Structural effects on the beta-scission reaction of tertiary arylcarbinyloxyl radicals. The role of alpha-cyclopropyl and alpha-cyclobutyl groups

A product and time-resolved kinetic study on the reactivity of tertiary arylcarbinyloxyl radicals bearing alpha-cyclopropyl and alpha-cyclobutyl groups has been carried out. Both the 1-cyclopropyl-1-phenylethoxyl (1.) and alpha,alpha-dicyclopropylphenylmethoxyl (2.) radicals undergo beta-scission to give cyclopropyl phenyl ketone as the major or exclusive product with rate constants higher than that measured for the cumyloxyl radical. It is proposed that in the transition state for beta-scission of 1. and 2., formation of the C=O double bond is assisted by overlap with the C-C bonding orbitals of the cyclopropane ring. With tertiary arylcarbinyloxyl radicals bearing alpha-cyclobutyl groups such as the 1-cyclobutyl-1-phenylethoxyl (4.) and 1-cyclobutyl-1-phenylpropoxyl (5.) radicals, the fragmentation regioselectivity is essentially governed by the stability of the radical formed by beta-scission. Accordingly, 4. undergoes exclusive C-cyclobutyl bond cleavage to give acetophenone, whereas with 5., competition between C-cyclobutyl and C-ethyl bond cleavage, leading to propiophenone and cyclobutylphenyl ketone in a 2:1 ratio, is observed.     

On the controversial formation of silver diboride: Processing of Ag + 2B powders by spark plasma sintering

Following recent theoretical studies based on electronic structure calculations conducted on Ag- and Au-borides which estimated their superconducting behaviour at elevated transition temperatures, the preparation of AgB₂ was attempted in this work by reactive Spark Plasma Sintering (SPS) from Ag and B elemental powders. It was found that, independently from the processing conditions adopted, the formation of a new phase, which corresponds to a small peak on the XRD pattern at 2θ equal to about 28°, cannot be attributed to AgB₂. In fact, it was shown that the new phase detected on sintered pellets is most likely boric acid which is formed only if the sample is left in contact with air. If SPSed samples were stored under inert (Ar) atmosphere, no additional phases other than unreacted elements were observed.     

Spatial distribution of hydrogen and other emitters in aluminum laser-induced plasma in air and consequences on spatially integrated Laser-Induced Breakdown Spectroscopy measurements

The Stark broadening of hydrogen Balmer α line is often measured in Laser-Induced Breakdown Spectroscopy (LIBS) to evaluate the electron number density of the plasma. When measurements are carried out in air, hydrogen atoms are supposedly supplied by the atmosphere. This hypothesis casts some doubts on the validity of hydrogen as an indicator of the conditions in the inner part of the plasma. In this experiment, we acquired spectrally resolved images of a Laser-Induced Breakdown Spectroscopy plasma generated in air on an aluminum target by irradiation with the Nd:YAG fundamental emission. The evolution of the plasma was studied by acquiring images at several delay times. In particular, we imaged the spatial distribution of plasma emitters along the direction orthogonal to the target surface. The spatial distribution of hydrogen emission was compared to the one of the species ablated from the sample. Moreover, electron density and temperature were evaluated in the time- and space-resolved spectra extracted from the images, obtaining thus a picture of the propagation and internal structure of the plasma. The fluid dynamics implications of the plasma expansion were discussed. The z-resolved characterization was compared with the picture of the plasma obtained by processing space-integrated spectra.     

The order of the QCD transition with two light flavors

We report on the status of our analysis on the order of the finite temperature transition in QCD with two light flavors. Our new simulations on larger lattices give preliminary evidence of the first order nature of the transition also at small non-zero quark masses.     

Quantum cellular automata and free quantum field theory

In a series of recent papers [1–4] it has been shown how free quantum field theory can be derived without using mechanical primitives (including space-time, special relativity, quantization rules, etc.), but only considering the easiest quantum algorithm encompassing a countable set of quantum systems whose network of interactions satisfies the simple principles of unitarity, homogeneity, locality, and isotropy. This has opened the route to extending the axiomatic information-theoretic derivation of the quantum theory of abstract systems [5, 6] to include quantum field theory. The inherent discrete nature of the informational axiomatization leads to an extension of quantum field theory to a quantum cellular automata theory, where the usual field theory is recovered in a regime where the discrete structure of the automata cannot be probed. A simple heuristic argument sets the scale of discreteness to the Planck scale, and the customary physical regime where discreteness is not visible is the relativistic one of small wavevectors.     

