SYNTHESIS AND CHARACTERIZATION OF A NOVEL BLUE LIGHT EMITTING ROD-COIL DIBLOCK OLIGOMER

Four new rod-coil diblock molecules, which had well-defined para-phenylene oligomers (PPP, from biphenyl toquinquephenyl) as rigid segments and poly(ethylene oxide) (PEO, M_w ca. 750) as flexible segments, were synhesized. Thechemical structure and the number of repeating unit in PEO coil and PPP rod were characterized by ~1H-NMR and MALDI-TOF mass spectromeny. The diblock oligomers showed good solubility in common organic solvents and aggregated in wateras characterized by a blue shift in UV-vis absorption spectra, a red shift in emission spectra, quenching of the fluorescenceand formation of the microfibrilla and fractal-like structures. The formation of different supramolecular structures meant thatthis effort might lead to commercial important highly organized functional materials.     

异戊二烯稀土催化聚合过程中配合物结构及其转化的~(13)C-NMR研究

本文用~(13)C-NMR研究了异戊二烯(IP)在均相催化剂(CF_3CO_2)_2LnCl·EtOH—(i-Bu)AlH—o-C_6D_4Cl_2作用下的聚合过程。单体首先被活化同稀土配位生成η~4-IP稀土配合物(反式和顺式),然后η~4-IP的C-3和C-4插入Ln-H键生成η~3-烯丙基稀土配合物——η~3-(2-甲基)丁烯基稀土配合物(同式和对式)。二维~(13)C-NMR交换谱表明η~4-IP和0η~3-烯丙基的每对异构体在常温下分别进行慢交换反应(互变异构),这一过程使插入反应在常温下得以进行。     

Crosslinking polydopamine/cellulose nanofibril composite aerogels by metal coordination bonds for significantly improved thermal stability,flame resistance,and thermal insulation properties

Cellulose nanofibril (CNF) aerogels have attracted great interests in recent years due to the low cost, sustainability and biocompatibility of raw CNF. However, the poor thermal stability and flammable feature of CNF aerogels have limited their wider applications. In this paper, polydopamine/CNF composite aerogels with good comprehensive properties are fabricated by modification of CNF with polydopamine and metal coordination bonds crosslinking. The microstructure and properties of composite aerogels are thoroughly characterized by a variety of tests. It is found that the microstructure of aerogels are more regular and the compressive strength of aerogels are enhanced by the incorporation of polydopamine and Fe³⁺ crosslinking. Importantly, the thermal stability and flame resistance of aerogels are significantly improved, which permit the application of composite aerogels in high-temperature thermal insulation. In addition, the reversible characteristic of metal coordination bonds allows the water induced healing of fractured composite aerogels. This study is expected to provide information for future development of green and high-performance aerogels.

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Advances in Electrochemical Decarboxylative Transformation Reactions

Owing to their non-toxic, stable, inexpensive properties, carboxylic acids are considered as environmentally benign alternatives as coupling partners in various organic transformations. Electrochemical mediated decarboxylation of carboxylic acid has emerged as a new and efficient methodology for the construction of carbon-carbon or carbon-heteroatom bonds. Compared with transition-metal catalysis and photoredox catalysis, electro-organic decarboxylative transformations are considered as a green and sustainable protocol due to the absence of chemical oxidants and strong bases. Further, it exhibits good tolerance with various functional groups. In this Minireview, we summarize the recent advances and discoveries on the electrochemical decarboxylative transformations on C−C and C−heteroatoms bond formations.     

新型咔唑类卟啉的合成与性能

以咔唑、对氟苯甲醛和吡咯为原料制得meso-四（4-咔唑）苯基卟啉（TCPP）。以对硝基苯甲醛与吡咯为原料制得meso-四(4-硝基)苯基卟啉（TNPP）； TNPP经还原反应制得meso-四（4-氨基苯基）卟啉（TAPP）; TAPP与咔唑苯甲醛经缩合反应制得新型meso-四[对-（P-N-咔唑基亚苄基亚氨基）]苯基卟啉(TCIPP)，其结构和性能经UV-Vis, ¹H NMR, ¹³C NMR, IR,元素分析和循环伏安法（CV）表征。结果表明：TCPP在270~300 nm处有新吸收峰；TCIPP的Q带和B带相比于TCPP有明显红移。TCPP和TCIPP的E_LUMO和E_HOMO分别为-3.18 eV, -5.17 eV和-3.49 eV, -5.08 eV，两者的能级结构与纳米TiO₂的导带能级相匹配。     

