Probing the C-H Activation of Linear and Cyclic Ethers at (PNP)Ir

Interaction of the amido/bis(phosphine)-supported (PNP)Ir fragment with a series of linear and cyclic ethers is shown to afford, depending on substrate, products of α,α-dehydrogenation (carbenes), α,β-dehydrogenation (vinyl ethers), or decarbonylation. While carbenes are exclusively obtained from tert-amyl methyl ether, sec-butyl methyl ether (SBME), n-butyl methyl ether (NBME), and tetrahydrofuran (THF), vinyl ethers or their adducts are observed upon reaction with diethyl ether and 1,4-dioxane. Decarbonylation occurs upon interaction of (PNP)Ir with benzyl methyl ether, and a mechanism is proposed for this unusual transformation, which occurs via a series of C−H, C−O, and C−C bond cleavage events. The intermediates characterized for several of these reactions as well as the α,α-dehydrogenation of tert-butyl methyl ether (MTBE) are used to outline a reaction pathway for the generation of PNP-supported iridium(I) carbene complexes, and it is shown that the long-lived, observable intermediates are substrate-dependent and differ for the related cases of MTBE and THF. Taken together, these findings highlight the variety of pathways utilized by the electron-rich, unsaturated (PNP)Ir fragment to stabilize itself by transferring electron density to ethereal substrates through oxidative addition and/or the formation of π-acidic ligands

Using diffusion tensor imaging to identify corticospinal tract projection patterns in children with unilateral spastic cerebral palsy.

AIM: To determine whether diffusion tensor imaging (DTI) can be an independent assessment for identifying the corticospinal tract (CST) projecting from the more-affected motor cortex in children with unilateral spastic cerebral palsy (CP). METHOD: Twenty children with unilateral spastic CP participated in this study (16 males, four females; mean age 9y 2mo [standard deviation (SD) 3y 2mo], Manual Ability Classification System [MACS] level I-III). We used DTI tractography to reconstruct the CST projecting from the more-affected motor cortex. We mapped the motor representation of the more-affected hand by stimulating the more- and the less-affected motor cortex measured with single-pulse transcranial magnetic stimulation (TMS). We then verified the presence or absence of the contralateral CST by comparing the TMS map and DTI tractography. Fisher's exact test was used to determine the association between findings of TMS and DTI. RESULTS: DTI tractography successfully identified the CST controlling the more-affected hand (sensitivity=82%, specificity=78%). INTERPRETATION: Contralateral CST projecting from the lesioned motor cortex assessed by DTI is consistent with findings of TMS mapping. Since CST connectivity may be predictive of response to certain upper extremity treatments, DTI-identified CST connectivity may potentially be valuable for determining such connectivity where TMS is unavailable or inadvisable for children with seizures.K08 NS073796 - NINDS NIH HHS; TL1 RR024158 - NCRR NIH HHS; K01 NS062116 - NINDS NIH HHS; UL1 RR024156 - NCRR NIH HHS; KL2 RR024157 - NCRR NIH HHS; R01 HD076436 - NICHD NIH HHSPublished versio

Weak convergence of Vervaat and Vervaat Error processes of long-range dependent sequences

Following Cs\"{o}rg\H{o}, Szyszkowicz and Wang (Ann. Statist. {\bf 34}, (2006), 1013--1044) we consider a long range dependent linear sequence. We prove weak convergence of the uniform Vervaat and the uniform Vervaat error processes, extending their results to distributions with unbounded support and removing normality assumption

Impact of flood disasters on Taiwan in the last quarter century

Copyright © Springer 2006. The final publication is available at Springer via http://dx.doi.org/10.1007/s11069-005-4667-7The increasing natural disasters, especially floods during the last quarter century, are raising the economic losses in Taiwan. The most severe hazard in Taiwan is flooding induced by typhoons and storms in summer and autumn. By comparing the rivers around the world, the ones in Taiwan have the steepest slopes, the largest discharge per unit drainage area, and the shortest time of concentrations. Rapid urbanization without proper land uses managements usually worsen the flood problems. Consequently, flood hazards mitigation has become the most essential task for Taiwan to deal with. Although the government keeps improving flood defense structures, the flood damage grows continuously. In this article, possible flood mitigation strategies are identified for coping with complex environmental and social decisions with flood risk involved.National Science and Technology Center for Disaster ReductionNational Science Council, RO

