Chelation-enforced metal-arene interactions : insights into substrate binding and catalysis by late transition metal complexes

Understanding and catalyzing chemical reactions requiring multiple electron transfers is an endeavor relevant to many outstanding challenges in the field of chemistry. To study multi-electron reactions, a terphenyl diphosphine framework was designed to support one or more metals in multiple redox states via stabilizing interactions with the central arene of the terphenyl backbone. A variety of unusual compounds and reactions and their relevance toward prominent research efforts in chemistry are the subject of this dissertation.

Chapter 2 introduces the para-terphenyl diphosphine framework and its coordination chemistry with group 10 transition metal centers. Both mononuclear and dinuclear compounds are characterized. In many cases, the metal center(s) are stabilized by the terphenyl central arene. These metal–arene interactions are characterized both statically, in the solid state, and fluxionally, in solution. As a proof-of-principle, a dinickel framework is shown to span multiple redox states, showing that multielectron chemistry can be supported by the coordinatively flexible terphenyl diphosphine.

Chapter 3 presents reactivity of the terphenyl diphosphine when bound to a metal center. Because of the dearomatizing effect of the metal center, the central arene of the ligand is susceptible to reactions that do not normally affect arenes. In particular, Ni-to-arene H-transfer and arene dihydrogenation reactions are presented. Additionally, evidence for reversibility of the Ni-to-arene H-transfer is discussed.

Chapter 4 expands beyond the chelated metal-arene interactions of the previous chapters. A dipalladium(I) terphenyl diphosphine framework is used to bind a variety of exogenous organic ligands including arenes, dienes, heteroarenes, thioethers, and anionic ligands. The compounds are structurally characterized, and many ligands exhibit unprecedented bindng modes across two metal centers. The relative binding affinities are evaluated spectroscopically, and equilibrium binding constants for the examined ligands are determined to span over 13 orders of magnitude. As an application of this framework, mild hydrogenation conditions of bound thiophene are presented.

Chapter 5 studies nickel-mediated C–O bond cleavage of aryl alkyl ethers, a transformation with emerging applications in fields such as lignin biofuels and organic methodology. Other group members have shown the mechanism of C–O bond cleavage of an aryl methyl ether incorporated into a meta-terphenyl diphosphine framework to proceed through β-H elimination of an alkoxide. First, the electronic selectivity of the model system is examined computationally and compared with catalytic systems. The lessons learned from the model system are then applied to isotopic labeling studies for catalytic aryl alkyl ether cleavage under dihydrogen. Results from selective deuteration experiments and mass spectrometry draw a clear analogy between the mechanisms of the model and catalytic systems that does not require dihydrogen for C–O bond cleavage, although dihydrogen is proposed to play a role in catalyst activation and catalytic turnover.

Appendix A presents initial efforts toward heterodinuclear complexes as models for CO dehydrogenase and Fischer Tropsch chemistry. A catechol-incorporating terphenyl diphosphine is reported, and metal complexes thereof are discussed.

Appendix B highlights some structurally characterized terphenyl diphosphine complexes that either do not thematically belong in the research chapters or proved to be difficult to reproduce. These compounds show unusual coordination modes of the terphenyl diphosphine from which other researchers may glean insights.

Testable models of aquatic systems: A NERC special topic for integrating experiments and modelling

A major part of the support for fundamental research on aquatic ecosystems continues to be provided by the Natural Environment Research Council (NERC). Funds are released for ”thematic” studies in a selected special topic or programme. ”Testable Models of Aquatic Ecosystems” was a Special Topic of the NERC, initiated in 1995, the aim of which was to promote ecological modelling by making new links between experimental aquatic biologists and state-of-the-art modellers. The Topic covered both marine and freshwater systems. This paper summarises projects on aspects of the responses of individual organisms to the effects of environmental variability, on the assembly, permanence and resilience of communities, and on aspects of spatial models. The authors conclude that the NERC Special Topic has been highly successful in promoting the development and application of models, most particularly through the interplay between experimental ecologists and formal modellers.

Transmission matrices and lumped parameter models for continuous systems

The use of transmission matrices and lumped parameter models for describing continuous systems is the subject of this study. Non-uniform continuous systems which play important roles in practical vibration problems, e.g., torsional oscillations in bars, transverse bending vibrations of beams, etc., are of primary importance.

