Band structures of Ni3Pt and NiPt3

The results of self-consistent, spin-polarized LMTO band structure calculations are shown for the compounds Ni₃Pt and NiPt₃, ofL12 (Cu₃Au) structure. Lattice constants are reported together with bulk moduli, and the electronic structure is studied in relation to magnetism in both cubic compounds. Covalent magnetism is shown to act against the magnetization in Ni₃Pt.     

Analytical potential of a laser ablation–glow discharge–optical emission spectrometry system for the analysis of conducting and insulating materials

The analytical capabilities of a glow discharge (GD) as a secondary source for excitation/ionization of the material provided by laser ablation (LA) have been compared to conventional laser induced breakdown spectroscopy (LIBS). In LA–GD both sources can be independently adjusted to optimize the sampling process and then its subsequent excitation. This could involve a number of analytical performance advantages, such as reduced matrix dependence, greater precision and sensitivity than those encountered in LIBS. For such purpose, an ablation chamber design including two electrodes to generate the GD discharge has been built and assayed. A comparison between LIBS and LA–GD–OES has been carried out, both, under reduced argon and helium atmospheres. Different sets of samples (conducting reference materials, glass and fluorine pellets) have been used to evaluate the novel coupled technique. The LA–GD coupled system has shown to provide lower detection limits. In addition, best linear correlations between intensities and concentrations and lower matrix effects have also been found using the coupled system. Moreover, special advantages of the LA–GD–OES have also been demonstrated for the analysis of fluorine.     

DFT studies on coordination models for adsorption essays of Cu(II) and Ni(II) solutions in modified silica gel with iminodiacetic groups

Research in functionalized inorganic supports faces special challenges regarding the inmobilization of organic chains and efficient computational methods for the quantum chemical modeling of coordination compounds. The silylant 3-cloropropyltriethoxysilyl (R1) was anchored over silica gel in anhydrous conditions, in order to react with diethyl Iminodiacetate (DIDA) to obtain modified silica gel (R2), which was hydrolized in basic conditions previously synthesized and characterized by S _BET, TGA and FTIR spectroscopy to obtain iminodiacetic acid groups IDA to prepare an modified inorganic support (R3) that is able to get hands on metals from the first transition series such as copper and nickel. The obtained experimental values showed that the functionalized grade of R3 corresponds to 0.1598 mmol of the nitrogen indicated that the adsorbed Cu(II) or Ni(II) have the stoichiometry for both cation of 1:1. Based on this relation, the three different structures were proposed to carry out the computational studies using density functional theory (DFT) in its LDA and PW91 with the TZP slater type basis set. The primary coordination sphere of copper(II) or nickel (II) ion in R3 are optimized, structural parameters are calculated, vibrational bands are assigned and energy gaps of frontier orbital (HOMO–LUMO) have been calculated. The calculated results reproduced the experimental data with good agreement. An energy decomposition analysis (EDA) of the different models proposed here was performed and suggest a 1:1 coordination form.     

A Safety Strategy for Producing Poly(Acrylic Acid) of Low Molar Mass

The synthesis of poly(acrylic acid) (PAA) of low molar mass under safe conditions is difficult due to the high polymerization rate of acrylic acid (AA) and the fast heat generation. The aqueous‐solution “semibatch” polymerization of non‐ionized AA in almost starved conditions involves high initiator loads when low molar masses are required. This article proposes the simultaneous feeding of AA and nonconventional chain transfer agents (CTA) as a strategy aimed at controlling both the molar masses and the generated heat rate. Three CTAs are investigated: 2‐mercaptoethanol, thioglycolic acid, and isopropyl alcohol. Even when PAA of relatively low molar mass can be produced by adequately selecting the flow rates and concentrations of both AA and CTA, it is found that the nature of CTA can have a significant effect on the polymerizations kinetics. The mechanisms responsible for these effects are discussed with the help of a representative mathematical model.

     

Higher regularity of the free boundary in the parabolic Signorini problem

We show that the quotient of two caloric functions which vanish on a portion of an \(H^{k+ \alpha }\) regular slit is \(H^{k+ \alpha }\) at the slit, for \(k \ge 2\). In the case \(k=1\), we show that the quotient is in \(H^{1+\alpha }\) if the slit is assumed to be space-time \(C^{1, \alpha }\) regular. This can be thought of as a parabolic analogue of a recent important result in De Silva and Savin (Boundary Harnack estimates in slit domains and applications to thin free boundary problems, 2014), whose ideas inspired us. As an application, we show that the free boundary near a regular point of the parabolic thin obstacle problem studied in Danielli et al. (Optimal regularity and the free boundary in the parabolic Signorini problem. Mem. Am. Math. Soc., 2013) with zero obstacle is \(C^{\infty }\) regular in space and time.     

