Increased Efficacies of an Individual Catalytic Site in Clustered Multivalent Dendritic Catalysts

In the studies reported so far on dendrimer-mediated catalysis, the efficacies of the catalytic units were studied and compared primarily across the generations. In order to identify the efficacy of an individual catalytic unit with respect to the number of such units present within a given generation, a series of catalysts were prepared within a generation. Dendrimers incorporated with phosphinemetal complexes were chosen for the study and as many as 11 catalysts within three generations were synthesized. The C-C bond-forming reactions, namely, the Heck and the Suzuki coupling reactions, were then selected to study the catalytic efficiencies of the series of partially and fully phosphine-metal complex functionalized dendrimers. The efficacies of the formation of cinnamate and biphenyl. catalyzed by the dendritic catalysts, were compared. The comparative analyses show that an individual catalytic site is far more effective in its catalytic activity when presented in multiple numbers, i.e., in a multivalent dendritic system, than as a single unit within the same generation, i.e., in a monovalent dendritic system. The study identifies the beneficial effects of the multivalent presentation of the catalytic moieties, both within and across the dendrimer generations.

Cyclometalated complexes derived from calix[4] arene bisphosphites and their catalytic applications in cross-coupling reactions

Palladium and platinum dichloride complexes of a series of symmetrically and unsymmetrically substituted 25,26;27,28-dibridged p-tert-butyl-calix[4]arene bisphosphites in which two proximal phenolic oxygen atoms of p-tert-butyl-or p-H-calix[4]arene are connected to a P(OR) ( R = substituted phenyl) moiety have been synthesized. The palladium dichloride complexes of calix[4]arene bisphosphites bearing sterically bulky aryl substituents undergo cyclometalation by C-C or C-H bond scission. An example of cycloplatinated complex is also reported. The complexes have been characterized by NMR spectroscopic and single crystal X-ray diffraction studies. During crystallization of the palladium dichloride complex of a symmetrically substituted calix[4]arene bisphosphite in dichloromethane, insertion of oxygen occurs into the Pd-P bond to give a P,O-coordinated palladium dichloride complex. The calix[4]arene framework in these bisphosphites and their metal complexes adopt distorted cone conformation; the cone conformation is more flattened in the metal complexes than in the free calix[4]arene bisphosphites. Some of these cyclometalated complexes proved to be active catalysts for Heck and Suzuki C-C cross-coupling reactions but, on an average, the yields are only modest. (C) 2011 Elsevier B.V. All rights reserved.

Branching out at C-2 of septanosides. Synthesis of 2-deoxy-2-C-alkyl/aryl septanosides from a bromo-oxepine

This paper deals with the synthesis of 2-deoxy-2-C-alkyl/aryl septanosides. A range of such septanoside derivatives was synthesized by using a common bromo-oxepine intermediate, involving C-C bond forming organometallic reactions. Unsaturated, seven-membered septanoside vinyl bromides or bromo-oxepines, obtained through a ring expansion methodology of the cyclopropane derivatives of oxyglycals, displayed a good reactivity towards several acceptor moieties in C-C bond forming Heck, Suzuki and Sonogashira coupling reactions, thus affording 2-deoxy-2-C-alkyl/aryl septanosides. Whereas Heck and Sonogashira coupling reactions afforded 2-deoxy-2-C-alkenyl and -alkynyl derivatives, respectively, the Suzuki reaction afforded 2-deoxy-2-C-aryl septanosides. Deprotection and reduction of the 2-deoxy-2-alkenyl derivative afforded the corresponding 2-deoxy-2-C-alkyl septanoside free of protecting groups. The present study illustrates the reactivity of bromo-oxepine in the synthesis of hitherto unknown septanosides, branching out at C-2, through C-C bond formation with alkyl and aryl substituents.

