Free radical oxidation reaction for selectively solvatochromic sensors with dynamic sensing ability

A novel BODIPY (boradiazaindacene) dye denoted as BODIPY-DT containing terpyridine unit has been designed and characterized. The dye is found to be selective and visual solvatochromic sensor toward DMF among test organic solvents. The sensing process displays time-controllable, dynamic signal outputs in the emission colors including red, purple, yellow and even white emission colors. It is presented that selective free radical oxidation reaction happens during the recognition process.     

GOSs-稀土配合物紫外增强材料的光谱分析与稳定性研究

氧化石墨烯薄片(GOSs)作为一种新型的二维片状材料,具有较高的比表面积、丰富的表面含氧官能团以及良好的光热稳定性。而稀土配合物通过无机稀土元素与有机配体的结合表现出优异的荧光特性。为了将两类材料具有的物化特性结合起来应用于紫外光谱探测领域。选取了合适的有机配体啉菲罗啉(1,10-邻二氮杂菲,phen)、2’2-联嘧啶(bpm)作为桥联分子,把氧化石墨烯(GOSs)与稀土配合物通过氢键自组装作用进行复合,制备了高效稳定可调的GOSs-稀土配合物复合荧光材料GOSs-Eu(BA)3phen和GOSs-Eu(TTA)3bpm,并且制备了相应的聚乙烯醇(PVA)共混紫外增强薄膜,对其光谱特性与稳定性进行了深入的研究。采用红外光谱、扫描电镜和金相显微镜等方法,对紫外增强材料进行了性能表征。采用吸收光谱,荧光光谱等方法,对紫外增强薄膜进行了性能表征。此外,通过热重测试(TGA)表征了GOSs氢键复合前后紫外增强材料的热稳定性,通过荧光强度-紫外光照次数表征了GOSs氢键复合前后紫外增强薄膜的光稳定性。红外光谱分析发现,进行配位前后有机配体的特征峰产生了频移,表明稀土配合物中Eu 3+与配体之间存在着明显的配位作用。在进行复合之后,桥联配体的特征峰也产生了偏移,表明GOSs与稀土配合物通过桥联分子的氢键作用进行了进行复合。吸收光谱与荧光光谱测定结果表明增强薄膜吸收峰在200~400 nm,荧光主峰在612 nm左右,为Eu 3+特征红色荧光峰,且不同配体可以实现不同范围的吸收产生差异化的荧光表现。扫描电镜和金相显微镜清晰地展示了稀土配合物复合前后的微观形貌,即颗粒状稀土配合物附着在石墨烯薄片上。光稳定性测试表明经过GOSs氢键复合之后,Eu(BA)3phen和Eu(TTA)3bpm稀土配合物荧光材料在进行25次荧光强度测试后光漂白程度分别下降了4.26%和6.41%,提高了其光稳定性。热重测试也表明在经过GOSs氢键复合之后,稀土配合物的热稳定性有了很大提高。总之,得益于GOSs和稀土配合物的特性结合,所制备的紫外增强材料表现出优异的荧光特性与稳定性,必将在紫外探测方面有着广阔的应用前景。     

Facile synthesis of temperature-sensitive ABA triblock copolymers by dispersion RAFT polymerization

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One-pot preparation of (RSe)2CF2 and (RS)2CF2 compounds via insertion of TMSCF3-derived difluorocarbene into diselenides and disulfides

A method for the first direct insertion of difluorcarbene, generated from TMSCF₃, into diselenides and disulfides is disclosed, producing novel difluoromethyl diselenoacetals and difluoromethyl dithioacetals. The reaction conditions tolerate a range of synthetically useful and biologically relevant functional groups. The process is scalable, with two representative compounds prepared at a gram-scale in good yields, and it utilizes cheap and available reagents.     

A Gibbs sampling method to determine biomarkers for asthma

PurposeTo identify potential biomarkers and to uncover the mechanisms underlying asthma based on Gibbs sampling.MethodsThe molecular functions (MFs) with genes greater than 5 were determined using AnnotationMFGO of BAGS package, and the obtained MFs were then transformed to Markov chain (MC). Gibbs sampling was conducted to obtain a new MC. Meanwhile, the average probabilities of MFs were computed via MC Monte Carlo (MCMC) algorithm, followed by identification of differentially expressed MFs based on the probabilities of MF more than 0.6. Moreover, the differentially expressed genes (DEGs) and their correlated genes were screened and merged, called as co-expressed genes. Pathways enrichment analysis was implemented for the co-expressed genes.ResultsBased on the gene set more than 5, overall 396 MFs were determined. After Gibbs sampling, 5 differentially expressed MF were acquired according to alfa.pi > 0.6. Moreover, the genes in these 5 differentially expressed MF were merged, and 110 DEGs were identified. Subsequently, 338 co-expressed genes were gained. Based on the P value < 0.01, the co-expressed genes were significantly enriched in 6 pathways. Among these, ubiquitin mediated proteolysis contained the maximum numbers of 35 co-expressed genes, and cell cycle were enriched by the second largest number of 11 co-expressed genes, respectively.ConclusionsThe identified pathways such as ubiquitin mediated proteolysis and cell cycle might play important roles in the development of asthma and may be useful for developing the credible therapeutic approaches for diagnosis and treatment of asthma in future.     

