Síntese e caracterização de complexo tetranuclear de cobre com o ligante resorcinareno

The main objective of the present work is to contribute to the development of the coordination chemistry of macromolecules such as resorcinarene with the synthesis and characterization of new copper complexes with chloride, vanillin and resorcinarene binders, all coordinated to phenanthroline, a biologically active molecule with important properties in biological systems. The complex [(Cu(phen))4(resvan)], was synthesized from the direct reaction of the metals with resorcinarene and generates several possibilities for coordination, which hinders its characterization. Therefore, in order to limit the coordination sites of the ligand, the complex [(Cu(phen))4(resvan)]Cl4 was formed from a new synthetic methodology. The complex cis-[Cu(phen)Cl2], cis-[Cu(phen)(van)]Cl, [(Cu(phen))4(resvan)] and [(Cu(phen))4(resvan)]Cl4 were characterized by spectroscopic techniques such as IR, UV-vis and EPR. By using infrared it has been possible to demonstrate the presence of the phenanthroline ligand in the synthesized complexes, and vanillin in the complex cis- [Cu(phen)(van)]Cl and resvan ligand in the complex [(Cu(phen))4(resvan)], besides this indicating the formation of resorcinarene in the complex [(Cu(phen))4(resvan)]Cl4. The electronic spectra of these coordination compounds indicated the presence of the phenanthroline ligand, by its intense bands in the ultraviolet region. For the complex cis- [Cu(phen)(van)]Cl it still indicated the presence of the ligand vanillin based on intraligand bands of vanillin and charge transfer, LMCT. Furthermore, the spectra showed d-d bands, confirming the formation of metal compounds. The amount of copper atoms present in the complex [(Cu(phen))4(resvan)]Cl4 was estimated from a comparative analysis of the absorbances of solutions of the same concentration of [(Cu(phen))4(resvan)]Cl4 and cis- [Cu(phen)(van)]Cl, which indicates that these compounds have copper atoms in the ratio 4:1. The EPR spectra of the complex cis-[Cu(phen)Cl2], cis-[Cu(phen)(van)]Cl and [(Cu(phen))4(resvan)]Cl4 showed axial profiles, while the complex [(Cu(phen))4(resvan)] showed of axial and rhombic profiles, indicating a change in the symmetry of the Cu (II) to this complex environment. The binders vanillin and resvan underwent biological assays with satisfactory results, both exhibited antioxidant activity and low toxicity, as well vanillin present antitoxoplásmico character.

Numerical study of the enlarged O(5) symmetry of the 3D antiferromagnetic RP^(2) spin model

We investigate by means of Monte Carlo simulation and finite-size scaling analysis the critical properties of the three dimensional O (5) non-linear σ model and of the antiferromagnetic RP^(2) model, both of them regularized on a lattice. High accuracy estimates are obtained for the critical exponents, universal dimensionless quantities and critical couplings. It is concluded that both models belong to the same universality class, provided that rather non-standard identifications are made for the momentum-space propagator of the RP^(2) model. We have also investigated the phase diagram of the RP^(2) model extended by a second-neighbor interaction. A rich phase diagram is found, where most of the phase transitions are of the first order.

Generic helical edge states due to Rashba spin-orbit coupling in a topological insulator

We study the helical edge states of a two-dimensional topological insulator without axial spin symmetry due to the Rashba spin-orbit interaction. Lack of axial spin symmetry can lead to so-called generic helical edge states, which have energy-dependent spin orientation. This opens the possibility of inelastic backscattering and thereby nonquantized transport. Here we find analytically the new dispersion relations and the energy dependent spin orientation of the generic helical edge states in the presence of Rashba spin-orbit coupling within the Bernevig-Hughes-Zhang model, for both a single isolated edge and for a finite width ribbon. In the single-edge case, we analytically quantify the energy dependence of the spin orientation, which turns out to be weak for a realistic HgTe quantum well. Nevertheless, finite size effects combined with Rashba spin-orbit coupling result in two avoided crossings in the energy dispersions, where the spin orientation variation of the edge states is very significantly increased for realistic parameters. Finally, our analytical results are found to compare well to a numerical tight-binding regularization of the model.