Pd-Catalyzed Cross-Coupling Reactions of Hydrazones: Regioselective Synthesis of Highly Branched Dienes

The regioselective formation of highly branched dienes is a challenging task. Design and exploration of alternative working models to achieve such a regioselectivity to accomplish highly branched dienes is considered to be a historical advancement of Heck reaction to construct branched dienes. On the basis of the utility of carbene transfer reactions, in the reaction of hydrazones with Pd(II) under oxidative conditions, we envisioned obtaining a Pd-bis-carbene complex with alpha-hydrogens, which can lead to branched dienes. Herein, we report a novel Pd-catalyzed selective coupling reaction of hydrazones in the presence of t-BuOLi and benzoquinone to form the corresponding branched dienes. The utility of the Pd catalyst for the cross-coupling reactions for synthesizing branched conjugated dienes is rare. The reaction is very versatile and compatible with a variety of functional groups and is useful in synthesizing heterocyclic molecules. We anticipate that this Pd-catalyzed cross-coupling reaction will open new avenues for synthesizing useful compounds.

Ru (II)-Catalyzed C-H Activation: Ketone-Directed Novel 1,4-Addition of Ortho C-H Bond to Maleimides

A 1,4-addition with the nucleophilic center generated at the ortho carbon atom of an aromatic ketone in the presence of the highly reactive alpha-C-H bond, using a directing group strategy, is presented. The reaction yields pharmaceutically useful 3-arylated succinimide derivatives. In order to gain understanding of this redox neutral reaction, despite the presence of copper acetate, and to substantiate the lack of Heck-type products, DFT calculations have been carried out.

Site-Selective Addition of Maleimide to Indole at the C-2 Position: Ru(II)-Catalyzed C-H Activation

Synthesis of 3-(indol-2-yl)succinimide derivatives is presented using a directing group strategy. Selective functionalization of C-2 in the presence of highly reactive C-3 in indole derivatives has been achieved. A conjugate addition product instead of Heck-type product has been brought about by careful selection of the alkene partner (maleimides and maleate esters) such that a beta-hydride elimination is avoided.

High Loading of Pd Nanoparticles by Interior Functionalization of MOFs for Heterogeneous Catalysis

In this report, the issue related to nanoparticle (NP) agglomeration upon increasing their loading amount into metal-organic frameworks (MOFs) has been addressed by functionalization of MOFs with alkyne groups. The alkynophilicity of the Pd2+ (or other noble metals) ions has been utilized successfully for significant loading of Pd NPs into alkyne functionalized MOFs. It has been shown here that the size and loading amount of Pd NPs are highly dependent on the surface area and pore width of the MOFs. The loading amount of Pd NPs was increased monotonically without altering their size distribution on a particular MOF. Importantly, the distinct role of alkyne groups for Pe(2+) stabilization has also been demonstrated by performing a control experiment considering a MOF without an alkyne moiety. The preparation of NPs involved two distinct steps viz. adsorption of metal ions inside MOFs and reduction of metal ions. Both of these steps were monitored by microscopic techniques. This report also demonstrates the applicability of Pd@MOF NPs as extremely efficient heterogeneous catalysts for Heck-coupling and hydrogenation reactions of aryl bromides or iodides and alkenes, respectively.

Astrophysics and Distributed Research utilising Advanced Computing (DiRAC)

Supporting presentation slides to accompany the Janet network end to end performance initiative workshop

Accelerating loss of seagrasses across the globe threatens coastal ecosystems

Coastal ecosystems and the services they provide are adversely affected by a wide variety of human activities. In particular, seagrass meadows are negatively affected by impacts accruing from the billion or more people who live within 50 km of them. Seagrass meadows provide important ecosystem services, including an estimated $1.9 trillion per year in the form of nutrient cycling; an order of magnitude enhancement of coral reef fish productivity; a habitat for thousands of fish, bird, and invertebrate species; and a major food source for endangered dugong, manatee, and green turtle. Although individual impacts from coastal development, degraded water quality, and climate change have been documented, there has been no quantitative global assessment of seagrass loss until now. Our comprehensive global assessment of 215 studies found that seagrasses have been disappearing at a rate of 110 square kilometers per year since 1980 and that 29% of the known areal extent has disappeared since seagrass areas were initially recorded in 1879. Furthermore, rates of decline have accelerated from a median of 0.9% per year before 1940 to 7% per year since 1990. Seagrass loss rates are comparable to those reported for mangroves, coral reefs, and tropical rainforests and place seagrass meadows among the most threatened ecosystems on earth.

