A Unified Approach to Local Quantum Uncertainty and Interferometric Power by Metric Adjusted Skew Information

Local quantum uncertainty and interferometric power were introduced by Girolami et al. as geometric quantifiers of quantum correlations. The aim of the present paper is to discuss their properties in a unified manner by means of the metric adjusted skew information defined by Hansen.     

The Early Steps of Molecule-to-Material Conversion in Chemical Vapor Deposition (CVD): A Case Study

Transition metal complexes with β-diketonate and diamine ligands are valuable precursors for chemical vapor deposition (CVD) of metal oxide nanomaterials, but the metal-ligand bond dissociation mechanism on the growth surface is not yet clarified in detail. We address this question by density functional theory (DFT) and ab initio molecular dynamics (AIMD) in combination with the Blue Moon (BM) statistical sampling approach. AIMD simulations of the Zn β-diketonate-diamine complex Zn(hfa)₂TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N′,N′-tetramethylethylenediamine), an amenable precursor for the CVD of ZnO nanosystems, show that rolling diffusion of this precursor at 500 K on a hydroxylated silica slab leads to an octahedral-to-square pyramidal rearrangement of its molecular geometry. The free energy profile of the octahedral-to-square pyramidal conversion indicates that the process barrier (5.8 kcal/mol) is of the order of magnitude of the thermal energy at the operating temperature. The formation of hydrogen bonds with surface hydroxyl groups plays a key role in aiding the dissociation of a Zn-O bond. In the square-pyramidal complex, the Zn center has a free coordination position, which might promote the interaction with incoming reagents on the deposition surface. These results provide a valuable atomistic insight on the molecule-to-material conversion process which, in perspective, might help to tailor by design the first nucleation stages of the target ZnO-based nanostructures.     

Secondary Formation of Aromatic Nitroderivatives of Environmental Concern: Photonitration Processes Triggered by the Photolysis of Nitrate and Nitrite Ions in Aqueous Solution

Aromatic nitroderivatives are compounds of considerable environmental concern, because some of them are phytotoxic (especially the nitrophenols, and particularly 2,4-dinitrophenol), others are mutagenic and potentially carcinogenic (e.g., the nitroderivatives of polycyclic aromatic hydrocarbons, such as 1-nitropyrene), and all of them absorb sunlight as components of the brown carbon. The latter has the potential to affect the climatic feedback of atmospheric aerosols. Most nitroderivatives are secondarily formed in the environment and, among their possible formation processes, photonitration upon irradiation of nitrate or nitrite is an important pathway that has periodically gained considerable attention. However, photonitration triggered by nitrate and nitrite is a very complex process, because the two ionic species under irradiation produce a wide range of nitrating agents (such as ^•NO₂, HNO₂, HOONO, and H₂OONO⁺), which are affected by pH and the presence of organic compounds and, in turn, deeply affect the nitration of aromatic precursors. Moreover, aromatic substrates can highly differ in their reactivity towards the various photogenerated species, thereby providing different behaviours towards photonitration. Despite the high complexity, it is possible to rationalise the different photonitration pathways in a coherent framework. In this context, this review paper has the goal of providing the reader with a guide on what to expect from the photonitration process under different conditions, how to study it, and how to determine which pathway(s) are prevailing in the formation of the observed nitroderivatives.     

Effect of limonene on the frontal ring opening metathesis polymerization of dicyclopentadiene

The frontal ring opening metathesis polymerization (FROMP) of dicyclopentadiene (DCPD) in the presence of limonene, using second generation Grubbs’ catalysts, is reported. The effect of limonene on the amount of catalyst and the typical frontal polymerization parameters, as maximum temperature (T_max) and velocity of the front (V_f), is studied. In addition, the influence of limonene on the mechanical properties of the polymeric samples is reported. Finally, a deep study on the swelling properties of polymers is done. It has been demonstrated that limonene acts as both inhibitor and solvent of the catalyst. The T_max, V_f, T_g, and Young modulus values decrease as the amount of limonene increases, and the polymer samples swell in THF depending on the amount of limonene. All results indicate that the limonene addition on FROMP of results in advantages on the polymerization reaction and its parameters and on the final polymer properties. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 63–68     

Extremal Curves in Nilpotent Lie Groups

We classify extremal curves in free nilpotent Lie groups. The classification is obtained via an explicit integration of the adjoint equation in Pontryagin maximum principle. It turns out that abnormal extremals are precisely the horizontal curves contained in algebraic varieties of a specific type. We also extend the results to the nonfree case.     