The Vortex Filament Equation as a Pseudorandom Generator

In this paper, we consider the evolution of the so-called vortex filament equation (VFE),

$$\mathbf{X}_t = \mathbf{X}_s\wedge\mathbf{X}_{ss}, $$

taking a planar regular polygon of M sides as initial datum. We study VFE from a completely novel point of view: that of an evolution equation which yields a very good generator of pseudorandom numbers in a completely natural way. This essential randomness of VFE is in agreement with the randomness of the physical phenomena upon which it is based.

     

Separation of enantiomers of ephedrine by capillary electrophoresis using cyclodextrins as chiral selectors: comparative CE, NMR and high resolution MS studies

The enantiomer migration order (EMO) of ephedrine was investigated in the presence of various CDs in CE. The molecular mechanisms of chiral recognition were followed for the ephedrine complexes with native α- and β-CD and heptakis(2,3-di-O-acetyl-6-O-sulfo)-β-CD (HDAS-β-CD) by CE, NMR spectroscopy and high-resolution MS. Minor structural differences were observed between the complexes of ephedrine with α- and β-CD although the migration order of enantiomers was opposite when these two CDs were applied as chiral selectors in CE. The EMO was also opposite between β-CD and HDAS-β-CD. Significant structural differences were observed between ephedrine complexes with the native CDs and HDAS-β-CD. The latter CD was advantageous as chiral CE selector not only due to its opposite electrophoretic mobility compared with that of the cationic chiral analyte, but also primarily due to its enhanced chiral recognition ability towards the enantiomers of ephedrine.     

Density functional study of the structures and electronic properties of nitrogen-doped Ni(n) clusters, n = 1-10

We present a first-principles study of the equilibrium geometries, electronic structure, and related properties (binding energies, ionization potentials, electron affinities, and magnetic moments) of free-standing Ni(n) (n = 1-10) clusters doped with one impurity of N. Calculations have been performed in the framework of the density functional theory, as implemented in the SIESTA code within the generalized gradient approximation to exchange and correlation. We show that, in contrast to the molecular adsorption of N(2), the adsorption of a single N atom can dramatically change the structure of the host Ni(n) cluster, examples of which are Ni(5)N, Ni(7)N, and Ni(10)N, and that noticeable structure relaxations take place otherwise. Doping with a nitrogen impurity increases the binding energy as well as the ionization potential (except for Ni(6)N), which proves that N-doping works in favor of stabilizing the Ni clusters. We also find that the magnetic moments decrease in most cases upon N-doping despite the fact that the average Ni-Ni distance increases. The HUMO-LUMO gap for one spin channel strongly changes as a function of size upon N-doping, in contrast with the HUMO-LUMO gap for the other spin channel. This might have important implication in electronic transport properties through these molecular contacts anchored to source and drain electrodes.     

Synthesis of chiral mesoporous silicas with oligo(saccharide) surfaces and their use in separation of stereoisomers

Novel chiral mesoporous silicas (SBA-15 motif) with chemically bonded oligo(saccharides) (1, 3, and 7 glucose units) were obtained through the cocondensation of organosilicon derivatives of the oligo(saccharides) and silica precursors in the presence of polymer surfactant template under mild acidic conditions. The pore order and structure of the materials prepared were characterized by transmission electron microscopy and nitrogen adsorption. The direct application of the oligo(saccharide)-grafted SBA-15 stationary phases in the HPLC separations of stereoisomers was demonstrated for the first time.     

Confinement of halide ions within homologous inverse coordination hosts; modification of halide-ion selectivity

The structures of a series of spherical host-guest complexes [{MeE(PPh)(3)Li(4)·3thf}(4)(μ(4)-X)](-) (E = Al, [1X](-); E = Ga, [2X](-); E = In, [3X](-)) reveal that changing the halide ions (X = Cl, Br, or I) within their central tetrahedral Li(4) sites has negligible effect on the structural parameters.