Transition metal clusters supported by multinucleating ligand frameworks as models of biological active sites

This dissertation describes efforts to model biological active sites with small molecule clusters. The approach used took advantage of a multinucleating ligand to control the structure and nuclearity of the product complexes, allowing the study of many different homo- and heterometallic clusters. Chapter 2 describes the synthesis of the multinucleating hexapyridyl trialkoxy ligand used throughout this thesis and the synthesis of trinuclear first row transition metal complexes supported by this framework, with an emphasis on tricopper systems as models of biological multicopper oxidases. The magnetic susceptibility of these complexes were studied, and a linear relation was found between the Cu-O(alkoxide)-Cu angles and the antiferromagnetic coupling between copper centers. The triiron(II) and trizinc(II) complexes of the ligand were also isolated and structurally characterized.

Chapter 3 describes the synthesis of a series of heterometallic tetranuclear manganese dioxido complexes with various incorporated apical redox-inactive metal cations (M = Na⁺, Ca²⁺, Sr²⁺, Zn²⁺, Y³⁺). Chapter 4 presents the synthesis of heterometallic trimanganese(IV) tetraoxido complexes structurally related to the CaMn₃ subsite of the oxygen-evolving complex (OEC) of Photosystem II. The reduction potentials of these complexes were studied, and it was found that each isostructural series displays a linear correlation between the reduction potentials and the Lewis acidities of the incorporated redox-inactive metals. The slopes of the plotted lines for both the dioxido and tetraoxido clusters are the same, suggesting a more general relationship between the electrochemical potentials of heterometallic manganese oxido clusters and their “spectator” cations. Additionally, these studies suggest that Ca²⁺ plays a role in modulating the redox potential of the OEC for water oxidation.

Chapter 5 presents studies of the effects of the redox-inactive metals on the reactivities of the heterometallic manganese complexes discussed in Chapters 3 and 4. Oxygen atom transfer from the clusters to phosphines is studied; although the reactivity is kinetically controlled in the tetraoxido clusters, the dioxido clusters with more Lewis acidic metal ions (Y³⁺ vs. Ca²⁺) appear to be more reactive. Investigations of hydrogen atom transfer and electron transfer rates are also discussed.

Appendix A describes the synthesis, and metallation reactions of a new dinucleating bis(N-heterocyclic carbene)ligand framework. Dicopper(I) and dicobalt(II) complexes of this ligand were prepared and structurally characterized. A dinickel(I) dichloride complex was synthesized, reduced, and found to activate carbon dioxide. Appendix B describes preliminary efforts to desymmetrize the manganese oxido clusters via functionalization of the basal multinucleating ligand used in the preceding sections of this dissertation. Finally, Appendix C presents some partially characterized side products and unexpected structures that were isolated throughout the course of these studies.

Two topics in elementary particle physics. I. Crossing as a group and elimination of exotic channels. II. Real parts of meson-nucleon forward scattering amplitudes.

I. Crossing transformations constitute a group of permutations under which the scattering amplitude is invariant. Using Mandelstem's analyticity, we decompose the amplitude into irreducible representations of this group. The usual quantum numbers, such as isospin or SU(3), are "crossing-invariant". Thus no higher symmetry is generated by crossing itself. However, elimination of certain quantum numbers in intermediate states is not crossing-invariant, and higher symmetries have to be introduced to make it possible. The current literature on exchange degeneracy is a manifestation of this statement. To exemplify application of our analysis, we show how, starting with SU(3) invariance, one can use crossing and the absence of exotic channels to derive the quark-model picture of the tensor nonet. No detailed dynamical input is used.

II. A dispersion relation calculation of the real parts of forward π^±p and K^±p scattering amplitudes is carried out under the assumption of constant total cross sections in the Serpukhov energy range. Comparison with existing experimental results as well as predictions for future high energy experiments are presented and discussed. Electromagnetic effects are found to be too small to account for the expected difference between the π^-p and π⁺p total cross sections at higher energies.

Heterometallic Complexes as Models of Enzymatic Active Sites

This dissertation describes studies on two multinucleating ligand architectures: the first scaffold was designed to support tricopper complexes, while the second platform was developed to support tri- and tetrametallic clusters.

