Between Aromatic and Quinoid Structure: A Symmetrical UV to Vis/NIR Benzothiadiazole Redox Switch

Reversibly switching the light absorption of organic molecules by redox processes is of interest for applications in sensors, light harvesting, smart materials, and medical diagnostics. This work presents a symmetrical benzothiadiazole (BTD) derivative with a high fluorescence quantum yield in solution and in the crystalline state and shows by spectroelectrochemical analysis that reversible switching of UV absorption in the neutral state, to broadband Vis/NIR absorption in the 1st oxidized state, to sharp band Vis absorption in the 2nd oxidized state, is possible. For the one-electron oxidized species, formation of a delocalized radical is confirmed by electron paramagnetic resonance spectroelectrochemistry. Furthermore, our results reveal an increasing quinoidal distortion upon the 1st and 2nd oxidation, which can be used as the leitmotif for the development of BTD based redox switches.     

Minimizing Side Product Formation in Alkyne Functionalization of Ruthenium Complexes by Introduction of Protecting Groups

The synthesis of alkyne functionalized bipyridine ruthenium complexes are reported. The improved synthetic approach through application of stable protecting groups prevents formation of possible side products while facilitating purification. By applying copper-catalysed azide-alkyne cycloaddition reactions (CuAAC) pyrene units with flexible alkyl linkers are introduced at the periphery of the complex, opening up various applications including surface immobilization and DNA intercalation. All complexes are characterized structurally as well as photophysically, especially regarding the influence of the introduced alkyne and triazolyl substituents on their photophysical behavior.     

Insights into the Structure and Energy of DNA Nanoassemblies

Since the pioneering work of Ned Seeman in the early 1980s, the use of the DNA molecule as a construction material experienced a rapid growth and led to the establishment of a new field of science, nowadays called structural DNA nanotechnology. Here, the self-recognition properties of DNA are employed to build micrometer-large molecular objects with nanometer-sized features, thus bridging the nano- to the microscopic world in a programmable fashion. Distinct design strategies and experimental procedures have been developed over the years, enabling the realization of extremely sophisticated structures with a level of control that approaches that of natural macromolecular assemblies. Nevertheless, our understanding of the building process, i.e., what defines the route that goes from the initial mixture of DNA strands to the final intertwined superstructure, is, in some cases, still limited. In this review, we describe the main structural and energetic features of DNA nanoconstructs, from the simple Holliday junction to more complicated DNA architectures, and present the theoretical frameworks that have been formulated until now to explain their self-assembly. Deeper insights into the underlying principles of DNA self-assembly may certainly help us to overcome current experimental challenges and foster the development of original strategies inspired to dissipative and evolutive assembly processes occurring in nature.     

Parabolic equations of Von Karman type on Kähler manifolds

We study a parabolic version of a system of Von Karman type on a compact Kähler manifold of arbitrary dimension. We provide local in time regular solutions, which can be extended to global bounded ones if the data of the problem are small.     

Thermal,Raman and dielectric study of 0.5K0.5Bi0.5TiO3–0.5PbTiO3 ceramics

The 0.5K_0.5Bi_0.5TiO₃–0.5PbTiO₃ ceramics were prepared by following a standard solid-state method. The Raman, thermal and dielectric properties of these ceramics were investigated. The X-ray measurements showed that samples have single perovskite-type structure with tetragonal symmetry. Dielectric study revealed that the dielectric behaviour of the investigated ceramics is rather of normal ferroelectrics with large thermal hysteresis. The transition temperature observed by means of differential scanning calorimetry measurements is in good agreement with that obtained from dielectric study.     

Palladium island growth on Ni(111) Stochastic classical trajectory — ghost atom calculations

We generalize previous stochastic classical trajectory-ghost atom calculations for describing palladium deposition onto the Ni(111) surface between 0.1 and 0.5 monolayers. The growth evolves through two-dimensional islands. The islands are formed following the downward funneling mechanism. Surface temperature does not affect the island growth.     

