Solvent extraction of Pu(IV) with TODGA in C6mimTf2N

Studies on the solvent extraction of Plutonium(Pu(IV)) from aqueous nitric acid by N,N,N′,N′-tetraoctyl-diglycolamide (TODGA) in 1-hexyl-3-methylimidazolium-bis(trifluoromethylsulfonyl) imide (C₆mimTf₂N) room temperature ionic liquid (RTIL) were carried out. It was found that Pu(IV) is extracted into RTIL phase as [Pu(NO₃)(TODGA)]³⁺ through cation exchange mechanism. Extraction reaction equation is obtained by the influence of acidity and extractant concentration, and the parameters of thermodynamic equilibrium constant was calculated.     

Self‐assembly of Functionalized Gold Nanoparticles with Rigid and Flexible Multifunctional Linkers

The interparticle spacing of carboxyl functionalized gold nanoparticles (Au‐COOH) were mediated by rigid crosslinkers, octa(3‐aminopropyl)octasilsesquioxane (POSS‐NH₃ ⁺) and poly(amidoamine) dendrimer terminated with hydroxyl groups (PAMAM‐OH), and a flexible polymeric linker, poly(hexanul viologen) (6‐VP). Regular interparticle spacing was achieved by utilizing POSS‐NH₃ ⁺ and PAMAM‐OH dendrimer as cross linkers, whereas size growth of Au‐COOH was observed featuring no interparticle spacing by utilizing 6‐VP as the crosslinker.     

Doping metal-organic frameworks for water oxidation, carbon dioxide reduction, and organic photocatalysis

Catalytically competent Ir, Re, and Ru complexes H(2)L(1)-H(2)L(6) with dicarboxylic acid functionalities were incorporated into a highly stable and porous Zr(6)O(4)(OH)(4)(bpdc)(6) (UiO-67, bpdc = para-biphenyldicarboxylic acid) framework using a mix-and-match synthetic strategy. The matching ligand lengths between bpdc and L(1)-L(6) ligands allowed the construction of highly crystalline UiO-67 frameworks (metal-organic frameworks (MOFs) 1-6) that were doped with L(1)-L(6) ligands. MOFs 1-6 were isostructural to the parent UiO-67 framework as shown by powder X-ray diffraction (PXRD) and exhibited high surface areas ranging from 1092 to 1497 m(2)/g. MOFs 1-6 were stable in air up to 400 °C and active catalysts in a range of reactions that are relevant to solar energy utilization. MOFs 1-3 containing [Cp*Ir(III)(dcppy)Cl] (H(2)L(1)), [Cp*Ir(III)(dcbpy)Cl]Cl (H(2)L(2)), and [Ir(III)(dcppy)(2)(H(2)O)(2)]OTf (H(2)L(3)) (where Cp* is pentamethylcyclopentadienyl, dcppy is 2-phenylpyridine-5,4'-dicarboxylic acid, and dcbpy is 2,2'-bipyridine-5,5'-dicarboxylic acid) were effective water oxidation catalysts (WOCs), with turnover frequencies (TOFs) of up to 4.8 h(-1). The [Re(I)(CO)(3)(dcbpy)Cl] (H(2)L(4)) derivatized MOF 4 served as an active catalyst for photocatalytic CO(2) reduction with a total turnover number (TON) of 10.9, three times higher than that of the homogeneous complex H(2)L(4). MOFs 5 and 6 contained phosphorescent [Ir(III)(ppy)(2)(dcbpy)]Cl (H(2)L(5)) and [Ru(II)(bpy)(2)(dcbpy)]Cl(2) (H(2)L(6)) (where ppy is 2-phenylpyridine and bpy is 2,2'-bipyridine) and were used in three photocatalytic organic transformations (aza-Henry reaction, aerobic amine coupling, and aerobic oxidation of thioanisole) with very high activities. The inactivity of the parent UiO-67 framework and the reaction supernatants in catalytic water oxidation, CO(2) reduction, and organic transformations indicate both the molecular origin and heterogeneous nature of these catalytic processes. The stability of the doped UiO-67 catalysts under catalytic conditions was also demonstrated by comparing PXRD patterns before and after catalysis. This work illustrates the potential of combining molecular catalysts and MOF structures in developing highly active heterogeneous catalysts for solar energy utilization.     

Highly stable and porous cross-linked polymers for efficient photocatalysis

Porous cross-linked polymers (PCPs) with phosphorescent [Ru(bpy)(3)](2+) and [Ir(ppy)(2)(bpy)](+) building blocks were obtained via octacarbonyldicobalt (Co(2)(CO)(8))-catalyzed alkyne trimerization reactions. The resultant Ru- and Ir-PCPs exhibited high porosity with specific surface areas of 1348 and 1547 m(2)/g, respectively. They are thermally stable at up to 350 °C in air and do not dissolve or decompose in all solvents tested, including concentrated hydrochloric acid. The photoactive PCPs were shown to be highly effective, recyclable, and reusable heterogeneous photocatalysts for aza-Henry reactions, α-arylation of bromomalonate, and oxyamination of an aldehyde, with catalytic activities comparable to those of the homogeneous [Ru(bpy)(3)](2+) and [Ir(ppy)(2)(bpy)](+) photocatalysts. This work highlights the potential of developing photoactive PCPs as highly stable, molecularly tunable, and recyclable and reusable heterogeneous photocatalysts for a variety of important organic transformations.     

