Rapid,General Synthesis of PdPt Bimetallic Alloy Nanosponges and Their Enhanced Catalytic Performance for Ethanol/Methanol Electrooxidation in an Alkaline Medium

We have demonstrated a rapid and general strategy to synthesize novel three‐dimensional PdPt bimetallic alloy nanosponges in the absence of a capping agent. Significantly, the as‐prepared PdPt bimetallic alloy nanosponges exhibited greatly enhanced activity and stability towards ethanol/methanol electrooxidation in an alkaline medium, which demonstrates the potential of applying these PdPt bimetallic alloy nanosponges as effective electrocatalysts for direct alcohol fuel cells. In addition, this simple method has also been applied for the synthesis of AuPt, AuPd bimetallic, and AuPtPd trimetallic alloy nanosponges. The as‐synthesized three‐dimensional bimetallic/trimetallic alloy nanosponges, because of their convenient preparation, well‐defined sponge‐like network, large‐scale production, and high electrocatalytic performance for ethanol/methanol electrooxidation, may find promising potential applications in various fields, such as formic acid oxidation or oxygen reduction reactions, electrochemical sensors, and hydrogen‐gas sensors.     

Expanded Organic Building Units for the Construction of Highly Porous Metal–Organic Frameworks

Two new organic building units that contain dicarboxylate sites for their self‐assembly with paddlewheel [Cu₂(CO₂)₄] units have been successfully developed to construct two isoreticular porous metal–organic frameworks (MOFs), ZJU‐35 and ZJU‐36, which have the same tbo topologies (Reticular Chemistry Structure Resource (RCSR) symbol) as HKUST‐1. Because the organic linkers in ZJU‐35 and ZJU‐36 are systematically enlarged, the pores in these two new porous MOFs vary from 10.8 Å in HKUST‐1 to 14.4 Å in ZJU‐35 and 16.5 Å in ZJU‐36, thus leading to their higher porosities with Brunauer–Emmett–Teller (BET) surface areas of 2899 and 4014 m² g^?1 for ZJU‐35 and ZJU‐36, respectively. High‐pressure gas‐sorption isotherms indicate that both ZJU‐35 and ZJU‐36 can take up large amounts of CH₄ and CO₂, and are among the few porous MOFs with the highest volumetric storage of CH₄ under 60 bar and CO₂ under 30 bar at room temperature. Their potential for high‐pressure swing adsorption (PSA) hydrogen purification was also preliminarily examined and compared with several reported MOFs, thus indicating the potential of ZJU‐35 and ZJU‐36 for this important application. Studies show that most of the highly porous MOFs that can volumetrically take up the greatest amount of CH₄ under 60 bar and CO₂ under 30 bar at room temperature are those self‐assembled from organic tetra‐ and hexacarboxylates that contain m‐benzenedicarboxylate units with the [Cu₂(CO₂)₄] units, because this series of MOFs can have balanced porosities, suitable pores, and framework densities to optimize their volumetric gas storage. The realization of the two new organic building units for their construction of highly porous MOFs through their self‐assembly with [Cu₂(CO₂)₄] units has provided great promise for the exploration of a large number of new tetra‐ and hexacarboxylate organic linkers based on these new organic building units in which different aromatic backbones can be readily incorporated into the frameworks to tune their porosities, pore structures, and framework densities, thus targeting some even better performing MOFs for very high gas storage and efficient gas separation under high pressure and at room temperature in the near future.     

Collective Total Synthesis of Englerin A and B,Orientalol E and F,and Oxyphyllol: Application of the Organocatalytic [4+3] Cycloaddition Reaction

The concise collective total synthesis of englerin A and B, orientalol E and F, and oxyphyllol has been accomplished in 10–15 steps, with the total synthesis of orientalol E and oxyphyllol being achieved for the first time. The success obtained was enabled by the realization of the [4+3] cycloaddition reaction of 9 and 10 . Other features of the synthesis include 1) the intramolecular Heck reaction to access the azulene core, 2) the epoxidation–S_N2′ reduction sequence to access the allylic alcohol, 3) the efficient regioselective and stereoselective formal hydration of the bridging C?C bond in the synthesis of englerins, and 4) the late‐stage chemo‐ and stereoselective C? H oxidation in the synthesis of orientalol E. The total synthesis of these natural products has enabled the structural revision of oxyphyllol and established the absolute stereochemical features of the organocatalytic [4+3] cycloaddition reaction. The identification of 5 as the natural product oxyphyllol, the success in converting 5 to orientalol E, along with the fact that englerins and oxyphyllol were isolated from plants of the same genus Phyllanthus gives support to our proposed biosynthetic pathways. This work may enable detailed biological evaluations of these natural products and their analogues and derivatives, especially of their potential in the fight against renal cell carcinoma (RCC).     

Direct grafting modification of pulp in ionic liquids and self-assembly behavior of the graft copolymers

In this paper, a novel biodegradable biomass-based amphiphile was prepared by direct grafting copolymerization of dissolved pulp with hydrophobic poly (l-lactide) in ionic liquids BmimCl. The molecular structures of the obtained copolymers were confirmed with ¹H-NMR, ¹³C-NMR and 2D HSQC NMR, and their physical properties were studied by TGA and XRD analysis. The self-assembly behaviors of these amphiphilies in aqueous solution was characterized by fluorescence spectrum and their critical micelle concentrations (CMC) were determined to be in the range of 0.326–0.062 mg/mL. TEM observations and DLS analysis revealed that the pulp-derived micelles had spherical and uniform morphology and small diameters (25–125 nm). It was also found that the surface tension of these copolymers solution firstly decreased dramatically with increasing concentration and then approached to a plateau value when the concentration was above their CMC value. MTT assay showed that the pulp-derived amphiphilic micelles exhibited good biocompatibility, which informed that these micelles could be expected to be used in biological regions, especially for the hydrophobic drug delivery system.     

