Influence of Equilibration Time in Solution on the Inclusion/Exclusion Topology Ratio of Host–Guest Complexes Probed by Ion Mobility and Collision‐Induced Dissociation

Host–guest complexes are formed by the creation of multiple noncovalent bonds between a large molecule (the host) and smaller molecule(s) or ion(s) (the guest(s)). Ion‐mobility separation coupled with mass spectrometry nowadays represents an ideal tool to assess whether the host–guest complexes, when transferred to the gas phase upon electrospray ionization, possess an exclusion or inclusion nature. Nevertheless, the influence of the solution conditions on the nature of the observed gas‐phase ions is often not considered. In the specific case of inclusion complexes, kinetic considerations must be taken into account beside thermodynamics; the guest ingression within the host cavity can be characterized by slow kinetics, which makes the complexation reaction kinetically driven on the timescale of the experiment. This is particularly the case for the cucurbituril family of macrocyclic host molecules. Herein, we selected para‐phenylenediamine and cucurbit[6]uril as a model system to demonstrate, by means of ion mobility and collision‐induced dissociation measurements, that the inclusion/exclusion topology ratio varies as a function of the equilibration time in solution prior to the electrospray process.     

Sticking and nonsticking orbits for a two-degree-of-freedom oscillator excited by dry friction and harmonic loading

We consider a system composed of two masses connected by linear springs. One of the masses is in contact with a rough surface. Friction force, with Coulomb’s characteristics, acts between the mass and the surface. Moreover, the mass is also subjected to a harmonic external force. Several periodic orbits are obtained in closed form. A first kind of orbits involves sticking phases: during these parts of the orbit, the mass in contact with the rough surface remains at rest for a finite time. Another kind of orbits includes one or more stops of the mass with zero duration. Normal and abnormal stops are obtained. Moreover, for some of these periodic solutions, we prove that symmetry in space and time occurs.     

Pd@SnO2 and SnO2@Pd Core@Shell Nanocomposite Sensors

Pd@SnO₂ and SnO₂@Pd core@shell nanocomposites are prepared via a microemulsion approach. Both nanocomposites exhibit high‐surface, porous matrices of SnO₂ shells (>150 m² g^?1) with very small SnO₂ crystallites (<10 nm) and palladium (Pd) nanoparticles (<10 nm) that are uniformly distributed in the porous SnO₂ matrix. Although similar by first sight, Pd@SnO₂ and SnO₂@Pd are significantly different in view of their structure with Pd inside or outside the SnO₂ shell and in view of their sensor performance. As SMOX‐based sensors (SMOX: semiconducting metal oxide), both nanocomposites show a very good sensor performance for the detection of CO and H₂. Especially, the Pd@SnO₂ core@shell nanocomposite is unique and shows a fast response time (τ₉₀ < 30 s) and a very good response at low temperature (<250 °C), especially under humid‐air conditions. Extraordinarily high sensor signals are observed when exposing the Pd@SnO₂ nanocomposite to CO in humid air. Under these conditions, even commercial sensors (Figaro TGS 2442, Applied Sensor MLC, E2V MICS 5521) are outperformed.     

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.     

A limiting distribution for maxima of discrete stationary triangular arrays with an application to risk due to avalanches

In this paper, we generalize earlier work dealing with maxima of discrete random variables. We show that row-wise stationary block maxima of a triangular array of integer valued random variables converge to a Gumbel extreme value distribution if row-wise variances grow sufficiently fast as the row-size increases. As a by-product, we derive analytical expressions of normalising constants for most classical unbounded discrete distributions. A brief simulation illustrates our theoretical result. Also, we highlight its usefulness in practice with a real risk assessment problem, namely the evaluation of extreme avalanche occurrence numbers in the French Alps.     

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.     

K-line X-ray fluorescence from highly charged iron ions under dense astrophysical plasma conditions

In the present work, we report an investigation of plasma environment effects on the atomic parameters associated with the K-vacancy states in highly charged iron ions within the astrophysical context of accretion disks around black holes. More particularly, the sensitivity of K-line X-ray fluorescence parameters (wavelengths, radiative transition probabilities, and Auger rates) in Fe XVII–Fe XXV ions has been estimated for plasma conditions characterized by an electron temperature ranging from 10⁵ to 10⁷ K and an electron density ranging from 10¹⁸ to 10²² cm⁻³. In order to do this, relativistic multiconfiguration Dirac-Fock atomic structure calculations have been carried out by considering a time averaged Debye-Hückel potential for both the electron–nucleus and electron–electron interactions.