Dynamical generation of a gauge symmetry in the double-exchange model

It is shown that a bosonic formulation of the double-exchange model, one of the classical models for magnetism, generates dynamically a gauge-invariant phase in a finite region of the phase diagram. We use analytical methods, Monte Carlo simulations and finite-size scaling analysis. We study the transition line between that region and the paramagnetic phase. The numerical results show that this transition line belongs to the universality class of the antiferromagnetic RP^(2) model. The fact that one can define a universality class for the antiferromagnetic RP^(2) model, different from the one of the O(N) models, is puzzling and somehow contradicts naive expectations about universality.

Predicting residual stiffness of cracked composite laminates subjected to multi-axial in-plane loading

Peer reviewed

Predicting residual stiffness of cracked composite laminates subjected to multi-axial in-plane loading

Peer reviewed

Modelling of stiffness degradation due to cracking in laminates subjected to multi-axial loading

Funding Financial support of this research by the Engineering and Physical Sciences Research Council (EPSRC/GR/L51348) and the British Ministry of Defence is gratefully acknowledged.

Ciliary muscle morphology in emmetropia and ocular biometric correlates

Purpose: Recent studies have documented a link between axial myopia and ciliary muscle morphology; yet, the variation in biometric characteristics of the emmetropic ciliary muscle are not fully known. Ciliary muscle morphology, including symmetry, was investigated between both eyes of emmetropic participants and correlated to ocular biometric parameters. Methods: Anterior segment optical coherence tomography (Zeiss, Visante) was utilised to image both eyes of 49 emmetropic participants (mean spherical equivalent refractive error (MSE) ≥ -0.55; < +0.75 D), aged 19 to 26 years. High resolution images were obtained of nasal and temporal aspects of the ciliary muscle in the relaxed state. MSE of both eyes was recorded using the Grand Seiko WAM 5500; axial length (AXL), anterior chamber depth (ACD) and lens thickness (LT) of the right eye were obtained using the Haag-streit Lenstar LS 900 biometer. A bespoke semi-objective analysis programme was used to measure a range of ciliary muscle parameters. Results: Temporal ciliary muscle overall length (CML) was greater than nasal CML, in both eyes (right: 3.58 ± 0.40 mm and 3.85 ± 0.39 mm for nasal and temporal aspects, respectively, P < 0.001; left: 3.65 ± 0.35 mm and 3.88 ± 0.41 mm for nasal and temporal aspects, respectively, P < 0.001). Temporal ciliary muscle thickness (CMT) was greater than nasal CMT at 2 mm and 3 mm from the scleral spur (CM2 and CM3, respectively) in each eye (right CM2: 0.29 ± 0.05 mm and 0.32 ± 0.05 mm for nasal and temporal aspects, respectively, P < 0.001; left CM2: 0.30 ± 0.05 mm and 0.32 ± 0.05 mm for nasal and temporal aspects, respectively, P < 0.001; right CM3: 0.13 ± 0.05 mm and 0.16 ± 0.04 mm for nasal and temporal aspects, respectively, P < 0.001; left CM3: 0.14 ± 0.04 mm and 0.17 ± 0.05 mm for nasal and temporal aspects, respectively, P < 0.001). AXL was positively correlated with ciliary muscle anterior length (AL) (e.g. P < 0.001, r2 = 0.262 for left temporal aspect), CML (P = 0.003, r2 = 0.175 for right nasal aspect) and ACD (P = 0.01, r2 = 0.181). Conclusions: Morphological characteristics of the ciliary muscle in emmetropic eyes display high levels of symmetry between the eyes. Greater CML and AL are linked to greater AXL and ACD, indicating ciliary muscle growth with normal ocular development.

Extended nonlinear analytical models of compliant parallelogram mechanisms: third-order models

This paper proposes extended nonlinear analytical models, third-order models, of compliant parallelogram mechanisms. These models are capable of capturing the accurate effects from the very large axial force within the transverse motion range of 10% of the beam length through incorporating the terms associated with the high-order (up to third-order) axial force. Firstly, the free-body diagram method is employed to derive the nonlinear analytical model for a basic compliant parallelogram mechanism based on load-displacement relations of a single beam, geometry compatibility conditions, and load-equilibrium conditions. The procedures for the forward solutions and inverse solutions are described. Nonlinear analytical models for guided compliant multi-beam parallelogram mechanisms are then obtained. A case study of the compound compliant parallelogram mechanism, composed of two basic compliant parallelogram mechanisms in symmetry, is further implemented. This work intends to estimate the internal axial force change, the transverse force change, and the transverse stiffness change with the transverse motion using the proposed third-order model in comparison with the first-order model proposed in the prior art. In addition, FEA (finite element analysis) results validate the accuracy of the third-order model for a typical example. It is shown that in the case study the slenderness ratio affects the result discrepancy between the third-order model and the first-order model significantly, and the third-order model can illustrate a non-monotonic transverse stiffness curve if the beam is thin enough.

