Concentration and medium micellar kinetic effects caused by morphological transitions

The reaction methyl naphthalene-2-sulfonate + Br(-) was investigated in several alkanediyl-α-ω-bis(dodecyldimethylammonium) bromide, 12-s-12,2Br(-) (with s = 2, 3, 4, 5, 6, 8, 10, 12), micellar solutions in the absence and in the presence of various additives. The additives were 1,2-propylene glycol, which remains in the bulk phase, N-decyl N-methylglucamide, MEGA10, which forms mixed micelles with the dimeric surfactants, and 1-butanol, which distributes between the aqueous and micellar phases. Information about the micellar reaction media was obtained by using conductivity and fluorescence measurements. In all cases, with the exception of water-1,2-prop 12-5-12,2Br(-) micellar solutions, with 30% weight percentage of the organic solvent, a sphere-to-rod transition takes place upon increasing surfactant concentration. In order to quantitatively explain the experimental data within the whole surfactant concentration range, a kinetic equation based on the pseudophase kinetic model was considered, together with the decrease in the micellar ionization degree accompanying micellar growth. However, theoretical predictions did not agree with the experimental kinetic data for surfactant concentrations above the morphological transition. An empirical kinetic equation was proposed in order to explain the data. It contains a parameter b which is assumed to account for the medium micellar kinetic effects caused by the morphological transition. The use of this empirical equation permits the quantitative rationalization of the kinetic micellar effects in the whole surfactant concentration range.     

The phenoxy/phenol/copper cation: a minimalistic model of bonding relations in active centers of mononuclear copper enzymes

The "bare" complex [Cu(PhOH)(PhO)](+) with a phenol (PhOH) and a phenoxy (PhO) ligand bound to copper is studied both experimentally and computationally. The binding energies and structure of this complex are probed by mass spectrometry, infrared multi-photon dissociation, and DFT calculations. Further, the monoligated complexes [Cu(PhO)](+) and [Cu(PhOH)](+) are investigated for comparison. DFT calculations on the [Cu(PhOH)(PhO)](+) complex predict that a phenolate anion interacts with copper(II) preferentially through the oxygen atom, and the bonding is associated with electron transfer to the metal center resulting in location of the unpaired electron at the aromatic moiety. Neutral phenol, on the other hand, interacts with copper preferentially through the aromatic ring. The same arrangements are also found in the monoligated complexes [Cu(PhO)](+) and [Cu(PhOH)](+). The calculations further indicate that the bond strength between the copper atom and the oxygen atom of the phenoxy radical is weakened by the presence of neutral phenol from 2.6 eV in bare [Cu(PhO)](+) to 2.1 eV in [Cu(PhOH)(PhO)](+).     

SERS-activating effect of chlorides on borate-stabilized silver nanoparticles: formation of new reduced adsorption sites and induced nanoparticle fusion

Changes in morphology, surface reactivity and surface-enhancement of Raman scattering induced by modification of borate-stabilized Ag nanoparticles by adsorbed chlorides have been explored using TEM, EDX analysis and SERS spectra of probing adsorbate 2,2'-bipyridine (bpy) excited at 514.5 nm and evaluated by factor analysis. At fractional coverages of the parent Ag nanoparticles by adsorbed chlorides <0.6, the Ag colloid/Cl(-)/bpy systems were found to be constituted by fractal aggregates of Ag nanoparticles fairly uniform in size (10 +/- 2 nm) and SERS spectra of Ag(+)-bpy surface species were detected. The latter result was interpreted in terms of the presence of oxidized Ag(+) and/or Ag(n)(+) adsorption sites, which have been encountered also in systems with the chemically untreated Ag nanoparticles. At chloride coverages >0.6, a fusion of fractal aggregates into the compact aggregates of touching and/or interpenetrating Ag nanoparticles has been observed and found to be accompanied by the formation of another surface species, Ag-bpy, as well as by the increase of the overall SERS enhancement of bpy by factor of 40. The same Ag-bpy surface species has been detected under the strongly reducing conditions of reduction of silver nitrate by sodium borohydride in the presence of bpy. The formation of Ag-bpy is thus interpreted in terms of the stabilization of reduced Ag(0) adsorption sites by adsorbed bpy. The formation of reduced adsorption sites on Ag nanoparticle surfaces at chloride coverages >0.6 is discussed in terms of local changes in the work function of Ag. Finally, the SERS spectral detection of Ag-bpy species is proposed as a tool for probing the presence of reduced Ag(0) adsorption sites in systems with chemically modified Ag nanoparticles.     