In Chapter 2, the synthesis of yttrium (and lanthanide) complexes supported by a tripodal ligand framework designed to bind three copper centers in close proximity is described. Tricopper complexes were shown to react with dioxygen in a 1:1 [Cu₃]/O₂ stoichiometry to form intermediates in which the O–O bond was fully cleaved, as characterized via UV-Vis spectroscopy and determination of the reaction stoichiometry. Pre-arrangement of the three Cu centers was pivotal to cooperative O₂ activation, as mono-copper complexes reacted differently with dioxgyen. The reactivity of the observed intermediates was studied with various substrates (reductants, O-atom acceptors, H-atom donors, Brønsted acids) to determine their properties. In Chapter 3, the reactivity of the same yttrium-tricopper complex with nitric oxide was explored. Reductive coupling to form a trans-hyponitrite complex (characterized by X-ray crystallography) was observed via cooperative reactivity by an yttrium and a copper center on two distinct tetrametallic units. The hyponitrite complex was observed to release nitrous oxide upon treatment with a Brønsted acid, supporting its viability as an intermediate in nitric oxide reduction to nitrous oxide.

In Chapter 4, a different multinucleating ligand scaffold was employed to synthesize heterometallic triiron clusters containing one oxide and one hydroxide bridges. The effects of the redox-inactive, Lewis acidic heterometals on redox potential was studied by cyclic voltammetry, unveiling a linear correlation between redox potential and heterometal Lewis acidity. Further studies on these complexes showed that the Lewis acidity of the redox-inactive metals also affected the oxygen-atom transfer reactivity of these clusters. Comparisons of this reactivity with manganese systems, collaborative efforts to reassign the structures of related manganese oxo-hydroxo clusters, and synthetic attempts to access related dioxo clusters are also described.

In Appendix A, ongoing efforts to synthesize new clusters supported by the same multinucleating ligand platform are described. Studies of novel approaches towards ligand exchange in tetrametallic clusters and incorporation of new supporting and bridging ligand motifs in trinuclear complexes are presented.

New Physics Models in the Diphoton Final State at CMS

Since the discovery of the Higgs boson at the LHC, its use as a probe to search for beyond the standard model physics, such as supersymmetry, has become important, as seen in a recent search by the CMS experiment using razor variables in the diphoton final state. Motivated by this search, this thesis examines the LHC discovery potential of a SUSY scenario involving bottom squark pair production with a Higgs boson in the final state. We design and implement a software-based trigger using the razor variables for the CMS experiment to record events with a bottom quark-antiquark pair from a Higgs boson. We characterize the full range of signatures at the LHC from this Higgs-aware SUSY scenario and demonstrate the sensitivity of the CMS data to this model.

Self-Organized Criticality, Plasticity and Sensorimotor Coupling. Explorations with a Neurorobotic Model in a Behavioural Preference Task

During the last two decades, analysis of 1/f noise in cognitive science has led to a considerable progress in the way we understand the organization of our mental life. However, there is still a lack of specific models providing explanations of how 1/f noise is generated in coupled brain-body-environment systems, since existing models and experiments typically target either externally observable behaviour or isolated neuronal systems but do not address the interplay between neuronal mechanisms and sensorimotor dynamics. We present a conceptual model of a minimal neurorobotic agent solving a behavioural task that makes it possible to relate mechanistic (neurodynamic) and behavioural levels of description. The model consists of a simulated robot controlled by a network of Kuramoto oscillators with homeostatic plasticity and the ability to develop behavioural preferences mediated by sensorimotor patterns. With only three oscillators, this simple model displays self-organized criticality in the form of robust 1/f noise and a wide multifractal spectrum. We show that the emergence of self-organized criticality and 1/f noise in our model is the result of three simultaneous conditions: a) non-linear interaction dynamics capable of generating stable collective patterns, b) internal plastic mechanisms modulating the sensorimotor flows, and c) strong sensorimotor coupling with the environment that induces transient metastable neurodynamic regimes. We carry out a number of experiments to show that both synaptic plasticity and strong sensorimotor coupling play a necessary role, as constituents of self-organized criticality, in the generation of 1/f noise. The experiments also shown to be useful to test the robustness of 1/f scaling comparing the results of different techniques. We finally discuss the role of conceptual models as mediators between nomothetic and mechanistic models and how they can inform future experimental research where self-organized critically includes sensorimotor coupling among the essential interaction-dominant process giving rise to 1/f noise.

Observational constraints on the unified dark matter and dark energy model based on the quark bag model

In this work we investigate if a small fraction of quarks and gluons, which escaped hadronization and survived as a uniformly spread perfect fluid, can play the role of both dark matter and dark energy. This fluid, as developed in [1], is characterized by two main parameters: beta, related to the amount of quarks and gluons which act as dark matter; and gamma, acting as the cosmological constant. We explore the feasibility of this model at cosmological scales using data from type Ia Supernovae (SNeIa), Long Gamma-Ray Bursts (LGRB) and direct observational Hubble data. We find that: (i) in general, beta cannot be constrained by SNeIa data nor by LGRB or H(z) data; (ii) gamma can be constrained quite well by all three data sets, contributing with approximate to 78% to the energy matter content; (iii) when a strong prior on (only) baryonic matter is assumed, the two parameters of the model are constrained successfully. (C) 2014 The Authors. Published by Elsevier B.V.