ClF-分子离子的结构与势能函数

采用单、双取代包括三重激发的二次组态相互作用[QCISD(T)]方法和单、双取代包括非迭代三重激发的耦合簇理论[CCSD(T)]方法, 结合相关一致基组aug-cc-pVXZ (X=D, T, Q, 5)对基态³⁵ClF^-和³⁷ClF^- (X²Σ⁺)分子离子进行了结构优化计算. 对CCSD(T)方法的计算结果用四种方法分别外推至基组极限, 得到了体系在基组极限的平衡结构常数. 在CCSD(T)/aug-cc-pVXZ (X=D, T, Q, 5)理论水平进行了单点能扫描. 对扫描计算结果进行基组外推并用Murrell-Sorbie 势能函数拟合得到了体系的解析势能函数表达式, 并进一步得到了³⁵ClF^-和³⁷ClF^-的光谱常数. 拟合所得势能曲线准确地再现了其离解能和平衡结构特征. 对ClF 中性自由基采用完全相同的理论方法进行了计算. 所得结果与有关文献中的实验结果符合得很好, 而且在一定程度上证明了将该理论方法应用于ClF^-分子离子的计算是合适而可靠的. ClF 自由基的优化计算结果还被用于计算其电子亲和能.ClF^-的垂直解离能也同时计算得出. 基于ClF^-的结构优化和单点能扫描计算结果, 通过求解核运动的径向薛定谔方程, 得到了无转动³⁵ClF^-和³⁷ClF^-(X²Σ⁺)的全部振动态及相应的分子常数.     

三维介孔氨基三亚甲基膦酸锆的合成及其担载铁催化剂的甲醛催化氧化活性

以氧氯化锆和氨基三亚甲基膦酸(ATMP)为原料合成了一种新型介孔材料氨基三亚甲基膦酸锆(NTAZP)。使用XRD、FTIR、TG-DTA和SEM等手段对所合成的介孔材料进行了结构表征和形貌分析。然后以NTAZP为载体,用Fe(NO3)3水溶液处理,得到担载Fe3+的氨基三亚甲基膦酸锆。研究结果表明,Fe3+被吸附到载体孔道中后,NTAZP结构未被破坏,Fe3+离子与NTAZP孔壁骨架上的N发生了配位作用。铁担载NTAZP(NTAZP-Fe3+)对甲醛氧化具有良好的催化活性,催化反应条件温和,催化剂稳定性良好。以载体NTAZP担载铁还避免了Fe3+进入水体,催化剂得以回收利用,避免造成二次污染。NTAZP-Fe3+是一种高效绿色的新型小分子醛类化合物氧化催化剂。     

基于FCS的海水痕量元素的通用测定平台

为了对海水痕量营养盐与重金属进行测定,基于FCS的设计思想,采用流动注射分光光度法研制了具有自适应外界设备、快速组建多种仪器及全数字化通信等特点的软硬件一体化的通用测定平台。平台以ARM(S3C2416)处理器为核心,Linux为操作系统,LCD作为人机交互显示,触摸屏或者USB鼠标完成输入控制,构成完整的嵌入式工控机系统;采用CAN总线并制定CAN应用层协议管理设备,提高了系统的可靠性及抗干扰能力。实际测试和应用证明,该平台自动化程度高,通用性、重用性及可扩展性均较强,可组建成亚硝氮、硝氮、氨氮、活性磷、铁等多种痕量元素的实验室、船载和原位分析系统,检测限为nmol/L级别。平台对样品的测试准确度与商品专用仪器无显著性差异。     

High‐Order Soliton Solution of Landau–Lifshitz Equation

The Landau–Lifshitz equation is analyzed via the inverse scattering method. First, we give the well‐posedness theory for Landau–Lifshitz equation with the frame of inverse scattering method. The generalized Darboux transformation is rigorous considered in the frame of inverse scattering transformation. Finally, we give the high‐order soliton solution formula of Landau–Lifshitz equation and vortex filament equation.     

Interactions of delta shock waves for the relativistic Chaplygin Euler equations with split delta functions

In this article, we are concerned with the interactions of delta shock waves with contact discontinuities for the relativistic Euler equations for Chaplygin gas by using split delta functions method. The solutions are obtained constructively and globally when the initial data consists of three piecewise constant states. The global structure and large time‐asymptotic behaviors of the solutions are analyzed case by case. During the process of the interaction, the strengths of delta shock waves are computed completely. Moreover, it can be found that the Riemann solutions are stable for such small perturbations with special initial data by letting perturbed parameter ε tends to zero. Copyright © 2014 John Wiley & Sons, Ltd.     

On Gradient Solitons of the Ricci–Harmonic Flow

In this paper, we study gradient solitons to the Ricci flow coupled with harmonic map heat flow. We derive new identities on solitons similar to those on gradient solitons of the Ricci flow. When the soliton is compact, we get a classification result. We also discuss the relation with quasi-Einstein manifolds.