Normal Projections in Krein Spaces

Given a complex Krein space ${\mathcal{H}}$ with fundamental symmetry J, the aim of this note is to characterize the set of J-normal projections $$\mathcal{Q}=\{Q \in L(\mathcal{H}) : Q^2=Q \,{\rm and}\, Q^{\#}Q=QQ^{\#}\}.$$ The ranges of the projections in ${\mathcal{Q}}$ are exactly those subspaces of ${\mathcal{H}}$ which are pseudo-regular. For a fixed pseudo-regular subspace ${\mathcal{S}}$ , there are infinitely many J-normal projections onto it, unless ${\mathcal{S}}$ is regular. Therefore, most of the material herein is devoted to parametrizing the set of J-normal projections onto a fixed pseudo-regular subspace ${\mathcal{S}}$ .     

Electroactive copper(II) bimetallic self-assembled multilayers on Si(100)

Silicon (100) surfaces were modified by reacting 4-aminopyridine and Si–Cl bond. These surfaces were further used for tethering copper bimetallic complexes and growing monolayers and multilayers by changing the axial position via Lewis acid–base reactions. In this way, coordination chemistry approach can be used as building blocks for controlling the design of functional surfaces. Furthermore, the outcomes of the several characterization techniques indicate that the complex is spatially oriented suggesting that this simple strategy allows the preparation of three dimensional molecular structures exhibiting spatial order. The structures on surface show interesting electroactive behaviors leading two cathodic signals, that can be related to Cu(II)/Cu(I) and Cu(I)/Cu(0) electro-reduction species (signals at ? 0.15 V and ? 0.50 V) and one peak in the anodic region (? 0.15 V) ascribed to the Cu(0)/Cu(II) electro-oxidation reaction, using an Ag/AgCl saturated electrode and platinum wire as reference and counter electrodes, respectively.     

Sol MWD During Styrene,Vinyl Acetate,Methyl Methacrylate,and Butyl Acrylate Homopolymerization: A Numerical Study Using the NFT Approach

Complete parameter sensitivity analyses using the numerical fractionation technique are presented for the cases of homopolymerization with chain transfer to polymer and termination by combination. Also, using reported values for the kinetic rate constants associated with the linear and non‐linear homopolymerizations of styrene, vinyl acetate, methyl methacrylate and butyl acrylate, overall molecular weight distributions and averages of the MWD were calculated using the NFT. Good agreement with the expected behavior, with MMA and STY not gelling while BA and VAc do, was obtained. It is concluded that the NFT produces coherent and reliable performance for known polymerization systems, whether linear or non‐linear.

     

Multifractal structure in Latin-American market indices

We study the multifractal nature of daily price and volatility returns of Latin-American stock markets employing the multifractal detrended fluctuation analysis. Comparing with the results obtained for a developed country (US) we conclude that the multifractality degree is higher for emerging markets. Moreover, we propose a stock market inefficiency ranking by considering the multifractality degree as a measure of inefficiency. Finally, we analyze the sources of multifractality quantifying the contributions of two factors, the long-range correlations of the time series and the broad fat-tail distributions. We find that the multifractal structure of Latin-American market indices can be mainly attributed to the latter.     

Effects of Pt content on the crystallinity and optical properties of Ag/Pt nanoboxes: from solid to single and polycrystalline mesoporous nanostructures

Synthetic methods to obtain hollow-like systems based on galvanic reaction are of wide importance due to the simplicity and efficiency of the method, yet due to fast and spontaneous reduction, the reaction for platinum-based structures is usually not well controlled. Systematic studies over the evolution of the galvanization process are still important in order to determine key feature on the structural transformation. On this paper, electron microscopy techniques were used to correlate the crystallinity of Ag/Pt nanoboxes of 78 nm in size with low and high-index facets surfaces from Ag nanocubes template. It was observed that 1.6 μmol addition of platinum precursor is enough to produce Ag/Pt nanoboxes. However, the crystallinity of the walls was tune from single crystal to polycrystalline by increasing the amount of platinum. More importantly, electron tomography reconstructions allow us to identify the concavities sides on the polycrystalline double-layer porous sample. Platinum content and nanostructure has been also associated to the optical properties were an extinction of the absorption band is observed after the solid template has been fully transformed to a nanobox. The final Ag/Pt porous/hollow nanoboxes with concave sides were tested on a model reaction for the reduction of 4-ntp to 4-amp.     