Electrochemically activated MnO as a cathode material for sodium-ion batteries

Besides classical electrode materials pertaining to Li-ion batteries, recent interest has been devoted to pairs of active redox composites having a redox center and an intercalant source. Taking advantage of the NaPF₆ salt decomposition above 4.2 V, we extrapolate this concept to the electrochemical in situ preparation of F-based MnO composite electrodes for Na-ion batteries. Such electrodes exhibit a reversible discharge capacity of 145 mAh g^− 1 at room temperature. The amorphization of pristine MnO electrode after activation is attributed to the electrochemical grinding effect caused by substantial atomic migration and lattice strain build-up upon cycling.     

Electrochemical C–H/N–H cross-coupling of 2-phenylindolizines with phenothiazines to synthesize novel N-aryl phenothiazine derivatives

A facile and elegant method for synthesis of novel N–aryl phenothiazine derivatives from 2-phenylindolizines and phenothiazines through direct electrochemical oxidation has been developed. This approach was performed smoothly at room temperature without external oxidant and catalyst. Cyclic voltammetry and in situ FTIR techniques were applied to analyze the cross-coupling process of phenothiazines and 2-phenylindolizines, which helped to select the appropriate reaction potential. Under the optimized conditions, a broad range of substrates were well tolerated, affording the desired products in moderate to excellent isolated yields (up to 91%) with high regioselectivity. Meanwhile, a plausible mechanism involving a radical pathway has been proposed.     

Enhanced water-induced effects enabled by alkali-stabilized Pd-OHx species for oxidation of benzyl alcohol

The water promotion effects, where water can provide a solution-mediated reaction pathway in various heterogeneous chemical catalysis, have been presented and attracted wide attention recently, yet, the rational design of catalysts with a certain ability of enhancing water-induced reaction process is full of challenges and difficulties. Here, we show that by incorporating alkali (Na, K) cations as an electronic and/or structural promoter into Pd/rGO-ZnCr₂O₄ (rGO, reduced graphene oxide), the obtained Pd(Na)/rGO-ZnCr₂O₄ as a representative example demonstrates an outstanding benzyl alcohol oxidation activity in the Pickering emulsion system in comparison to the alkali-free counterpart. The response experiments of water injection confirm the enhanced activity, and the Na-modified catalyst can further enhance the promotion effects of water on the reaction. The effects of alkali cations for Pd nanoparticles are identified and deciphered by a series of experimental characterizations (XPS, in situ CO-DRIFTS, and CO-TPR coupled with MS), showing that there is abundant −OH on the surface of the catalyst, which is stabilized by the formation of Pd−OH_x. The alkali-stabilized Pd−OH_x is helpful to enhance the water-induced reaction process. According to the results of in situ Raman as well as UV-vis absorption spectra, the Na-modulated Pd(Na)/rGO-ZnCr₂O₄ enables the beneficial characteristics for distorting the benzyl alcohol structure and enhancing the adsorption of benzyl alcohol. Further, the mechanism for enhanced water promotion effects is rationally proposed. The strategy of alkali cations-modified catalysts can provide a new direction to effectively enhance the chemical reaction involving small molecule water.     

A Lewis acid-catalyzed tandem reaction enabling 2-arylglycerol derivative as a versatile 1,3-biselectrophile for the synthesis of 4H-chromenes and 2-pyridinones

Acid-catalyzed tandem reactions were established by employing a novel class of 2-arylglycerol derivative,5-aryl-1,3-dioxan-5-ol, as versatile 1,3-biselectrophile. In the reactions, 5-aryl-1,3-dioxan-5-ol works like atropaldehydes or 2-aryl malondialdehydes, and can react with 2-naphthols and β-keto amides, allowing the synthesis of 4H-chromenes and 5-aryl-2-pyridinones. High yields, good functional group tolerance,broad substrate scope and simple reaction operation make this protocol attractive.