Magnetic,Spectroscopic and Thermal Study of [Cu(NO3)(PyTz)2](NO3). A Copper(II) Complex Containing Thiazine Derivative Ligand

The copper(II) complex [Cu(NO₃)(PyTz)₂](NO₃) has been previously characterized means X‐ray powder diffraction and now studied by IR spectroscopy, UV‐Vis‐NIR diffuse reflectance, magnetic susceptibility measurement, electronic spin resonance (ESR) and thermal analysis. The results are correlated with a distorted square pyramidal coordination around copper(II) ion rather than the cis‐distorted octahedral stereochemistry of a CuN₄OO′ chromophore in good concordance with their structure. Likewise, in order to indicate towards what square pyramidal isomer the complex is distorted, the method proposed by Carugo and Bisi has been applied to the structural data of [Cu(NO₃)(PyTz)₂](NO₃). It is deduced that there is a large distortion from the trigonal bipyramid geometry, close to a square pyramid geometry, being produced almost exclusively through the B route of the Berry mechanism.     

A compilation of wavelengths and energy levels for the spectrum of neutral rubidium (Rb I)

We are presenting a complete list of wavelengths for all classified lines of Rb I. The data are based mainly on the observations and analysis of this spectrum by many authors. The tabulated data include 615 observed lines in the spectral range 103-, classified as transitions among 22 even-parity and 414 odd-parity levels. Vacuum wavelengths are given for all the lines, and wavelengths in air are also included for the region above . We also present the results of the doppler-free two-photon absorption spectrum for the transition n2S←52S and n2D←52S of atomic rubidium.     

Investigation of a Pt–Fe/C catalyst for oxygen reduction reaction in direct ethanol fuel cells

Three cathode catalysts (60% Pt/C, 30% Pt/C and 60% Pt–Fe/C), with a particle size of about 2–3 nm, were prepared to investigate the effect of ethanol cross-over on cathode surfaces. All samples were studied in terms of structure and morphology by using X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses. Their electrocatalytic behavior in terms of oxygen reduction reaction (ORR) was investigated and compared using a rotating disk electrode (RDE). The tolerance of cathode catalysts in the presence of ethanol was evaluated. The Pt–Fe/C catalyst showed both higher ORR activity and tolerance to ethanol cross-over than Pt/C catalysts. Moreover, the more promising catalysts were tested in 5 cm² DEFC single cells at 60 and 80 °C. An improvement in single cell performance was observed in the presence of the Pt–Fe catalyst, due to an enhancement in the oxygen reduction kinetics. The maximum power density was 53 mW cm⁻² at 2 bar rel. cathode pressure and 80 °C.     

Determination of arsenic in diesel, gasoline and naphtha by graphite furnace atomic absorption spectrometry using microemulsion medium for sample stabilization

A procedure for the determination of As in diesel, gasoline and naphtha at μg L⁻¹ levels by GFAAS is proposed. Sample stabilization was achieved by the formation of three component solutions prepared by mixing appropriate volumes of the samples propan-1-ol and nitric acid aqueous solution. This mixture resulted in a one-phase medium, which was indefinitely stable. No changes in the analyte signals were observed over several days in spiked samples, proving long-term stabilization ability. The use of conventional (Pd) and permanent (Ir) modification was investigated and the former was preferred. Central composite design multivariate optimization defined the optimum microemulsion composition as well as the temperature program. In this way, calibration using aqueous analytical solutions was possible, since the same sensitivity was observed in the investigated microemulsion media and in 0.2% v/v HNO₃. Coefficients of correlation larger than 0.999 and an As characteristic mass of 22 pg were observed. Recoveries (n=4) obtained from spiked samples were 98±4, 99±3 and 103±5%, and the limits of detection in the original samples were 1.8, 1.2 and 1.5 μg L⁻¹ for diesel, gasoline and naphtha, respectively. Validation was performed by the analysis of a set of commercial samples by independent comparative procedures. No significant difference (Student’s t-test, p<0.05) was observed between comparative and proposed procedure results. The total determination cycle lasted 4 min for diesel and 3 min for gasoline and naphtha, equivalent to a sample throughput of 7 h⁻¹ for diesel and 10 h⁻¹ for gasoline and naphtha.     

