Stable Aqueous Solutions of Naked Titanate Nanotubes

Aqueous solutions of naked nanotubes with Ti concentration up to 10 mM are obtained by hydrothermal synthesis followed by extensive ultrasound treatment. The morphology, surface characteristics, and solution behavior of the solubilized nanotubes are investigated. The time course of the solubilization process driven by ultrasound follows a first‐order kinetic law and is mediated by the competition between Na⁺ and H⁺ for surface sites. The dynamics of interaction with small cations (i.e. the sodium ion) is studied by nuclear magnetic resonance spectroscopy and is demonstrated to be a multifaced process, since Na⁺ is in part free to exchange between the binding sites on nanotubes and the bulk and in part is confined to slowly exchanging nanotube sites. The aqueous titanate nanotube solutions are stable for months, thus opening new perspectives for the use of this material in drug delivery and in homogeneous photocatalysis.     

Quantification of plasma carnitine and acylcarnitines by high-performance liquid chromatography-tandem mass spectrometry using online solid-phase extraction

Carnitine is an amino acid derivative that plays a key role in energy metabolism. Endogenous carnitine is found in its free form or esterified with acyl groups of several chain lengths. Quantification of carnitine and acylcarnitines is of particular interest for screening for research and metabolic disorders. We developed a method with online solid-phase extraction coupled to high-performance liquid chromatography and tandem mass spectrometry to quantify carnitine and three acylcarnitines with different polarity (acetylcarnitine, octanoylcarnitine, and palmitoylcarnitine). Plasma samples were deproteinized with methanol, loaded on a cation exchange trapping column and separated on a reversed-phase C8 column using heptafluorobutyric acid as an ion-pairing reagent. Considering the endogenous nature of the analytes, we quantified with the standard addition method and with external deuterated standards. Solid-phase extraction and separation were achieved within 8 min. Recoveries of carnitine and acylcarnitines were between 98 and 105 %. Both quantification methods were equally accurate (all values within 84 to 116 % of target concentrations) and precise (day-to-day variation of less than 18 %) for all carnitine species and concentrations analyzed. The method was used successfully for determination of carnitine and acylcarnitines in different human samples. In conclusion, we present a method for simultaneous quantification of carnitine and acylcarnitines with a rapid sample work-up. This approach requires small sample volumes and a short analysis time, and it can be applied for the determination of other acylcarnitines than the acylcarnitines tested. The method is useful for applications in research and clinical routine.

The extended Bloch representation of quantum mechanics and the hidden-measurement solution to the measurement problem

A generalized Bloch sphere, in which the states of a quantum entity of arbitrary dimension are geometrically represented, is investigated and further extended, to also incorporate the measurements. This extended representation constitutes a general solution to the measurement problem, inasmuch it allows to derive the Born rule as an average over hidden-variables, describing not the state of the quantum entity, but its interaction with the measuring system. According to this modelization, a quantum measurement is to be understood, in general, as a tripartite process, formed by an initial deterministic decoherence-like process, a subsequent indeterministic collapse-like process, and a final deterministic purification-like process. We also show that quantum probabilities can be generally interpreted as the probabilities of a first-order non-classical theory, describing situations of maximal lack of knowledge regarding the process of actualization of potential interactions, during a measurement.     

d-strong Edge Colorings of Graphs

For a proper edge coloring of a graph G the palette S(v) of a vertex v is the set of the colors of the incident edges. If S(u) ≠ S(v) then the two vertices u and v of G are distinguished by the coloring. A d-strong edge coloring of G is a proper edge coloring that distinguishes all pairs of vertices u and v with distance 1 ≤ d (u, v) ≤ d. The d-strong chromatic index ${\chi_{d}^{\prime}(G)}$ of G is the minimum number of colors of a d-strong edge coloring of G. Such colorings generalize strong edge colorings and adjacent strong edge colorings as well. We prove some general bounds for ${\chi_{d}^{\prime}(G)}$ , determine ${\chi_{d}^{\prime}(G)}$ completely for paths and give exact values for cycles disproving a general conjecture of Zhang et al. (Acta Math Sinica Chin Ser 49:703–708 2006)).     

A 3D Griffith peeling model to unify and generalize single and double peeling theories

It has been shown in recent years that many species in Nature employ hierarchy and contact splitting as a strategy to enhance the adhesive properties of their attachments. Maximizing the adhesive force is however not the only goal. Many animals can achieve a tunable adhesive force, which allows them to both strongly attach to a surface and easily detach when necessary. Here, we study the adhesive properties of 3D dendritic attachments, which are structures that are widely occurring in nature and which allow to achieve these goals. These structures exploit branching to provide high variability in the geometry, and thus tunability, and contact splitting, to increase the total peeling line and thus the adhesion force. By applying the same principles presented by A.A. Griffith 100 years ago, we derive an analytical model for the detachment forces as a function of their defining angles in 3D space, finding as limit cases 2D double peeling and 1D single peeling. We also develop a numerical model, including a nonlinear elastic constitutive law, for the validation of analytical calculations, allowing additionally to simulate the entire detachment phase, and discuss how geometrical variations influence the adhesive properties of the structure. Finally, we also realize a proof of concept experiment to further validate theoretical/numerical results. Overall, we show how this generalized attachment structure can achieve large variations in its adhesive and mechanical properties, exploiting variations of its geometrical parameters, and thus tunability. The in-depth study of similar basic structural units and their combination can in future lead to a better understanding of the mechanical properties of complex architectures found in Nature.