A new approach for deriving closed form transmission matrices is applied to several classes of non-uniform continuous segments of one dimensional and beam systems. A power series expansion method is presented for determining approximate transmission matrices of any order for segments of non-uniform systems whose solutions cannot be found in closed form. This direct series method is shown to give results comparable to those of the improved lumped parameter models for one dimensional systems.

Four types of lumped parameter models are evaluated on the basis of the uniform continuous one dimensional system by comparing the behavior of the frequency root errors. The lumped parameter models which are based upon a close fit to the low frequency approximation of the exact transmission matrix, at the segment level, are shown to be superior. On this basis an improved lumped parameter model is recommended for approximating non-uniform segments. This new model is compared to a uniform segment approximation and error curves are presented for systems whose areas very quadratically and linearly. The effect of varying segment lengths is investigated for one dimensional systems and results indicate very little improvement in comparison to the use of equal length segments. For purposes of completeness, a brief summary of various lumped parameter models and other techniques which have previously been used to approximate the uniform Bernoulli-Euler beam is a given.

Photorefractive performance of a novel multifunctional inorganic-organic hybridized nanocomposite sensitized by CdS nanoparticles

A novel multifunctional inorganic-organic photorefractive (PR) poly(N-vinyl)-3-[p-nitrophenylazolcarbazolyl-CdS nanocomposites with different molar ratios of US to poly(N-vinyl)-3-[p-nitrophenylazo]carbazolyl (PVNPAK) were synthesized via a postazo-coupling reaction and chemically hybridized approach, respectively. The nanocomposites are highly soluble and could be obtained as film-forming materials with appreciably high molecular weights and low glass transition temperature (T,) due to the flexible spacers. The PVNPAK matrix possesses a highest-occupied molecular orbital value of about -5.36 eV determined from cyclic voltammetry. Second harmonic generation (SHG) could be observed in PVNPAK film without any poling procedure and 4.7 pm/V of effective second-order nonlinear optical susceptibility is obtained. The US particles as photosensitizers had a nanoscale size in PVNPAK adopting transmission electron microscopy. The improvement of interface quality between US and polymer matrix is responsible for efficient photoinduced charge generation efficiency in the nanocomposites. An asymmetric optical energy exchange between two beams on the polymer composites PVNPAK-CdS/ECZ has been found even without an external field in two-beam coupling (TBC) experiment, and the TBC gain and diffraction efficiency of 14.26 cm(-1) and 3.4% for PVNPAK-5-CdS/ECZ, 16.43 cm(-1) and 4.4% for PVNPAK-15-CdS/ECZ were measured at a 647.1 nm wavelength, respectively.

New generation of two-dimensional spintronic systems realized by coupling of Rashba and Dirac fermions

Intriguing phenomena and novel physics predicted for two-dimensional (2D) systems formed by electrons in Dirac or Rashba states motivate an active search for new materials or combinations of the already revealed ones. Being very promising ingredients in themselves, interplaying Dirac and Rashba systems can provide a base for next generation of spintronics devices, to a considerable extent, by mixing their striking properties or by improving technically significant characteristics of each other. Here, we demonstrate that in BiTeI@PbSb2Te4 composed of a BiTeI trilayer on top of the topological insulator (TI) PbSb2Te4 weakly- and strongly-coupled Dirac-Rashba hybrid systems are realized. The coupling strength depends on both interface hexagonal stacking and trilayer-stacking order. The weakly-coupled system can serve as a prototype to examine, e.g., plasmonic excitations, frictional drag, spin-polarized transport, and charge-spin separation effect in multilayer helical metals. In the strongly-coupled regime, within similar to 100 meV energy interval of the bulk TI projected bandgap a helical state substituting for the TI surface state appears. This new state is characterized by a larger momentum, similar velocity, and strong localization within BiTeI. We anticipate that our findings pave the way for designing a new type of spintronics devices based on Rashba-Dirac coupled systems.

A new approach for analyzing and comparing coastal resource systems

ICLARM has recently developed a strategic Plan for International research on living aquatic resources management which identifies tropical coastal resource systems as one of its areas of research emphasis. Details are given of a new approach for analysing and comparing coastal resource systems - the coastal cross-section concept. Agroecosystems analysis and farming systems research were used as a basis for the development of this concept.