FATIGUE LIFE ANALYSIS OF BONDED OFFSHORE LOADING HOSE UNDER ENVIRONMENTAL LOADS1)

海上漂浮软管是浮式生产储卸油装置上外输系统的关键设备.漂浮软管结构复杂且常年漂浮于海面上,极易受到风、浪、流等环境载荷的作用产生疲劳破坏而造成原油泄漏.首先,采用ABAQUS软件,建立了软管的有限元模型,得到了漂浮软管在弯矩和内压作用下的有限元结果;其次,采用水平方向的Morison方程和风载荷来描述漂浮软管在海面上复杂的载荷情况;再次,将静力学分析结果导入到FE-Safe疲劳分析软件中,将节点应力结果作为时间载荷历程,乘以相应的载荷倍数,得到疲劳分析的载荷谱,载入此载荷谱计算,得到了漂浮软管的寿命分布云图,其最小寿命满足工程要求;最后,分析了内压对疲劳寿命的影响,结果表明,一定大小的内压能提高软管的疲劳性能.     

A new convenient way to synthesize 1,3,4‐thiadiazol‐2‐yl urea derivatives under microwave irradiation

A simple and efficient method was developed for the synthesis of 1‐(substituted)‐3‐(5‐(substituted)‐1,3,4‐thiadiazol‐2‐yl) ureas from heterocyclic amino compounds and phenyl‐5‐(pyridine‐3‐yl)‐1,3,4‐thiadiazol‐2‐ylcarbamate( 2 ) or phenyl‐5‐(trifluoro‐methyl)‐1,3,4‐thiadiazol‐2‐ylcarbamate( 5 ) under solvent conditions using microwave irradiation. The products were obtained in satisfactory yield as we expected. The reactions can be realized by conventional heating, but we find that the condition of microwave is better according to the reaction time. New 1‐(substituted)‐3‐(5‐(substituted)‐1,3,4‐thiadiazol‐2‐yl) urea derivatives are reported. The products were characterized by ¹H NMR, ESI‐MS, and Elemental analysis. The crystal structure of compound 6h was determined by X‐ray single crystal diffraction. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:621–629, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20489     

对三联苯有机晶体的生长及性能

对三联苯是一种常见的有机闪烁剂,通常用作闪烁计数器的发光材料。对三联苯闪烁晶体具有对中子探测效率高以及不易潮解等特性,这使其在实际应用中具有广阔的前景。本文采用坩埚下降法,使用单层安瓿成功生长出φ12 mm×30 mm对三联苯晶体。在生长开始前通过差热分析,确定晶体的生长温度。生长完成后测试了晶体粉末的X射线衍射谱、摇摆曲线、红外光谱、荧光光谱和拉曼光谱。X射线衍射结果表明,生长的晶体为纯对三联苯相。从摇摆曲线结果可以看出,生长晶体质量良好。红外和拉曼分析结果显示,峰位并没有出现明显的偏移,表明晶体中杂质含量较少并未引起晶体分子化学结构的变化。荧光光谱没有杂质峰的出现也说明对三联苯晶体存在较少杂质或晶格缺陷。     

Functional Polythioamides Derived from Thiocarbonyl Fluoride**

Polythioamide is a unique type of sulfur-containing polymer with advanced functionalities. Nonetheless, the elemental sulfur commonly used in their synthesis tends to react readily with unsaturated functional groups, thereby limiting the scope of eligible substrates. Inspired by the highly efficient sulfur-fluoride exchange ( SuFEx ) polymerization through discrete hubs, we present herein a pioneering and versatile approach to the synthesis of polythioamides from diboronic acids, secondary diamines, and thiocarbonyl fluoride as the central connective hub. Well-defined structures, including previously inaccessible unsaturated substrates, were realized. These newly devised polythioamides can efficiently and selectively bind to metal ions and were applied in precious-metal recovery. Further development resulted in Pd^II-crosslinked single-chain nanoparticles serving as recyclable homogeneous catalysts, thus demonstrating the vast potential of these unprecedented polythioamides. We anticipate that thiocarbonyl fluoride could emerge as a potent hub for facilitating the intricate synthesis of sulfur-containing polymers.     

钙钛矿氧化物CaRu0.5Ti0.5O3中Ti掺杂诱导的铁磁性和自旋玻璃态

有钙钛矿结构的钌氧化物是一种典型的电子关联体系, 对其化学掺杂后将表现出丰富的新奇磁学性质. 我们采用传统的固相反应法制备了钙钛矿型 CaRu0 .5Ti0 .5 O3 块材(CRTO) . 相比于母体材料 CaRuO3 的顺磁性,CRTO 表现出截然不同的铁磁-顺磁转变, 居里温度为45 K. 根据对 CRTO 的晶体结构分析, 我们发现 Ti 元素的掺杂会导致氧八面体旋转畸变的减弱, 可能导致 Ru 离子之间的交换作用变强. 我们同时还进行了场冷-零场冷条件下的磁矩-温度测量和交流磁化率测量, 发现该体系出现了类自旋玻璃态.     

Room Temperature Anhydrous Suzuki–Miyaura Polymerization Enabled by C−S Bond Activation

The Suzuki–Miyaura cross-coupling is one of the most important and powerful methods for constructing C−C bonds. However, the protodeboronation of arylboronic acids hinder the development of Suzuki–Miyaura coupling in the precise synthesis of conjugated polymers (CPs). Here, an anhydrous room temperature Suzuki–Miyaura cross-coupling reaction between (hetero)aryl boronic esters and aryl sulfides was explored, of which universality was exemplified by thirty small molecules and twelve CPs. Meanwhile, the mechanistic studies involving with capturing four coordinated borate intermediate revealed the direct transmetalation of boronic esters in the absence of H₂O suppressing the protodeboronation. Additionally, the room temperature reaction significantly reduced the homocoupling defects and enhanced the optoelectronic properties of the CPs. In all, this work provides a green protocol to synthesize alternating CPs.