Synthesis and Stereochemistry of New Bis(1,3-Oxathian-2-yl) Derivatives: Epimerisation and Chair–Twist Equilibria

The synthesis and stereochemistry of some new bis(1,3-oxathian-2-yl) derivatives are reported. The conformational behavior of these compounds and the orientation of their substituents are deduced from the NMR spectra, from the X-ray crystal structures of two compounds and from the ab-initio level calculations. The epimerization of diastereoisomers and the chair ⇌ 22,5-twist equilibria were studied by variable temperature NMR.     

Femtosecond study of Cu(H(2)O) dynamics

The short-time nuclear dynamics of Cu(H(2)O) is investigated using femtosecond photodetachment-photoionization spectroscopy and time-dependent quantum wave packet calculations. The Cu(H(2)O) dynamics is initiated in the electronic ground state of the complex by electron photodetachment from the Cu(-)(H(2)O) complex, where hydrogen atoms are oriented toward Cu. Several time-resolved resonant multiphoton ionization schemes are used to probe the ensuing reorientation and dissociation. Immediately following photodetachment, the neutral complex is far from its minimum energy geometry and possesses an internal energy comparable to the Cu-H(2)O dissociation energy and undergoes both large-amplitude H(2)O motion and dissociation. Dissociation is observed to occur on three distinct time scales: 0.6, 8, and 100 ps. These results are compared to the results of time-dependent J=0 wave packet calculations, propagating the initial anion vibrational wave functions on the ground-state potential of the neutral complex. An excellent agreement is obtained between the experimental results and the ionization signals derived from the calculated probability amplitudes. Related experiments and calculations are carried out on the Cu(D(2)O) complex, with results very similar to those of Cu(H(2)O).     

Adsorption of Ni(II) from model solutions using co-precipitated inorganic oxides

The aim of this work was to obtain an inorganic oxide system containing silica and magnesium oxide, and characterized by specific physicochemical properties, in particular well-defined adsorption parameters. The preparation process was carried out according to a co-precipitation method using solutions of sodium silicate and selected inorganic magnesium salt. The oxide system obtained (MgO·SiO₂) was used as a support (adsorbent) of nickel(II) ions, whose precursors were model solutions of nitrates. The effectiveness of the adsorption process was evaluated using many different analytical techniques, including atomic absorption spectroscopy, energy dispersive X-ray spectroscopy and equivalent point titration. Moreover the stability of adsorbent/adsorbate bonding was estimated. The oxide systems—adsorbents—used in the process were also analyzed according to their physicochemical properties, especially changes in adsorption parameters. The last part of the study involved evaluation of the kinetics of the adsorption process depending on time and the pH of the reaction system.     

Simultaneous Carbohydrate Chromatography and Unsuppressed Ion Chromatography in Detecting Fruit Juices Adulteration

This paper is the first one investigating the simultaneous use of carbohydrate chromatography and ion chromatography to obtain in one run conclusive data on juice’s authenticity. A hybrid liquid chromatographic system with conductivity and differential refractive index detection, equipped with an Universal Cation 7u column for cation analysis and with a EC 250/4 Nucleodur 100-5 NH₂ RP column for carbohydrate analysis, was designed for this study. In less than 18 min, this configuration can separate simultaneously six cations (lithium, sodium, ammonium, potassium, magnesium and calcium) and four carbohydrates (fructose, glucose, saccharose and maltose). Commercial orange and apple juices obtained from the Romanian market were analyzed during this research.     

Reputation-based network selection mechanism using game theory

Current and future wireless environments are based on the coexistence of multiple networks supported by various access technologies deployed by different operators. As wireless network deployments increase, their usage is also experiencing a significant growth. In this heterogeneous multi-technology multi-application multi-terminal multi-user environment users will be able to freely connect to any of the available access technologies. Network selection mechanisms will be required in order to keep mobile users “always best connected” anywhere and anytime. In such a heterogeneous environment, game theory techniques can be adopted in order to understand and model competitive or cooperative scenarios between rational decision makers. In this work we propose a theoretical framework for combining reputation-based systems, game theory and network selection mechanism. We define a network reputation factor which reflects the network’s previous behaviour in assuring service guarantees to the user. Using the repeated Prisoner’s Dilemma game, we model the user–network interaction as a cooperative game and we show that by defining incentives for cooperation and disincentives against defecting on service guarantees, repeated interaction sustains cooperation.     

Comparison of silica gel modified with three different functional groups with C-18 and styrene-divinylbenzene adsorbents for the analysis of selected volatile flavor compounds

A comparison of SPE cartridges produced in authors laboratory containing silica modified by addition of three functional moieties with standard C-18 and SDVB cartridges was made in terms of their applicability for the isolation of flavor compounds. Compounds found in wine and grapes were used for model mixture, which was spiked into a grape juice. Functionalized phases for SPE were prepared modifying silica gel with alkoxysilanes with different functional groups: (3-(phenylamino)-propyltrimethoxysilane, octyltriethoxysilane and octadecyl-silane. The functionalization was carried out by the dry method, which resulted 5, 10 and 20 weight parts of initial support. Functionalized phases were characterized using FT-IR, elemental analysis and NMR.Performance for new phases compared to “standard” ones (C-18 and SDVB (styrene–divinylbenzene) varied, depending on the group or type of analyzed compound. They were more efficient in extraction of methyl anthranilate and vanilins. For extraction of terpenes, C-6 alcohols, isoprenoids, benzene derivatives and phenols their efficiency was comparable to that of C-18.Functionalized laboratory-made mixed phases are suitable for extraction of flavor compounds from grape juice. They are suitable for extraction of compounds belonging to different chemical classes with the efficiency comparable to C-18 and SDVB phases. The production of such functionalized phases can be easily performed in the laboratory, at a very low cost, comparing to C-18 or SDVB cartridges. This makes the proposed functionalized phases an interesting alternative, in sample preparation for analysis and particularly in preparative/flash chromatography.     

A pulse sequence for averaging the strong homonuclear scalar coupling in AB spin systems

A pulse sequence is proposed for the suppression of the strong homonuclear scalar coupling in the case of AB spin systems. The theoretical treatment is presented in terms of the average Hamiltonian theory in the case of aperiodic perturbations. The zero-order and the first-order correction terms in the full average Hamiltonian are calculated. It is shown that the chemical shift interaction for one of the spins is completely refocused and the conditions in which the interactions bilinear in spin operators are efficiently suppressed are analyzed.     

Unbounded divergence of simple quadrature formulas

Given a sequence of real or complex coefficients c_i and a sequence of distinct nodes t_i in a compact interval T, we prove the divergence and the unbounded divergence on superdense sets in the space C(T) of the simple quadrature formulas ∝_Tx(t)du(t) = Q_n(x) + R_n(x) and ∝_Tw(t)x(t)dt = Q_n(x) + R_n(x), where Q_n(x)=∑_i=1^m_n c_ix(t_i), ε C(T).The divergence (not certainly unbounded) for at most one continuous function of the first simple quadrature formula, with m_n = n and u(t) = t, was established by P. J. Davis in 1953.