Resilient livelihoods and food security in coastal aquatic agricultural systems: Investing in transformational change

Aquatic agricultural systems (AAS) are diverse production and livelihood systems where families cultivate a range of crops, raise livestock, farm or catch fish, gather fruits and other tree crops, and harness natural resources such as timber, reeds, and wildlife. Aquatic agricultural systems occur along freshwater floodplains, coastal deltas, and inshore marine waters, and are characterized by dependence on seasonal changes in productivity, driven by seasonal variation in rainfall, river flow, and/or coastal and marine processes. Despite this natural productivity, the farming, fishing, and herding communities who live in these systems are among the poorest and most vulnerable in their countries and regions. This report provides an overview of the scale and scope of development challenges in coastal aquatic agricultural systems, their significance for poor and vulnerable communities, and the opportunities for partnership and investment that support efforts of these communities to secure resilient livelihoods in the face of multiple risks.

Near and distant connection of atmospheric systems to ocean temperature change in the coastal California Current region

In studying hydrosphere, atmosphere, and biosphere interactions, it is useful to focus on specific subsystem processes and energy exchanges (forcing). Since subsystem scales range over ten orders of magnitude, it may be difficult to focus research on scales that will yield useful results in terms of establishing causal and predictive connections between more easily and less easily observed subsystems. In an effort to find pertinent scales, we have begun empirical investigations into relationships between atmospheric, oceanic, and biological systems having spatial scales exceeding 10^3 kilometers and temporal scales of six months or more.

Limnology and fishery biology of the streams at Horton Plains, Sri Lanka (Ceylon)

The present study deals with the chemical, algal and faunal characteristics of the stream system at Horton Plains, the highest plains in Ceylon (altitude 2'225 m). The cultivation of seed potatoes and subsequent use of fertilizers have caused extensive silting and severe eutrophication of the stream systems. Since there are no indigenous fish, the trout Salmo gairdnerii has been introduced and it is the only fish found in these streams. The commonest fauna in the streams are crabs (Paratelphusa sp.), shrimps (Caridimr sp.), Simulium sp. and Chironomus sp. Their increase in number is probably correlated with increase in organic and detritus matter. The most important food items of the trout are the crabs living abundantly in the stream, insect larvae and terrestrial insects were also commonly found in the guts. Records of stocking and taking of trout in the Horton plains streams have shown that now less trout are taken relatively to the numbers stocked. This decrease may be possibly due to the eutrophication of the stream and also due to the possible use of pollutants in connection with the cultivation of seed potatoes.

Modular distributed manufacturing systems and the implications for integrated control

Driven by the need for more responsive manufacturing processes and as a consequence of increasing complexity in products and production systems, this short paper introduces a number of developments in the area of modular, distributed manufacturing systems. Requirements for the development of such systems are addressed and, in particular, the relevance to current and future integrated control systems is examined. One of the key issues for integrated control systems in the future is the need to provide support for distributed decision-making in addition to existing distributed control capabilities.

A matter of life and death: sociomateriality, information systems and critical care

Sociomateriality has been attracting growing attention in the Organization Studies and Information Systems literatures since 2007, with more than 140 journal articles now referring to the concept. Over 80 percent of these articles have been published since January 2011 and almost all cite the work of Orlikowski (2007, 2010; Orlikowski and Scott 2008) as the source of the concept. Only a few, however, address all of the notions that Orlikowski suggests are entailed in sociomateriality, namely materiality, inseparability, relationality, performativity, and practices, with many employing the concept quite selectively. The contribution of sociomateriality to these literatures is, therefore, still unclear. Drawing on evidence from an ongoing study of the adoption of a computer-based clinical information system in a hospital critical care unit, this paper explores whether the notions, individually and collectively, offer a distinctive and coherent account of the relationship between the social and the material that may be useful in Information Systems research. It is argued that if sociomateriality is to be more than simply a label for research employing a number of loosely related existing theoretical approaches, then studies employing the concept need to pay greater attention to the notions entailed in it and to differences in their interpretation.