On-line coupling of physiologically relevant bioaccessibility testing to inductively coupled plasma spectrometry: Proof of concept for fast assessment of gastrointestinal bioaccessibility of micronutrients from soybeans

In-vitro physiologically relevant gastrointestinal extraction based on the validated Unified BARGE Method (UBM) is in this work hyphenated to inductively coupled plasma optical emission spectrometry in a batch-flow configuration for real-time monitoring of oral bioaccessibility assays with high temporal resolution. A fully automated flow analyzer is designed to foster in-line filtration of gastrointestinal extracts at predefined times (≤15 min) followed by on-line multi-elemental analysis of bioaccessible micro-nutrients, viz., Cu, Fe and Mn, in well-defined volumes of extracts (300 μL) of transgenic and non-transgenic soybean seeds taken as model samples.     

Kinetics and mechanism of the aminolysis of 4-methylphenyl and 4-chlorophenyl 4-nitrophenyl carbonates in aqueous ethanol

Reactions of 4-methylphenyl 4-nitrophenyl carbonate (MPNPC) and 4-chlorophenyl 4-nitrophenyl carbonate (ClPNPC) with a series of quinuclidines (QUIN) and the latter carbonate with a series of secondary alicyclic amines (SAA) are subjected to a kinetic investigation in 44 wt % ethanol-water, at 25.0 degrees C and an ionic strength of 0.2 M. The reactions were followed spectrophotometrically at 330 or 400 nm (4-nitrophenol or 4-nitrophenoxide anion appearance, respectively). Under excess amine, pseudo-first-order rate coefficients (k(obsd)) are found. For all these reactions, plots of k(obsd) vs free amine concentration at constant pH are linear, the slope (k(N)) being independent of pH. The Br?nsted-type plots (log k(N) vs pK(a) of the conjugate acids of the amines) for the reactions of the series of QUIN with MPNPC and ClPNPC are linear with slopes (beta(N)) 0.88 and 0.87, respectively, which are explained by a stepwise process where breakdown of a zwitterionic tetrahedral intermediate (T(+/-)) to products is rate limiting. The Br?nsted-type plot for the reactions of the series of SAA with ClPNPC is biphasic with slopes beta(1) = 0.2 (high pK(a) region) and beta(2) = 0.9 (low pK(a) region) and a curvature center at pK(a)(0) = 10.6. This plot is in accordance with a stepwise mechanism through T(+/-) and a change in the rate-determining step, from T(+/-) breakdown to T(+/-) formation as the basicity of the SAA increases. Two conclusions arise from these results: (i) QUIN are better leaving groups from T(+/-) than isobasic SAA, and (ii) the non-leaving group effect on k(N) for these reactions is small, since beta(nlg) ranges from -0.2 to - 0.3. From these values, it is deduced that ClPNPC is ca. 70% more reactive than MPNPC toward SAA and QUIN, when expulsion of the leaving group from T(+/-) is the rate determining step.     

The interaction parameter of crosslinked networks and star polymers

Recent results on blends containing star polymers have revived the interest on the interaction parameters of structures that contain junctions between chains, a matter which can be connected with the earlier studies on the influence of crosslinks on the interaction parameters of polymer networks and gels. Here, we review results on crosslinked networks and star polymer solutions together with the more recent work on star polymer blends. The review covers swelling and elastic deformation of gels, differential vapour sorption between crosslinked and uncrosslinked polymers, osmotic equilibrium of gels and of star polymer solutions, and neutron scattering of polymer blends containing star polymers. In the systems reviewed, the interaction parameters of stars and networks differ from those of linear chains, and the difference is attributed mainly to entropic effects.     

Stable Luminescent [Cu(NN)(PP)]+ Complexes Incorporating a β-Cyclodextrin-Based Diphosphane Ligand with Metal-Confining Properties

A β-cyclodextrin-based diphosphane with metal-confining properties was efficiently synthesized thanks to an unprecedented Smiles-like rearrangement of diphenyl-(2-phosphanylphenyl)phosphane in the presence of excess n-BuLi. The cis-chelating bidentate ligand is capable of forming very stable heteroleptic [Cu(NN)(PP)]⁺ complexes in which a metal-bound diimine ligand (bpy, phen, or mmp) is located within the cyclodextrin cavity. As a result of ligand encapsulation, flattening of the metal tetrahedral geometry in the excited state is disfavored, thereby resulting in enhanced luminescent properties.