On the Stability and Equilibrium Points of Multistaged SI (n) R Epidemic Models

This paper relies on the concept of next generation matrix defined ad hoc for a new proposed extended SEIR model referred to as SI(n)R-model to study its stability. The model includes n successive stages of infectious subpopulations, each one acting at the exposed subpopulation of the next infectious stage in a cascade global disposal where each infectious population acts as the exposed subpopulation of the next infectious stage. The model also has internal delays which characterize the time intervals of the coupling of the susceptible dynamics with the infectious populations of the various cascade infectious stages. Since the susceptible subpopulation is common, and then unique, to all the infectious stages, its coupled dynamic action on each of those stages is modeled with an increasing delay as the infectious stage index increases from 1 to n. The physical interpretation of the model is that the dynamics of the disease exhibits different stages in which the infectivity and the mortality rates vary as the individual numbers go through the process of recovery, each stage with a characteristic average time.

Constantes de acoplamento de vértices com mésons estranhos e charmosos usando as regras de soma da QCD

Neste trabalho, foram calculados os fatores de forma e as constantes de acoplamento dos vértices mesônicos J/ψ DsDs, J/ψ Ds*Ds e J/ψ Ds*Ds*usando a técnica das regras de soma da QCD (RSQCD) até a ordem 5 da OPE. Estes três vértices estão envolvidos em algumas das numerosas hipóteses que tentam explicar a estrutura interna de alguns mésons charmosos exóticos que começaram a ser observados a partir de 2003. Tais mésons não se encaixam no espectro do charmonium e/ou apresentam números quânticos exóticos dentro do modelo CQM (constituent quark model). Um exemplo é o méson Y(4140), cujo decaimento observado é no par J/ψφ enquanto o esperado seria que tivesse decaimento predominante em mésons com open charm, devido à sua massa. Uma das propostas para se entender este méson consiste em estudá-lo como um estado molecular Ds*ar{D}s*, de modo que seu decaimento seria Y(4140) → Ds* ar{D}s* → J/ψφ. Neste processo, aparecerão os vértices de interação estudados neste trabalho, de maneira que o conhecimento mais preciso de seus fatores de forma e de suas constantes de acoplamento pode beneficiar a compreensão sobre a constituição fundamental do Y(4140) assim como a de outros novos estados como o X(4350), Y(4274) e Y(4660) por exemplo. Foram considerados neste trabalho, todos os casos off-shell possíveis para cada um dos três vértices, obtendo assim dois fatores de forma distintos para o vértice J/ψ DsDs, três para o vértice J/ψ Ds*Ds e dois para o vértice J/ψ Ds* Ds*. Nestes três vértices, os fatores de forma para o caso J/ψ off-shell foram bem ajustados por curvas monopolares enquanto os casos Ds e Ds* foram ajustados por curvas exponenciais, o que está de acordo com o comportamento encontrado em trabalhos anteriores do grupo. Os cálculos das constantes de acoplamento tiveram como resultados: g_{J/ψ Ds Ds} = 5.98^{+0.67}_{ -0.58}, g_{J/ψ D*s Ds} = 4.30_{+0.41}^{-0.35}GeV^{-1} e g_{J/ψ Ds* Ds*} = 7.47^{+1.04}_{-0.71}, resultados estes que estão compatíveis com os trabalhos anteriores que utilizaram as RSQCD para o cálculo das constantes de acoplamento dos vértices J/ψ D(*)D(*).

Singing flames - The coupling of acoustics and combustion

An overview of the physics of the interaction between sound and flames is presented. The flame dynamics are investigated through experiment and computer modelling. The complementary rôles of wave analysis, low-order models for unsteady combustion, Computational Fluid Dynamics and experiment are illustrated by examples of oscillations in gas turbine combustors and in generic premixed ducted flames. The potential for 'antisound' and passive acoustic absorbers to eliminate the instability is also discussed.

Oscillator models and collective motion: Splay state stabilization of self-propelled particles

This paper presents a Lyapunov design for the stabilization of collective motion in a planar kinematic model of N particles moving at constant speed. We derive a control law that achieves asymptotic stability of the splay state formation, characterized by uniform rotation of N evenly spaced particles on a circle. In designing the control law, the particle headings are treated as a system of coupled phase oscillators. The coupling function which exponentially stabilizes the splay state of particle phases is combined with a decentralized beacon control law that stabilizes circular motion of the particles. © 2005 IEEE.