Multistabilities and symmetry-broken one-color and two-color states in closely coupled single-mode lasers

We theoretically investigate the dynamics of two mutually coupled, identical single-mode semi-conductor lasers. For small separation and large coupling between the lasers, symmetry-broken one-color states are shown to be stable. In this case the light outputs of the lasers have significantly different intensities while at the same time the lasers are locked to a single common frequency. For intermediate coupling we observe stable symmetry-broken two-color states, where both lasers lase simultaneously at two optical frequencies which are separated by up to 150 GHz. Using a five-dimensional model, we identify the bifurcation structure which is responsible for the appearance of symmetric and symmetry-broken one-color and two-color states. Several of these states give rise to multistabilities and therefore allow for the design of all-optical memory elements on the basis of two coupled single-mode lasers. The switching performance of selected designs of optical memory elements is studied numerically.

Fermion Mass Generation without Spontaneous Symmetry Breaking

The conventional mechanism of fermion mass generation in the Standard Model involves Spontaneous Symmetry Breaking (SSB). In this thesis, we study an alternate mechanism for the generation of fermion masses that does not require SSB, in the context of lattice field theories. Being inherently strongly coupled, this mechanism requires a non-perturbative approach like the lattice approach.

In order to explore this mechanism, we study a simple lattice model with a four-fermion interaction that has massless fermions at weak couplings and massive fermions at strong couplings, but without any spontaneous symmetry breaking. Prior work on this type of mass generation mechanism in 4D, was done long ago using either mean-field theory or Monte-Carlo calculations on small lattices. In this thesis, we have developed a new computational approach that enables us to perform large scale quantum Monte-Carlo calculations to study the phase structure of this theory. In 4D, our results confirm prior results, but differ in some quantitative details of the phase diagram. In contrast, in 3D, we discover a new second order critical point using calculations on lattices up to size $ 60^3$. Such large scale calculations are unprecedented. The presence of the critical point implies the existence of an alternate mechanism of fermion mass generation without any SSB, that could be of interest in continuum quantum field theory.

The Effect of Foam Core Density on the Flexural and Axial Behaviour of Sandwich Panels of Varying Slenderness with Natural Flax-FRP and Glass-FRP Composite Skins

This study investigates the effect of foam core density and skin type on the behaviour of sandwich panels as structural beams tested in four-point bending and axially compressed columns of varying slenderness and skin thickness. Bio-composite unidirectional flax fibre-reinforced polymer (FFRP) is compared to conventional glass-FRP (GFRP) as the skin material used in conjunction with three polyisocyanurate (PIR) foam cores with densities of 32, 64 and 96 kg/m3. Eighteen 1000 mm long flexural specimens were fabricated and tested to failure comparing the effects of foam core density between three-layer FFRP skinned and single-layer GFRP skinned panels. A total of 132 columns with slenderness ratios (kLe/r) ranging from 22 to 62 were fabricated with single-layer GFRP skins, and one-, three-, and five-layer FFRP skins for each of the three foam core densities. The columns were tested to failure in concentric axial compression using pinned-end conditions to compare the effects of each material type and panel height. All specimens had a foam core cross-section of 100x50 mm with 100 mm wide skins of equal thickness. In both flexural and axial loading, panels with skins comprised of three FFRP layers showed equivalent strength to those with a single GFRP layer for all slenderness ratios and core densities examined. Doubling the core density from 32 to 64 kg/m3 and tripling the density to 96 kg/m3 led to flexural strength increases of 82 and 213%, respectively. Both FFRP and GFRP columns showed a similar variety of failure modes related to slenderness. Low slenderness of 22-25 failed largely due to localized single skin buckling, while those with high slenderness of 51-61 failed primarily by global buckling followed by secondary skin buckling. Columns with intermediate slenderness experienced both localized and global failure modes. High density foam cores more commonly exhibited core shear failure. Doubling the core density of the columns resulted in peak axial load increases, across all slenderness ratios, of 73, 56, 72 and 71% for skins with one, three and five FFRP layers, and one GFRP layer, respectively. Tripling the core density resulted in respective peak load increases of 116, 130, 176 and 170%.