Free surface flow impact on a vertical wall: a numerical assessment

The sudden impact of a free surface flow upon a solid wall is a common occurrence in many situations in nature and technology. The design of marine structures is probably the most obvious example, but also river and dam hydraulics as well as the necessity of understanding flood and debris flow-induced damage have led to theoretical and experimental work on the mechanism of fluid slamming loads. This is therefore a very old and rich research field, which has not yet reached full maturity, so that semi-empirical methods in design practice are still the rule in many sectors. Up-to-date CFD technology with both Eulerian and Lagrangian approaches is employed to investigate highly non-stationary fluid impact on a solid wall. The development of the pressure wave produced by the impact is examined as it propagates and interacts with the fluid boundaries, as well as the subsequent build-up of high-pressure gradients of high fluid velocities. The geometry and the velocity field of the problem considered are very simple, but the results seem to provide new insight, in particular, into the connection between phenomena with different timescales.     

The Wehrl entropy has Gaussian optimizers

We determine the minimum Wehrl entropy among the quantum states with a given von Neumann entropy and prove that it is achieved by thermal Gaussian states. This result determines the relation between the von Neumann and the Wehrl entropies. The key idea is proving that the quantum-classical channel that associates with a quantum state its Husimi Q representation is asymptotically equivalent to the Gaussian quantum-limited amplifier with infinite amplification parameter. This equivalence also permits to determine the \(p\rightarrow q\) norms of the aforementioned quantum-classical channel in the two particular cases of one mode and \(p=q\) and prove that they are achieved by thermal Gaussian states. The same equivalence permits to prove that the Husimi Q representation of a one-mode passive state (i.e., a state diagonal in the Fock basis with eigenvalues decreasing as the energy increases) majorizes the Husimi Q representation of any other one-mode state with the same spectrum, i.e., it maximizes any convex functional.     

Wave propagation and reflection-transmission in a stratified viscoelastic solid

The paper investigates time-harmonic wave propagation in continuously stratified solids and provides the results of a reflection-transmission process generated by a layer sandwiched between homogeneous half-spaces. The layer is continuously stratified and allows for jump discontinuities at a finite number of planes. The dissipative effects are accounted for through the classical Boltzmann law of viscoelasticity. By using displacement and traction as convenient vector variables, the governing equations are considered in a vector Volterra integral equation and the solution is determined by means of a matricant. Next the matricant is applied to determine the reflection and transmission coefficients of a layer, with a generic piecewise continuous profile of the material properties. The reflection-transmission process produced by an obliquely incident wave, is considered for horizontally-polarized waves. The low-frequency approximation is derived for the reflection and transmission coefficients. Next, the high-frequency approximation is investigated by a WKB-like procedure which involves a complex valued frequency-dependent shear modulus. The displacement solution is obtained for the forward- and the backward-propagating waves in the layer along with the reflection and transmission coefficients.     

Independence of friction self-locking from kinematic singularity

Self-locking analysis in closed kinematic chains is sometimes likened to kinematic singularity. Here a novel approach to tackle self-locking analysis due to joints friction is exploited, that is completely different from the classical kinematic analysis based on the jacobian conditioning. It is shown that an inverse kinematic singularity always entails a self-locking phenomenon because of the general increasing of joints reactions and, then, friction forces; hence, a self-locking domain can be always identified including such a locus. On the other side, this paper is aimed at demonstrating that the aforementioned condition is not necessary: namely, self-locking may occurs also if the mechanism kinematics is well-conditioned. Then, the theoretical result is clarified performing the self-locking analysis on a simple crank-slider mechanism.     

Metal‐Chelated Polymer Nanodiscs for NMR Studies

Paramagnetic relaxation enhancement (PRE) is commonly used to speed up spin lattice relaxation time (T₁) for rapid data acquisition in NMR structural studies. Consequently, there is significant interest in novel paramagnetic labels for enhanced NMR studies on biomolecules. Herein, we report the synthesis and characterization of a modified poly(styrene‐co‐maleic acid) polymer which forms nanodiscs while showing the ability to chelate metal ions. Cu²⁺‐chelated nanodiscs are demonstrated to reduce the T₁ of protons for both polymer and lipid‐nanodisc components. The chelated nanodiscs also decrease the proton T₁ values for a water‐soluble DNA G‐quadruplex. These results suggest that polymer nanodiscs functionalized with paramagnetic tags can be used to speed‐up data acquisition from lipid bilayer samples and also to provide structural information from water‐soluble biomolecules.