     

Monolayer control of discotic liquid crystal by electromigration of dewetted layers in thin film devices

We show that ultrathin films of a semiconductive discotic liquid crystal, viz. phthalocyanines, can be organized to form a conductive channel tens of microns long between Au electrodes with thickness control over a single monolayer. Our approach exploits the electromigration of the isotropic phase formed starting from the pretransitional region of the columnar-isotropic phase transition. Dewetted isotropic material accumulates to the negative electrode by applying a longitudinal electric field of about 1 V/microm. Dewetting and electromigration expose an ultrathin film, a few monolayers thick, exhibiting columnar liquid crystal order. The layers of this ultrathin film melt progressively above T(C) and can be individually exfoliated by electromigration, starting from the ninth down to the first monolayer. The analysis of the current flowing through the junction as a function of the temperature, together with the comparative imaging of the evolution of morphology, yields a detailed picture of the changes in the dimensionality of the conductive phthalocyanine film and allows us to extract the behavior of the order parameter. The phenomenon of electromigration opens interesting questions on the technological control of individual monolayers on device patterns.     

Study of the order-disorder transitions in methoxy-functionalized polyalkylthiophenes

This article describes the solvatochromic properties of two polyalkylthiophene (PAT) samples functionalized at the end of the hexamethylenic side-chains with a methoxy group, which is able to strongly enhance the solubility, workability and filmability of this kind of polymers. The latter are obtained using either a regioselective or a regiospecific polymerization procedure, thus leading to a different configurational order in the final polymer. The optical features of the synthesized samples—which are very interesting for chemosensor and electrooptical applications—are observed in many solvent/non-solvent systems and derive from the conformational modification of the conjugated backbone induced by side-chain order-disorder transitions. These transitions strongly depend on the content of HT dyads; a fact which undeniably shows the importance of the polymer configuration, directly deriving from the adopted polymerization method, on the final electrical and electronic properties of the obtained material. The low sensitivity of the regioregular sample towards the temperature changes together with its higher tendency to give thick, semicrystalline and self-consisting films makes it very promising for the obtainment of organic semiconductors for electronic devices subjected to high temperature variations.     

Accurate ab initio intermolecular potential energy surface for the quintet state of the O2(3Sigma(g)-)-O2(3Sigma(g)-) dimer

A new potential energy surface (PES) for the quintet state of rigid O(2)((3)Sigma(g)(-)) + O(2)((3)Sigma(g)(-)) has been obtained using restricted coupled-cluster theory with singles, doubles, and perturbative triple excitations [RCCSD(T)]. A large number of relative orientations of the monomers (65) and intermolecular distances (17) have been considered. A spherical harmonic expansion of the interaction potential has been built from the ab initio data. It involves 29 terms, as a consequence of the large anisotropy of the interaction. The spherically averaged term agrees quite well with the one obtained from analysis of total integral cross sections. The absolute minimum of the PES corresponds to the crossed (D(2d)) structure (X shape) with an intermolecular distance of 6.224 bohrs and a well depth of 16.27 meV. Interestingly, the PES presents another (local) minimum close in energy (15.66 meV) at 6.50 bohrs and within a planar skewed geometry (S shape). We find that the origin of this second structure is due to the orientational dependence of the spin-exchange interactions which break the spin degeneracy and leads to three distinct intermolecular PESs with singlet, triplet, and quintet multiplicities. The lowest vibrational bound states of the O(2)-O(2) dimer have been obtained and it is found that they reflect the above mentioned topological features of the PES: The first allowed bound state for the (16)O isotope has an X structure but the next state is just 0.12 meV higher in energy and exhibits an S shape.     

Parallel Jacobi–Davidson with block FSAI preconditioning and controlled inner iterations

The Jacobi–Davidson (JD) algorithm is considered one of the most efficient eigensolvers currently available for non‐Hermitian problems. It can be viewed as a coupled inner‐outer iteration, where the inner one expands the search subspace and the outer one reduces the eigenpair residual. One of the difficulties in the JD efficient use stems from the definition of the most appropriate inner tolerance, so as to avoid useless extra work and keep the number of outer iterations under control. To this aim, the use of an efficient preconditioner for the inner iterative solver is of paramount importance. The present paper describes a fresh implementation of the JD algorithm with controlled inner iterations and block factorized sparse approximate inverse preconditioning for non‐Hermitian eigenproblems in a parallel computational environment. The algorithm performance is investigated by comparison with a freely available software package such as SLEPc. The results show that combining the inner tolerance control with an efficient preconditioning technique can allow for a significant improvement of the JD performance, preserving a good scalability. Copyright © 2016 John Wiley & Sons, Ltd.