Acousto-optical spectrum analysis of ultra-high-frequency radio-wave analogue signals with an improved resolution exploiting the collinear acoustic wave heterodyning

This article is devoted to the problem of improving the frequency resolution inherent in a parallel acousto-optical spectrum analysis via involving an additional nonlinear phenomenon into the data processing. In so doing, we examine possible application of the wave heterodyning to the real-time scale acousto-optical analysis of the frequency spectrum belonging to ultra-high-frequency radio-wave signals peculiar, for example, for radio-astronomy. The nonlinear process of wave heterodyning is realized through providing a co-directional collinear interaction of the longitudinal acoustic waves of finite amplitudes. This process, which is beforehand studied theoretically and investigated experimentally via the acousto-optical technique as well, allows us either to improve the frequency resolution of spectrum analysis at a given frequency range or to increase by a few times the current frequencies of radio-wave signals under processing. The first step along this way is connected with the experimental modeling of the acoustic wave heterodyning in solids via exploitation of the specific acousto-optical cell based on a liquid, which allows the simplest realization of a cell with the needed properties. Then, these theoretical and practical findings are used in our experimental studies aimed at creating a new type of acousto-optical cells, which are able to improve the resolution inherent in acousto-optical spectrum analyzer operating over ultra-high-frequency radio-wave signals. In particular, the possibility of upgrading the frequency resolution through the acoustic wave heterodyning is experimentally demonstrated using the cell made of lead molybdate crystal. The obtained results demonstrate practical efficiency of the novel approach presented.     

Integer programming models and linearizations for the traveling car renter problem

The traveling car renter problem (CaRS) is an extension of the classical traveling salesman problem (TSP) where different cars are available for use during the salesman’s tour. In this study we present three integer programming formulations for CaRS, of which two have quadratic objective functions and the other has quadratic constraints. The first model with a quadratic objective function is grounded on the TSP interpreted as a special case of the quadratic assignment problem in which the assignment variables refer to visitation orders. The second model with a quadratic objective function is based on the Gavish and Grave’s formulation for the TSP. The model with quadratic constraints is based on the Dantzig–Fulkerson–Johnson’s formulation for the TSP. The formulations are linearized and implemented in two solvers. An experiment with 50 instances is reported.     

Simulation of RAFT Dispersion Polymerization in Supercritical Carbon Dioxide

The RAFT radical polymerization of vinyl monomers in supercritical carbon dioxide was modeled using the Predici® simulation package. The sensitivity of polymerization responses on formulation and process variables was analyzed. The simulations were carried out using kinetic and physical parameters corresponding to the polymerization of methyl methacrylate in supercritical carbon dioxide, using AIBN as initiator, at 65 °C and 200 bar, and using values of the addition and fragmentation kinetic rate constants of a “typical” RAFT agent, as reference conditions. This is the first report in the literature addressing the modeling or simulation of RAFT polymerization in supercritical carbon dioxide.

     

Plasma surface modification of chitosan membranes: characterization and preliminary cell response studies

Surface modification of biomaterials is a way to tailor cell responses whilst retaining the bulk properties. In this work, chitosan membranes were prepared by solvent casting and treated with nitrogen or argon plasma at 20 W for 10-40 min. AFM indicated an increase in the surface roughness as a result of the ongoing etching process. XPS and contact angle measurements showed different surface elemental compositions and higher surface free energy. The MTS test and direct contact assays with an L929 fibroblast cell line indicated that the plasma treatment improved the cell adhesion and proliferation. Overall, the results demonstrated that such plasma treatments could significantly improve the biocompatibility of chitosan membranes and thus improve their potential in wound dressings and tissue engineering applications.     

A Comparison of Modeling Approaches for Dispersion Homopolymerization of MMA and Styrene in Supercritical CO2

A comparison of kinetic models for dispersion polymerization of MMA and styrene in supercritical CO₂ is presented. The limiting case of solution polymerization, as a simplified case, was also addressed. Calculation of the partition of components between the continuous and dispersed phases was emphasized. Experimental data for the solution and dispersion polymerizations of styrene and MMA, using different types of stabilizers, were used to guide the study. Although all the models analyzed can be considered as “adequate” in representing the behavior of the system, some of their strengths and drawbacks have been highlighted.

     

Stereoselective NaN3-catalyzed halonitroaldol-type reaction of azetidine-2,3-diones in aqueous media

Azetidine-2,3-diones (alpha-oxo-beta-lactams) and bromonitromethane undergo coupling in aqueous media in the presence of catalytic amounts of sodium azide. The stereoselectivity of the process was generally good, proceeding with reasonable anti : syn ratios under substrate control. On this basis, a simple and fast protocol for the synthesis of the potentially bioactive 3-substituted 3-hydroxy-beta-lactam moiety has been developed. Besides, 2-azetidinone-tethered 1-halo-1-nitroalkan-2-ols are quite useful building blocks; for example, reactions of the above nitrobromohydrins provided spiranic and fused bicyclic-beta-lactams.