The challenge in managing new financial risks: adopting an heuristic or theoretical approach

The financial crisis began with the collapse of Lehman Brothers and the subprime asset backed securities debacle. Credit risk was turned into liquidity risk, resulting in a lack of confidence among financial institutions. In this article, we will propose a way to model liquidity risk and the credit risk in best practices. We will show that liquidity risk is a new type of risk and the current way to deal with it is based solely on observed variables without any theoretical link. We propose an heuristic approach to combine the numerous liquidity risk indicators with a logistic regression for the first time. In regards to credit risk, several articles prove that the best practice is to use an option model to appreciate this risk. We will present our methodology using stochastic diffusion for the interest rate because currently the yield curves aren’t liquid. This approach is more relevant because the basis model in prior publications has a constant interest rate or a forward rate. Both models allow a better understanding of liquidity and credit risks and the further development of research deals with the link between these two financial risks.     

Orthogonal polynomials on the unit circle and their derivatives

We characterize the sequences of orthogonal polynomials on the unit circle whose derivatives are also orthogonal polynomials on the unit circle. Some relations for the sequences of derivatives of orthogonal polynomials are provided. Finally, we pose some problems about orthogonality-preserving maps and differential equations for orthogonal polynomials on the unit circle.     

Conical stochastic maximal L^p-regularity for 1\leqslant p<\infty

Let \(A = -\mathrm{div} \,a(\cdot ) \nabla \) be a second order divergence form elliptic operator on \({\mathbb R}^n\) with bounded measurable real-valued coefficients and let \(W\) be a cylindrical Brownian motion in a Hilbert space \(H\) . Our main result implies that the stochastic convolution process $$\begin{aligned} u(t) = \int _0^t e^{-(t-s)A}g(s)\,dW(s), \quad t\geqslant 0, \end{aligned}$$ satisfies, for all \(1\leqslant p<\infty \) , a conical maximal \(L^p\) -regularity estimate $$\begin{aligned} {\mathbb E}\Vert \nabla u \Vert _{ T_2^{p,2}({\mathbb R}_+\times {\mathbb R}^n)}^p \leqslant C_p^p {\mathbb E}\Vert g \Vert _{ T_2^{p,2}({\mathbb R}_+\times {\mathbb R}^n;H)}^p. \end{aligned}$$ Here, \(T_2^{p,2}({\mathbb R}_+\times {\mathbb R}^n)\) and \(T_2^{p,2}({\mathbb R}_+\times {\mathbb R}^n;H)\) are the parabolic tent spaces of real-valued and \(H\) -valued functions, respectively. This contrasts with Krylov’s maximal \(L^p\) -regularity estimate $$\begin{aligned} {\mathbb E}\Vert \nabla u \Vert _{L^p({\mathbb R}_+;L^2({\mathbb R}^n;{\mathbb R}^n))}^p \leqslant C^p {\mathbb E}\Vert g \Vert _{L^p({\mathbb R}_+;L^2({\mathbb R}^n;H))}^p \end{aligned}$$ which is known to hold only for \(2\leqslant p<\infty \) , even when \(A = -\Delta \) and \(H = {\mathbb R}\) . The proof is based on an \(L^2\) -estimate and extrapolation arguments which use the fact that \(A\) satisfies suitable off-diagonal bounds. Our results are applied to obtain conical stochastic maximal \(L^p\) -regularity for a class of nonlinear SPDEs with rough initial data.     

Spin and Majorana polarization in topological superconducting wires

We study a one-dimensional wire with strong Rashba and Dresselhaus spin-orbit coupling (SOC), which supports Majorana fermions when subject to a Zeeman magnetic field and in the proximity of a superconductor. Using both analytical and numerical techniques we calculate the electronic spin texture of the Majorana end states. We find that the spin polarization of these states depends on the relative magnitude of the Rashba and Dresselhaus SOC components. Moreover, we define and calculate a local "Majorana polarization" and "Majorana density" and argue that they can be used as order parameters to characterize the topological transition between the trivial system and the system exhibiting Majorana bound modes. We find that the local Majorana polarization is correlated to the transverse spin polarization, and we propose to test the presence of Majorana fermions in a 1D system by a spin-polarized density of states measurement.