A lattice Boltzmann model for diffusion of binary gas mixtures that includes diffusion slip

This paper describes the development of a lattice Boltzmann (LB) model for a binary gas mixture, and applications to channel flow driven by a density gradient with diffusion slip occurring at the wall. LB methods for single component gases typically use a non‐physical equation of state in which the relationship between pressure and density varies according to the scaling used. This is fundamentally unsuitable for extension to multi‐component systems containing gases of differing molecular masses. Substantial variations in the species densities and pressures may exist even at low Mach numbers; hence, the usual linearized equation of state for small fluctuations is unsuitable. Also, existing methods for implementing boundary conditions do not extend easily to novel boundary conditions, such as diffusion slip. The new model developed for multi‐component gases avoids the pitfalls of some other LB models. A single computational grid is shared by all the species, and the diffusivity is independent of the viscosity. The Navier–Stokes equation for the mixture and the Stefan–Maxwell diffusion equation are both recovered by the model. Diffusion slip, the non‐zero velocity of a gas mixture at a wall parallel to a concentration gradient, is successfully modelled and validated against a simple one‐dimensional model for channel flow. To increase the accuracy of the scheme, a second‐order numerical implementation is needed. This may be achieved using a variable transformation method that does not increase the computational time. Simulations were carried out on hydrogen and water diffusion through a narrow channel for varying total pressure and concentration gradients. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of infiltration material on a LSM15/CGO10 electrochemical reactor in the electrochemical oxidation of propene

The effect of infiltrating on a La_0.85Sr_0.15MnO₃/Ce_0.9Gd_0.1O_1.95 11-layer electrochemical reactor with CeO₂ and Ce_0.8Pr_0.2O_2?δ was studied in propene oxidation at open-circuit voltage and under polarization as a function of reaction temperature. This work outlined the importance of catalytic and electrochemical properties of infiltrated material on the ability to increase propene conversion under polarization with good faradaic efficiency. Electrochemical impedance spectroscopy was used to study the effect of infiltration material on electrode properties. The infiltration of a mixed ionic and electronic conductor, like Ce_0.8Pr_0.2O_2?δ , increased the electrode performance at low temperature but decreased the lifetime of the oxygen ion promoters on the catalyst/electrode surface, reducing the faradaic efficiency of the reaction. The infiltration of CeO₂ provided high propene conversion at open circuit and high effect of polarization associated with good faradaic efficiency, especially at low temperature.     

Ultra high performance liquid chromatography with ion‐trap TOF‐MS for the fast characterization of flavonoids in Citrus bergamia juice

We have developed a fast ultra HPLC with ion‐trap TOF‐MS method for the analysis of flavonoids in Citrus bergamia juice. With respect to the typical methods for the analysis of these matrices based on conventional HPLC techniques, a tenfold faster separation was attained. The use of a core–shell particle column ensured high resolution within the fast analysis time of only 5 min. Unambiguous determination of flavonoid identity was obtained by the employment of a hybrid ion‐trap TOF mass spectrometer with high mass accuracy (average error 1.69 ppm). The system showed good retention time and peak area repeatability, with maximum RSD% values of 0.36 and 3.86, respectively, as well as good linearity (R² ≥ 0.99). Our results show that ultra HPLC can be a useful tool for ultra fast qualitative/quantitative analysis of flavonoid compounds in citrus fruit juices.