control rate,DCR)为72.5%(37/51),中位无进展生存期(median progression-free survival,mPFS)为5.9个月,2年总生存期(overall survival,OS)为24.9%。最常见的不良反应为Ⅰ~Ⅱ级高血压和乏力。肿瘤体积的变化与用药后血清中sPD-1、sPD-L1和IL-6的变化显著相关(r=−0.846,P=0.001;r=0.874,P<0.001;r=0.769,P=0.003);与IL-10的变化弱相关(r=0.538,P=0.071)。结论:阿帕替尼治疗TMZ耐药的GBM安全有效,且治疗中免疫因子发生变化并与疗效密切相关。

成人新诊断高危低级别胶质瘤术后治疗的现状及争议

高危低级别胶质瘤为世界卫生组织(WHO)Ⅱ级是一组起源于中枢神经系统胶质细胞的异质性肿瘤。手术通常作为首选的治疗方法,然而术后最佳治疗方法暂无共识。术后放疗、化疗可以提高部分患者的局部控制率和总生存率(overall survival,OS),但对于高危低级别胶质瘤术后最佳放疗时机、放疗的剂量、化疗药物的选择、靶向治疗和免疫治疗等目前尚存争议。本文就国内外文献进行归纳总结,并对高危低级别胶质瘤术后辅助治疗的现状及争议进行探讨。

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.

正畸治疗中阻生牙助萌术1例

目的以正畸治疗中阻生牙助萌术为例,探讨正畸患者的牙周手术设计中应注意的问题。诊治过程:25岁男性患者,牙龈呈炎症表现,牙列不齐,右上颌侧切牙阻生。前牙深覆牙合,双侧第一磨牙及尖牙远中关系,右上颌中切牙和尖牙间存在间隙。前期通过正畸治疗排齐牙列,并开辟右上颌侧切牙处的间隙。在完成牙周基础治疗的前提下,设计偏腭侧切口,在有效暴露阻生牙的前提下尽可能保存所有软组织,同时根据正畸牙移动的目标位置行骨增量和软组织增量,术后牵引并排齐右上颌侧切牙。结果通过合理的牙周手术设计,本病例在正畸过程中保持了牙周软硬组织的健康。结论正畸患者的牙周手术设计应同时关注正畸需求和牙周健康。

Classification and treatment of orbital venous malformations: an updated review

Orbital venous malformation (OVM) is a congenital vascular disease. As a common type of vascular malformation in the orbit, OVM may result in vision deterioration and cosmetic defect. Classification of orbital vascular malformations, especially OVMs, is carried out on the basis of different categories, such as angiogenesis, hemodynamics, and locations. Management of OVM is complicated and challenging. Treatment approaches include sclerotherapy, laser therapy, embolization, surgical resection, and radiotherapy. A satisfactory outcome can be achieved only by selecting the appropriate treatment according to lesion characteristics and following the sequential multi-method treatment strategy. This article summarizes the current classification and treatment advances in OVM.

The critical role of m^(6)A methylation in the pathogenesis of Graves'ophthalmopathy

Purpose:To investigate the role of N6-methyladenosine(m^(6)A)RNA modification in the pathogenesis of Graves'ophthalmopathy(GO).Methods:Surgically excised extraocular muscles from 7 patients with GO and 5 subjects without GO were used.The global m^(6)A levels in the specimens were determined using an m^(6)A RNA methylation quantification kit.RNA sequencing(RNA-seq)was used to analyze the molecules involved in the regulation of m^(6)A RNA methylation and the differential expression of mRNAs between the two groups(4 eyes,respectively).The expression of m^(6)A RNA modification genes was evaluated by real-time PCR.The functional implications of the gene alterations between the GO and control specimens were determined by Gene Ontology analysis.Results:The m^(6)A level was significantly increased in the specimens of GO patients compared to the control specimens(P<0.05).The expression of m^(6)A methylation regulators,such as WT1 associated protein(WTAP),alkylation repair homolog protein 5(ALKBH5),E74 like ETS transcription factor 3(ELF3),YTH N6-methyladenosine RNA binding protein 2(YTHDF2),YTHDF3 and YTH domain containing 2(YTHDC2),was significantly upregulated(P<0.05).Gene Ontology enrichment analysis showed that the most highly upregulated genes and biological pathways were related to the immune response and inflammatory processes such as lymphocyte activation,leukocyte differentiation,cytokine production and cytokine-mediated signaling pathways.Conclusions:Our results suggest that m^(6)A methylation may play a critical role in the pathogenesis of GO and that targeting genes that regulate m^(6)A methylation may provide a new therapeutic approach for GO.