Viscoelastic analysis of single-component and composite PEG and alginate hydrogels

Hydrogels, three-dimensional hydrophilic polymer networks, are appealing candidate materials for studying the cellular microenvironment as their substantial water content helps to better mimic soft tissue. However, hydrogels can lack mechanical stiffness, strength, and toughness. Composite hydrogel systems have been shown to improve upon mechanical properties compared to their singlecomponent counterparts. Poly (ethylene glycol) dimethacrylate (PEGDMA) and alginate are polymers that have been used to form hydrogels for biological applications. Singlecomponent and composite PEGDMA and alginate systems were fabricated with a range of total polymer concentrations. Bulk gels were mechanically characterized using spherical indentation testing and a viscoelastic analysis framework. An increase in shear modulus with increasing polymer concentration was demonstrated for all systems. Alginate hydrogels were shown to have a smaller viscoelastic ratio than the PEGDMA gels, indicating more extensive relaxation over time. Composite alginate and PEGDMA hydrogels exhibited a combination of the mechanical properties of the constituents, as well as a qualitative increase in toughness. Additionally, multiple hydrogel systems were produced that had similar shear moduli, but different viscoelastic behaviors. Accurate measurement of the mechanical properties of hydrogels is necessary in order to determine what parameters are key in modeling the cellular microenvironment. © 2014 The Chinese Society of Theoretical and Applied Mechanics; Institute of Mechanics, Chinese Academy of Sciences and Springer-Verlag Berlin Heidelberg.

Coalition and distribution in fuzzy dynamic supply chain systems

In this paper, two models of coalition and income's distribution in FSCS (fuzzy supply chain systems) are proposed based on the fuzzy set theory and fuzzy cooperative game theory. The fuzzy dynamic coalition choice's recursive equations are constructed in terms of sup-t composition of fuzzy relations, where t is a triangular norm. The existence of the fuzzy relations in FSCS is also proved. On the other hand, the approaches to ascertain the fuzzy coalition through the choice's recursive equations and distribute the fuzzy income in FSCS by the fuzzy Shapley values are also given. These models are discussed in two parts: the fuzzy dynamic coalition choice of different units in FSCS; the fuzzy income's distribution model among different participators in the same coalition. Furthermore, numerical examples are given aiming at illustrating these models., and the results show that these models are feasible and validity in FSCS.

Effect of the electrostatic interactions of chromophores on the macroscopic second-order nonlinear optical properties of the polymer films

The polyetherketone (PEK-c) guest-host system thin films doped with 3-(1,1-dicyanothenyl)-1-phenyl-4,5-dihydro-1H-pryazole (DCNP) were prepared. Their second-order nonlinear optical (NLO) coefficients chi(33)((2)) were measured by using Maker fringe method for the polymer films doped with different weight percents of DCNP. Experimental results indicate that the second-order NLO properties of the poled polymer films could decrease with the chromophore loading increasing when the chromophore loading reaches a fairly high level. In this paper, the relationship between the macroscopic second-order NLO coefficient and the chromophore number density was modified under considering the role of the electrostatic interactions of chromophores in the polymer film. According to the modified relationship, the macroscopic second-order NLO coefficient is no longer in direct proportion with the chromophore number density in the polymer film. The effect of the electrostatic interactions of chromophores on second-order NLO properties was discussed. The attenuation of the macroscopic second-order NLO activity can be demonstrated by the role of the chromophore electrostatic interactions at high loading of chromophore in the polymer systems.

Behavior of Pentacene Initial Nucleation on Various Dielectrics and Its Effect on Carrier Transport in Organic Field-Effect Transistor

The influence of dielectric surface energy on the initial nucleation and the growth of pentacene films as well as the electrical properties of the pentacene-based field-effect transistors are investigated. We have examined a range of organic and inorganic dielectrics with different surface energies, such as polycarbonate/SiO2, polystyrene/SiO2, and PMMA/SiO2 bi-layered dielectrics and also the bare SiO2 dielectric. Atomic force microscopy measurements of sub-monolayer and thick pentacene films indicated that the growth of pentacene film was in Stranski-Kranstanow growth mode on all the dielectrics. However, the initial nucleation density and the size of the first-layered pentacene islands deposited on different dielectrics are drastically influenced by the dielectric surface energy. With the increasing of the surface energy, the nucleation density increased and thus the average size of pentacene islands for the first mono-layer deposition decreased. The performance of fabricated pentacene-based thin film transistors was found to be highly related to nucleation density and the island size of deposited Pentacene film, and it had no relationship to the final particle size of the thick pentacene film. The field effect mobility of the thin film transistor could be achieved as high as 1.38 cm(2)/Vs with on/off ratio over 3 x 10(7) on the PS/SiO2 where the lowest surface energy existed among all the dielectrics. For comparison, the values of mobility and on/off ratio were 0.42 cm(2)/Vs and 1 x 10(6) for thin film transistor deposited directly on bare SiO2 having the highest surface energy.