Structural Analysis of a Helical Peptide Unfolding Pathway

The analysis of the folding mechanism in peptides adopting well‐defined secondary structure is fundamental to understand protein folding. Herein, we describe the thermal unfolding of a 15‐mer vascular endothelial growth factor mimicking α‐helical peptide (QK_L10A) through the combination of spectroscopic and computational analyses. In particular, on the basis of the temperature dependencies of QK_L10A H_α chemical shifts we show that the first phase of the thermal helix unfolding, ending at around 320 K, involves mainly the terminal regions. A second phase of the transition, ending at around 333 K, comprises the central helical region of the peptide. The determination of high‐resolution QK_L10A conformational preferences in water at 313 K allowed us to identify, at atomic resolution, one intermediate of the folding–unfolding pathway. Molecular dynamics simulations corroborate experimental observations detecting a stable central helical turn, which represents the most probable site for the helix nucleation in the folding direction. The data presented herein allows us to draw a folding–unfolding picture for the small peptide QK_L10A compatible with the nucleation–propagation model. This study, besides contributing to the basic field of peptide helix folding, is useful to gain an insight into the design of stable helical peptides, which could find applications as molecular scaffolds to target protein–protein interactions.     

A Structural Diversity of Molecular Alkaline-Earth-Metal Polyphosphides: From Supramolecular Wheel to Zintl Ion

A series of molecular group 2 polyphosphides has been synthesized by using air-stable [Cp*Fe(η⁵-P₅)] (Cp*=C₅Me₅) or white phosphorus as polyphosphorus precursors. Different types of group 2 reagents such as organo-magnesium, mono-valent magnesium, and molecular calcium hydride complexes have been investigated to activate these polyphosphorus sources. The organo-magnesium complex [(^DippBDI−Mg(CH₃))₂] (^DippBDI={[2,6-ⁱPr₂C₆H₃NCMe]₂CH}⁻) reacts with [Cp*Fe(η⁵-P₅)] to give an unprecedented Mg/Fe-supramolecular wheel. Kinetically controlled activation of [Cp*Fe(η⁵-P₅)] by different mono-valent magnesium complexes allowed the isolation of Mg-coordinated formally mono- and di-reduced products of [Cp*Fe(η⁵-P₅)]. To obtain the first examples of molecular calcium-polyphosphides, a molecular calcium hydride complex was used to reduce the aromatic cyclo-P₅ ring of [Cp*Fe(η⁵-P₅)]. The Ca-Fe-polyphosphide is also characterized by quantum chemical calculations and compared with the corresponding Mg complex. Moreover, a calcium coordinated Zintl ion (P₇)³⁻ was obtained by molecular calcium hydride mediated P₄ reduction.     

The redox chemistry of sulfenic acids

A persistent triptycenyl sulfenic acid is used as a model for cysteine-derived and other biologically relevant sulfenic acids in experiments which define their redox chemistry. EPR spectroscopy reveals that sulfinyl radicals are persistent and unreactive toward O(2), allowing the O-H bonding dissociation enthalpy (BDE) of the sulfenic acid to be readily determined by equilibration with TEMPO as 71.9 kcal/mol. The E° (RSO?/RSO(-)) and pK(a) of this sulfenic acid are also reported.     

A tail dependence-based dissimilarity measure for financial time series clustering

In this paper we propose a clustering procedure aimed at grouping time series with an association between extremely low values, measured by the lower tail dependence coefficient. Firstly, we estimate the coefficient using an Archimedean copula function. Then, we propose a dissimilarity measure based on tail dependence coefficients and a two-step procedure to be used with clustering algorithms which require that the objects we want to cluster have a geometric interpretation. We show how the results of the clustering applied to financial returns could be used to construct defensive portfolios reducing the effect of a simultaneous financial crisis.     