Foundations of character: methodological aspects of a study of character development in three- to six-year-old children with a focus on sharing behaviours

This article focuses on methodological issues arising in a study of character development, using illustrations of ‘sharing behaviours.’ Based primarily in six early years settings in southeast England the research records naturalistic observations of peer interactions for 55 children aged three to six years. Applying grounded theory to the processes of observing, analysing and interpreting evidence required a cautious and collectively reflective approach. The methodology sought to moderate the influence of the researchers' prior knowledge of ‘grand theories’ of moral development and assumptions about relevance to the observation records. The study's originality lay in the exploration of moral development without reference to any particular grand theory as an explanatory framework; and in the reluctance to be drawn to potentially simplistic rationalisations of the children's intentions on the basis of their observed behaviours. Exploring young children's subjective experiences, this research provides insights into the intricacy of this process, steering away from ‘neat’ findings and attempting to reflect the sophistication of the children's skilful and sometimes surprising negotiations of moral dilemmas. Implications for practice relate to the complexities involved in attempts to unravel the developing moral characters of young children and the practice through which this may be nurtured

Soap opera : polymer-surfactant interactions on thin film surfaces /

Surfactants are macromolecules with unique properties. They commonly contain a polar head group with a nonpolar hydrocarbon chain. These properties allow surfactants to solubilize greases and other nonpolar molecules. One particular way that this is accomplished is through the formation of micelles. Micelles are formed at the critical micelle concentration (cmc), which varies depending upon the nature of the surfactant and also the media in which the surfactant resides. These micelles can take a variety of shapes, but are generally characterized by surrounding the grease with the nonpolar hydrocarbon chains, exposing only the polarized head groups to the media, usually water. This property of easy solubilization has made surfactants a very attractive industrial agent, They are used most conventionally as industrial cleaning agents and detergents. However, they also have lesser-known applications in conjunction with polymers and other macromolecular mixtures, often creating a system with novel properties, such as increased solubilization and smoother mixture consistency. A recently developed field has investigated the self-assembly of polymers and polyelectrolytes onto thin film surfaces. There are many reasons for studying this process, such as for second harmonic generation purposes and bioassays. In this study, the interaction between the anionic polyelectrolyte poly[1-[4-(3-carboxy-4-hydroxyphenylazo)benzenesulfonamido]-1,2-ethanediyl, sodium salt] (PAZO) and two surfactants of opposite charge, Sodium Dodecyl Sulfate (SDS) and Dodecyl Trimethyl Ammonium Bromide (DTAB), in their assembly onto thin film surfaces was investigated. The kinetics of adsorbance onto the thin films was examined, followed by construction of 10-bilayer films using an alternating layer of the cationic polyelectrolyte poly(ethylenimine) (PEI) to provide the electrostatic means for the PAZO/surfactant combination to assemble onto the thin film. The kinetics of adsorption is being characterized primarily with UV-visible spectroscopy, whereas the ten bilayers are being studied with both UV-visible spectroscopy and ellipsometry. Preliminary results suggest that the rate of adsorbance of various concentrations of SDS below and above the cmc in PAZO is not significantly different from the rate of adsorbance of pure PAZO. However, the amount of adsorbed material decreases as the concentration of SDS dissolved into PAZO increases. This has allowed for less PAZO adsorbance to be detected in the 10-bilayer systems. Preliminary kinetics data suggest longer saturation times for DTAB/PAZO systems, but amount adsorbed may be increased from pure PAZO systems. Further work is being conducted on the kinetics, and more 10 bilayer films remain to be built and characterized. In situ methods of studying the films will also be examined in the future