Gas chromatography/mass spectrometry of oils and oil binders in paintings

A GC/MS procedure has been developed, optimized, and applied to characterization of oil binders in paintings. The procedure involves hydrolysis of lipids to fatty acids (FAs) and derivatization of FAs to fatty acid methyl esters (FAMEs) by a solution of sodium methanolate in methanol at an elevated temperature. FAMEs are analyzed by temperature-programed GC followed by full-scan MS. Old and dried samples are subjected to extraction of nonpolymerized FAMEs into dichloromethane prior to hydrolysis. The method provides a good repeatability of results and has been applied to the characterization of common plant oils used in paintings, to commercial oil and tempera paints, to model painting samples, and to samples taken from real paintings. The fresh oils and binders can readily be identified and characterized. The ratio of the methyl esters of palmitic and stearic acids can be used to characterize oil binders in old works of art.     

一种高双折射大模场面积的光子晶体光纤

为了解决光纤在大的模场面积、高的双折射、低的弯曲损耗以及单模传输方面的均衡问题,设计了一种具有高双折射的大模场面积光子晶体光纤.该光纤包层由四圈三角晶格圆形空气孔组成,纤芯由矩形晶格椭圆空气孔组成,研究了结构参数对光纤的有效模面积、双折射、泄露损耗、弯曲损耗以及单模传输等特性的影响.数值分析证明,在1.55 μm波长处,通过对光纤参数的调整,可实现4.47×10^-4的双折射,377 μm²的有效模面积,0.08 dB·km^-1的泄露损耗以及0.156 m的可容许弯曲半径.与此同时,通过对参数的进一步设计,可得到1.3~1.68 μm波长范围内的低泄露损耗单模单偏振光子晶体光纤,有效克服了光纤在偏振串扰、偏振模色散以及偏振相关损耗等方面的问题.     

Z0 boson associated b-jet production in high-energy nuclear collisions

The production of vector boson tagged heavy quark jets potentially provides new tools to probe the jet quenching effect. In this paper, we present the first theoretical study on the angular correlations (\begin{document}$ \Delta\phi_{bZ} $\end{document}), transverse momentum imbalance (\begin{document}$ x_{bZ} $\end{document}), and nuclear modification factor (\begin{document}$ I_{AA} $\end{document}) of \begin{document}$ Z^0 $\end{document} boson tagged b-jets in heavy-ion collisions, which was performed using a Monte Carlo transport model. We find that the medium modification of the \begin{document}$ \Delta\phi_{bZ} $\end{document} for \begin{document}$ Z^0$\end{document} + b-jet has a weaker dependence on \begin{document}$ \Delta\phi_{bZ} $\end{document} than that for \begin{document}$ Z^0$\end{document} + jet, and the modification patterns are sensitive to the initial jet \begin{document}$ p_T $\end{document} distribution. Additionally, with the high purity of the quark jet in \begin{document}$ Z^0$\end{document} + (b-) jet production, we calculate the momentum imbalance \begin{document}$ x_{bZ} $\end{document} and the nuclear modification factor \begin{document}$ I_{AA} $\end{document} of \begin{document}$ Z^0$\end{document} + b-jet in Pb+Pb collisions. We observe a smaller \begin{document}$ \Delta \langle x_{jZ} \rangle $\end{document} and larger \begin{document}$ I_{AA} $\end{document} of \begin{document}$ Z^0$\end{document} + b-jet in Pb+Pb collisions relative to those of \begin{document}$ Z^0$\end{document} + jet, which may be an indication of the mass effect of jet quenching and can be tested in future measurements.     

Tabu search approaches for solving the two-group classification problem

The two-group classification problem consists in constructing a classifier that can distinguish between the two groups. In this paper, we consider the two-group classification problem which consists in determining a hyperplane that minimizes the number of misclassified points. We assume that the data set is numeric and with no missing data. We develop a tabu search (TS) heuristic for solving this NP-hard problem. The TS approach is based on a more convenient equivalent formulation of the classification problem. We also propose supplementary new intensification phases based on surrogate constraints. The results of the conducted computational experiments show that our TS algorithms produce solutions very close to the optimum and require significantly lower computational effort, so it is a valuable alternative to the MIP approaches. Moreover the tabu search procedures showed in this paper can be extended in a natural way to the general classification problem, which consists of generating more than one separating hyperplanes.