Limit of hanger linearity in suspension footbridge dynamics: A new section model

The mechanical behaviour of suspension bridges is characterised by nonlinearities due to the main cables geometric effects and to the inability of the hangers to sustain compressive loads. The nonlinear effects due to hanger slackening are expected to increase in suspension footbridges due to lightweight decks, that is, low dead to live load ratio, and to shallow plate-girder decks with very low flexural and torsional stiffness. In this paper a new section model is proposed to study the limit of hanger linearity in lightweight suspension footbridges. The model is inspired to a four degrees-of-freedom model already proposed in the literature, but is expressed with a new formalism that allows some interesting properties to be outlined. Specifically, the expression of a particular frequency, herein called relative antiresonance frequency, as a function of the model generalised properties is derived: if the system is loaded with a harmonic force having that frequency, the linear behaviour of the hangers is assured for every value of the force amplitude. The proposed section model is applied to a footbridge benchmark subject to the pedestrian harmonic load and results are compared with those obtained through a nonlinear dynamic analysis on a 3D Finite Element model of the bridge.     

Cation disorder in NaW2O6+δ·nH2−zO post-ion exchange with K, Rb, Sr, and Cs

The structure of the defect pyrochlore NaW₂O_6+δ·nH_2−zO after ion exchange with K, Rb, Sr or Cs for Na has been investigated using thermal analysis, solid-state nuclear magnetic resonance, laboratory X-ray and neutron diffraction methods. Neutron diffraction studies show that both the A-type cations (Na⁺, K⁺, Rb⁺, and/or Cs⁺) and the water molecules reside within the channels that form in the 111 direction of the W₂O₆ framework and that these strongly interact. The analytical results suggest that the water and A-type cations compete for space in the tunnels within the W₂O₆ pyrochlore framework, with the total number of water molecules and cations being approximately constant in the six samples investigated. The interplay between the cations and water explains the non-linear dependence of the a lattice parameter on the choice of cation. It appears that the ion-exchange capacity of the material will be controlled by the amount of water initially present in the sample.     

Genuine quantum and classical correlations in multipartite systems

Generalizing the quantifiers used to classify correlations in bipartite systems, we define genuine total, quantum, and classical correlations in multipartite systems. The measure we give is based on the use of relative entropy to quantify the distance between two density matrices. Moreover, we show that, for pure states of three qubits, both quantum and classical bipartite correlations obey a ladder ordering law fixed by two-body mutual informations, or, equivalently, by one-qubit entropies.     

Magnesium nanoparticles with transition metal decoration for hydrogen storage

We report on the hydrogen storage behaviour of Mg nanoparticles (NPs) (size range 100 nm–1 μm) with metal-oxide core–shell morphology synthesized by inert gas condensation and decorated by transition metal (TM) (Pd or Ti) clusters via in situ vacuum deposition. The structure and morphology of the as-prepared and hydrogenated NPs is studied by electron microscopy, X-ray diffraction including in situ experiments and X-ray absorption spectroscopy, in order to investigate the relationships with the hydrogen storage kinetics measured by the volumetric Sieverts method. With both Pd and Ti, the decoration deeply improves the hydrogen sorption properties: previously inert NPs exhibit complete hydrogenation with fast transformation kinetics, good stability and reversible gravimetric capacity that can attain 6 wt%. In the case of Pd-decoration, the occurrence of Mg–Pd alloying is observed at high temperatures and in dependence of the hydrogen pressure conditions. These structural transformations modify both the kinetics and thermodynamics of hydride formation, while Ti-decoration has an effect only on the kinetics. The experimental results are discussed in relation with key issues such as the amount of decoration, the heat of mixing between TM and Mg and the binding energy between TM and hydrogen.     

Refined methods for the identifiability of tensors

We prove that the general tensor of size \(2^n\) and rank \(k\) has a unique decomposition as the sum of decomposable tensors if \(k\le 0.9997\frac{2^n}{n+1}\) (the constant 1 being the optimal value). Similarly, the general tensor of size \(3^n\) and rank \(k\) has a unique decomposition as the sum of decomposable tensors if \(k\le 0.998\frac{3^n}{2n+1}\) (the constant 1 being the optimal value). Some results of this flavor are obtained for tensors of any size, but the explicit bounds obtained are weaker.