Multi-objective optimization of inverse planning for accurate radiotherapy

The multi-objective optimization of inverse planning based on the Pareto solution set, according to the multi-objective character of inverse planning in accurate radiotherapy, was studied in this paper. Firstly,the clinical requirements of a treatment plan were transformed into a multi-objective optimization problem with multiple constraints. Then, the fast and elitist multi-objective Non-dominated Sorting Genetic Algorithm (NSGA-Ⅱ)was introduced to optimize the problem. A clinical example was tested using this method. The results show that an obtained set of non-dominated solutions were uniformly distributed and the corresponding dose distribution of each solution not only approached the expected dose distribution, but also met the dosevolume constraints. It was indicated that the clinical requirements were better satisfied using the method and the planner could select the optimal treatment plan from the non-dominated solution set.     

ZrO2修饰Cu催化剂还原以及反应过程中表面组成的变化

通过热分解法制备Cu模型催化剂,然后经浸渍制备ZrO₂/Cu催化剂,采用SEM、XPS考察了催化剂表面形态和组成,并采用in-situ Raman考察了催化剂在还原和吸附CO和水的过程中随时间的变化。结果表明,还原前Cu催化剂表面主要存在CuO物种,而在ZrO₂/Cu表面,除了CuO物种,还存在着大量的表面羟基物种。ZrO₂/Cu相对Cu更加容易还原为Cu⁰,同时,ZrO₂在催化剂表面聚集形成絮状态,而Cu催化剂还原后主要形成Cu₂O物种。Cu催化剂表面吸附CO后,除了形成Cu-CO外,Cu₂O物种均会迅速消失形成CO₂。Cu催化剂对水的作用比较弱,但是ZrO₂/Cu催化剂和水作用较强,并且通过Cu-OH中间物形成Cu₂O物种。     

酸性AlCl3-BMIC离子液体中的铝阳极溶解

采用线性扫描伏安法研究了Lewis 酸性AlCl₃-BMIC (BMIC: 1-butyl-3-methylimidazolium chloride)离子液体中铝电极的溶解. 铝电极在阳极极化时出现了钝化现象, 钝化是由于在铝电极表面形成了固体AlCl₃钝化膜造成的. 铝的电化学溶解过程可以依次分为三个区: 电化学控制区、过渡区和钝化区. 在电化学控制区, 铝的电化学溶解速率随着电位的正移而逐渐增加; 在过渡区, 由于电极表面AlCl₄^-和Al₂Cl₇^-浓度发生改变而析出固体AlCl₃使得铝电化学溶解速率随着电位的正移而逐渐减小; 当钝化膜形成之后, 铝的电化学溶解速率不再随着电位的正移而发生改变, 铝溶解进入钝化区. 增加搅拌、升高温度、降低离子液体AlCl₃摩尔分数都可以增加铝溶解阳极极限电流密度.     

水热法制备富锂型Li_(2+4x)Mn_(0.6+2x)Ni_(0.6-6x)Cr_(0.8)O_4及其结构与电化学特性

采用水热法制备了系列富锂尖晶石型正极材料Li2+4xMn0.6+2xNi0.6-6xCr0.8O4(x=1/30,1/20,1/15,1/12),通过X射线衍射(XRD)、电感耦合等离子体-原子发射光谱(ICP-AES)、扫描电子显微镜(SEM)、X射线光电子能谱(XPS)、傅里叶变换红外光谱(FTIR)、拉曼光谱、循环伏安(CV)和充放电测试等手段对其结构及电化学性能进行表征.结果表明,所制备的系列材料为富锂型高电压尖晶石结构正极材料,该系列样品在4.7 V左右有放电平台.x=1/15和x=1/12时,样品中的Cr为+3价,没有观测到Cr6+.随着x值的增大,样品中Li离子与过渡金属离子的混排减小,样品的充放电比容量逐渐增大,且2.7 V处的放电平台容量也增加.当x=1/12时,样品具有较好的充放电比容量和倍率特性,首次放电比容量为107.3 mA·h/g,20次循环后容量保持率为84.9%.