Biographical Sketch of Spencer Fullerton Baird

Spencer Fullerton Baird was born in Reading, Pennsylvania, February 3, 1823. In 1834 he was sent to a Quaker boarding-school kept by Dr. McGraw, at Port Deposit, Maryland, and the year following to the Reading Grammar School. In 1836 he entered Dickinson College, and was graduated at the age of seventeen. After leaving college, his time for several years was devoted to studies in general natural history, to long pedestrian excursions for the purpose of observing animals and plants and collecting specimens, and to the organization of a private cabinet of natural history, which a few years later became the nucleus of the museum of the Smithsonian Institution. During this period he published a number of original papers on natural history. He also read medicine with Dr. Middleton Goldsmith, attending a winter course of lectures at the College of Physicians and Surgeons, in New York, in 1842. His medical course was never formally completed, although in 1848 he received the degree of M. D., honoris causa, from the Philadelphia Medical College. In 1845 he was chosen professor of natural history in Dickinson College, and in 1846 his duties and emoluments were increased by election to the chair of natural history and chemistry in the same institution. In 1848 he declined a call to the professorship of natural science in the University of Vermont. In 1849 he undertook his first extensive literary work, translating and editing the text for the "Iconographic Encyclopedia," an English version of Heck's Bilder Atlas, published in connection with Brockhaus's Conversations Lexikon.

Accelerating loss of seagrasses across the globe threatens coastal ecosystems

Coastal ecosystems and the services they provide are adversely affected by a wide variety of human activities. In particular, seagrass meadows are negatively affected by impacts accruing from the billion or more people who live within 50 km of them. Seagrass meadows provide important ecosystem services, including an estimated $1.9 trillion per year in the form of nutrient cycling; an order of magnitude enhancement of coral reef fish productivity; a habitat for thousands of fish, bird, and invertebrate species; and a major food source for endangered dugong, manatee, and green turtle. Although individual impacts from coastal development, degraded water quality, and climate change have been documented, there has been no quantitative global assessment of seagrass loss until now. Our comprehensive global assessment of 215 studies found that seagrasses have been disappearing at a rate of 110 square kilometers per year since 1980 and that 29% of the known areal extent has disappeared since seagrass areas were initially recorded in 1879. Furthermore, rates of decline have accelerated from a median of 0.9% per year before 1940 to 7% per year since 1990. Seagrass loss rates are comparable to those reported for mangroves, coral reefs, and tropical rainforests and place seagrass meadows among the most threatened ecosystems on earth.