Effects of multistage coupling and disk flexibility on mistuned bladed disk dynamics

The effects ofdisk flexibility and multistage coupling on the dynamics of bladed disks with and without blade mistuning are investigated. Both free and forced responses are examined using finite element representations of example single and two-stage rotor models. The reported work demonstrates the importance of proper treatment of interstage (stage-to-stage) boundaries in order to yield adequate capture of disk-blade modal interaction in eigenfrequency veering regions. The modified disk-blade modal interactions resulting from interstage-coupling-induced changes in disk flexibility are found to have a significant impact on (a) tuned responses due to excitations passing through eigenfrequency veering regions, and (b) a design's sensitivity to blade mistuning. Hence, the findings in this paper suggest that multistage analyses may be required when excitations are expected to fall in or near eigenfrequency veering regions or when the sensitivity to blade mistuning is to be accounted for Conversely, the observed sensitivity to disk flexibility also indicates that the severity of unfavorable structural interblade coupling may be reduced significantly by redesigning the disk(s) and stage-to-stage connectivity. The relatively drastic effects of such modifications illustrated in this work indicate that the design modifications required to alleviate veering-related response problems may be less comprehensive than what might have been expected.

Combined study of gamma p ->eta p and pi(-)p ->eta n in a chiral constituent quark approach

Within a chiral constituent quark model approach, η-meson production on the proton via electromagnetic and hadron probes is studied. With few parameters, the differential cross section and polarized beam asymmetry for γp → ηp and differential cross section for π − p → ηn processes are calculated and successfully compared with the data in the center-of-mass energy range from threshold up to 2 GeV. The five known resonances S11(1535), S11(1650), P13(1720),D13(1520), and F15(1680) are found to be dominant in the reaction mechanisms in both channels. Possible roles played by new resonances are also investigated; and in the photoproduction channel, significant contribution from S11 and D15 resonances, with masses around 1715 and 2090 MeV, respectively, are deduced. For the so-called missing resonances, no evidence is found within the investigated reactions. The helicity amplitudes and decay widths of N ∗ → πN, ηN are also presented and found to be consistent with the Particle Data Group values.

eta-production on the proton via electromagnetic and hadronic probes

The reactions pi(-)p -> eta n and gamma p -> eta p are investigated within a dynamical coupled-channels model of meson production reactions in the nucleon resonance region The meson-baryon channels included are pi N, pi Delta, sigma N, and rho N The direct eta-photoproduction process is studied within a formalism based on a chiral constituent quark model approach, complemented with a one-gluon-exchange mechanism, to take into account the breakdown of the SU(6)circle times O(3) symmetry In the models search, the following known nucleon resonances are embodied S-11(1535), S-11(1650), P-11(1440), P-11(1710), P-13(1720), D-13(1520), D-13(1700), D-15(1675), and F-15(1680). Data for the pi(-)p -> eta n reaction from threshold up to a total center-of-mass energy of W approximate to 2 GeV are satisfactorily reproduced For the photoproduction channel: two additional higher mass known resonances, P-13(1900) and F-15(2000), are also considered However, reproducing the data for gamma p -> eta p requires, within our approach, two new nucleon resonances, for which we extract, mass and width

Study of nucleon resonances in a chiral quark model via eta productions

In this report we investigate eta-meson productions oil the proton via electromagnetic and hadron probes in a chiral quark model approach. The observables, such as, differential cross section and beam asymmetry for the two productions are calculated and compared with the experiment. The five known resonances S-11(1535) S-11(1650); P-13(1720) D-13(1520), and F-15(1680) are found to be dominant in the reaction mech-anisms in both channels. Significant, contribution from a new S-11 resonances are deduced. For the so-called "missing resonances", no evidence is found within the investigated reactions. The partial wave amplitudes for pi(-)p -> eta n are also presented.

eta photoproduction on the proton in a chiral constituent quark approach via a one-gluon-exchange model

A formalism based on a chiral quark model (chi QM) approach complemented with a one-gluon-exchange model, to take into account the breakdown of the SU(6)circle times O(3) symmetry, is presented. The configuration mixing of wave functions for nucleon and resonances are derived. With few adjustable parameters, differential cross-section and polarized-beam asymmetry for the gamma p -> eta p process are calculated and successfully compared with the data in the center-of-mass energy range from threshold to 2 GeV. The known resonances S-11(1535), S-11(1650), P-13(1720), D-13(1520), and F-15(1680), as well as two new S-11 and D-15 resonances, are found to be dominant in the reaction mechanism. Moreover, connections among the scattering amplitudes of the chi QM approach and the helicity amplitudes, as well as decay widths of resonances, are established. Possible contributions from the so-called missing resonances are investigated and found to be negligible.