端基官能化共轭齐聚物的设计与合成

和共轭聚合物相比，单分散共轭齐聚物具有结构确定、易提纯等优点，不仅是建立共轭体系结构与性能关系的最佳模型，而且是一类高纯度光电子材料，还是构造具有规整结构嵌段共聚物和超分子体系的理想构造单元。鉴于基于芴单元的共轭齐聚物与聚合物具有优异的光电性能，引入不同端基能够有效调节共轭齐聚物的性能，本论文以端基官能化齐聚芴为研究对象，设计与合成了具有不同端基结构的系列单分散齐聚芴，研究了它们基本的物理化学性质，主要成果与创新点如下： 1、利用Horner-Wadsworth-Emmons反应、Wittig反应和Heck偶联反应，交替引入极性、非极性反应端基，成功解决了发散法合成较长单分散共轭齐聚物过程中产物难以提纯的技术问题，合成了系列芴撑乙烯撑共轭齐聚物。其中，最长的齐聚物含11个芴单元，光谱外推得到的有效共轭长度可达19个重复单元。DSC和偏光显微镜研究表明，芴单元数大于5的齐聚物可形成向列型液晶相。含7个芴单元以上的齐聚物可用于制备有机发光二极管，含11个芴单元的齐聚物电致发光效率是相应聚合物的5倍。 2、通过Hagigara-Sonogashira偶联、Diels-Alder环加成等反应合成了一系列端基为刚性的苯乙炔基和五苯基苯的单分散齐聚芴。但典型Scholl反应条件不能实现完全氧化脱氢，获得六苯并晕苯封端的齐聚芴。光谱研究表明苯乙炔基的引入导致吸收光谱和荧光光谱有1-2 nm的红移。五苯基苯结构的引入能显著提高齐聚芴的Tg，从而提高齐聚物的形态稳定性。 3、利用Yamamoto反应，采用端基溴代的齐聚芴大分子单体聚合结合制备色谱分离，成功地制备了分子量超过20000 Da的单分散共轭聚合物，说明大分子单体聚合结合制备色谱分离制备单分散共轭聚合物是可行的。 4、通过Horner-Wadsworth-Emmons反应合成一系列端基为三苯胺乙烯撑的单分散齐聚芴，其中，最长的齐聚物含9个芴单元。光谱研究表明，随芴单元数的增加，两个三苯胺乙烯撑端基间共轭作用显著减弱，最大吸收波长蓝移；当芴的单元数≥3时，最大发射波长均位于450 nm，和聚芴和齐聚芴相比，这类共轭齐聚物的蓝光发光峰位更佳。电化学研究表明三苯胺乙烯撑单元的氧化还原过程不受齐聚芴单元长度的影响，该封端齐聚芴的HOMO能级主要是由三苯胺乙烯撑单元决定。 关键词：端基官能化，齐聚芴，单分散共轭聚合物

分子导线的合成、组装及电子传输性能研究

分子导线作为未来分子电子学的重要组成部分，其合成、组装及电子传输性能研究是当今化学、物理、生物及微电子工程学等领域里一个非常热门的课题，而我国在这方面的研究几乎空白。本人在王献红研究员和王佛松院士的悉心指导下在国内率先开展了分子导线的研究工作。总结起来，前一段时间的工作成果主要有以下几个方面：一、功能化分子导线的合成 通过以Heck偶联为主的反应，我们合成出八种功能化的分子导线，其两端所带的功能团(-SAc, -NH_2, -NO_2, N_2BF_4)不仅可以使它们在不同的基底上实现组装，而且对于研究分子导线的电子传输性能，探讨分子导线在生物、化学传感器中的应用具有重大意义。我们对关键组分的合成作了重大改进。所有化合物都经过红外、核磁、质谱、元素分析或紫外－可见光谱等表征手段的鉴定。二、分子导线的固定相合成 分子导线在溶液相中合成碰到的最大难题是分离纯化。经过一段时间的积累，我们提出了一个双向快速增长的固定相合成路线，并采用该方案合成出长度接近50A两端为乙酰巯基“分子钳“的可溶性分子导线。我们的方案允许对分子导线进行精确地裁剪，并有望在现有的合成基础上经过简单的几步反应合成出具有逻辑、记忆和放大功能的单分子器件。三、分子导线的组装 我们将合成出的功能化分子导线组装在单晶或多晶金电极表面，通过扫描隧道显微镜观察了组装上分子导线单层后单晶金电极表面的形貌，通过电化学技术研究了分子导线自组膜的钝化行为，并现场观察了分子导线的组装过程。我们还讨论了分子导线的结构、长度及组装条件对自组膜性能的影响。四、分子导线的电子传输性能研究 我们将自组装技术和电化学纳米粒子沉积技术结合起来构筑了几种“金电极－分子导线－金的纳米粒子“的夹心结构，通过STM观察了整个过程中修饰电极表面形貌的变化。循环伏安和交流阻抗技术测定了这种夹心结构的电子传输性能，发现夹在两个金电极之间的分子导线单层具有很好的电子导通能力。作为比较，我们采用一种巧妙的办法将柔性的双硫醇单层夹在两个金电极之间，发现其电子传输性能明显比分子导线单层差。结合MM2力场理论计算结果，我们详细地讨论了分子导线的骨架结构、长度、对称性以及界面接触对分子导线电子传输性能的影响。