Synthesis, molecular and electronic structure, and TDDFT and TDDFT-PCM study of the solvatochromic properties of (Me2Pipdt)Mo(CO)4 complex (Me2Pipdt = N,N'-dimethylpiperazine-2,3-dithione)

The synthesis, spectroscopic, and structural characterization of the (Me2Pipdt)Mo(CO)4 complex (Me2Pipdt = N,N'-piperazine-2,3-dithione) are presented in this paper. The title complex crystallizes in the P2(1)/n space group with a = 25.541(3) A, b = 10.3936(14) A, c = 10.9012(12) A, beta = 92.261(9) degrees , V = 2891.6(6) A(3), and Z = 8. Gas- and solution-phase structural and electronic features of (Me2Pipdt)Mo(CO)4 and Me2Pipdt have been investigated using density functional theory. The molecular structure underscores the flexibility of the NC(S)C(S)N fragment in both the free ligand and the metal complex. On the basis of structural, spectroscopic, and theoretical results, the bidentate ligand in (Me2Pipdt)Mo(CO)4 is considered to be in the dithione, not dithiolate, form. Time-dependent density functional theory has been used for the investigation of the excited states and solvatochromic properties of (Me2Pipdt)Mo(CO)4. The calculated vertical excitation energies in solution are consistent with the experimental data, showing that the metal-to-ligand charge-transfer transitions, in both the visible and UV regions, dominate over the ligand-based pi-pi transitions.     

Study of the gamma irradiation effects on the PMMA/HA and PMMA/SW

The behavior of the poly(methyl methacrylate) (PMMA) under the action of gamma radiation has been sufficiently studied. In this work, we present results from melt flow index (MFI), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and electron paramagnetic resonance (EPR) of PMMA composites with hydroxyapatite (HA) and seaweed residues (SW) irradiated with gamma rays at 1.08 kGy/h. Composites of PMMA/HA and PMMA/SW with 10%, 20% and 30% of the filler were prepared. The results show an increase in the MFI values with the integral dose of radiation, being consistent with chain-scission reactions. No EPR signal was observed in pure PMMA, while in the composites, the typical EPR signal of the PMMA radicals was observed, which increased with the amount of HA or SW. When comparing the relative intensities of the EPR signals for both types of composites, a slight increase in the concentration of free radicals generated in the sample with SW respect to that of PMMA/HA composite was obtained. A decay of the total free radical concentration was observed as time elapsed.     

An in situ Al K-edge XAS investigation of the local environment of H+- and Cu+-exchanged USY and ZSM-5 zeolites

Aluminum coordination in the framework of USY and ZSM-5 zeolites containing charge-compensating cations (NH4+, H+, or Cu+) was investigated by Al K-edge EXAFS and XANES. This work was performed using a newly developed in-situ cell designed especially for acquiring soft X-ray absorption data. Both tetrahedrally and octahedrally coordinated Al were observed for hydrated H-USY and H-ZSM-5, in good agreement with 27Al NMR analyses. Upon dehydration, water desorbed from the zeolite, and octahedrally coordinated Al was converted progressively to tetrahedrally coordinated Al. These observations confirmed the hypothesis that the interaction of water with Br?nsted acid protons can lead to octahedral coordination of Al without loss of Al from the zeolite lattice. When H+ is replaced with NH4+ or Cu+, charge compensating species that absorb less water, less octahedrally coordinated Al was observed. Analysis of Al K-edge EXAFS data indicates that the Al-O bond distance for tetrahedrally coordinated Al in dehydrated USY and ZSM-5 is 1.67 angstroms. Simulation of k3chi(k) for Cu+ exchanged ZSM-5 leads to an estimated distance between Cu+ and framework Al atoms of 2.79 angstroms.     

Resonant inelastic scattering in dilute magnetic semiconductors by soft X-ray fluorescence spectroscopy

1-x Mn_xS (where 0.05<x<1) were measured as the energy of the exciting radiation was tuned across the S and Mn-L_2,3 absorption edges of these compounds. Strong resonance peaks in Mn-L emission spectra and the systematic appearance of new spectral features in S-L emission spectra were observed. Partial substitution of Zn by a magnetic Mn ion results in strong hybridization of the Mn 3d orbitals with the sp band of the host semiconductor. A detailed study of resonant inelastic scattering in the vicinity of the S and Mn-L_2,3 absorption edges of these DMS is presented. Received: 6 March 1997     

Parallel asynchronous focal plane array processing

A new approach to focal plane processing based on silicon injection mode devices is suggested. These devices provide a natural basis for parallel asynchronous focal plane image preprocessing. The simplicity and novel properties of the devices would permit an independent analog processing channel to be dedicated to every pixel. A laminar architecture built from arrays of the devices would form a two-dimensional (2-D) array processor with a 2-D array of inputs located directly behind the focal plane detector array. A 2-D image data stream would propagate in neuronlike asynchronous pulse coded form through the laminar processor. No multiplexing, digitization or serial processing would occur in the preprocessing stage. High performance is expected because approximately linear pulse coding has already been observed for input currents ranging over six orders of magnitude down to one picoampere with noise referred to input of about 10 femtoamperes. Very low power requirements suggest utility in space and in conjunction with very large arrays. Multispectral processing is possible because of compatibility with the cryogenic environment of high performance infrared detectors.     

Near-edge X-ray absorption fine structure study of disordering in Gd2(Ti1-yZry)2O7 pyrochlores

Disorder in Gd2(Ti(1-y)Zry)2O7 pyrochlores, for y = 0.0-1.0, is investigated by Ti 2p and O 1s near-edge X-ray absorption fine structure spectroscopy. Ti(4+) ions are found to occupy octahedral sites in Gd2Ti2O7 with a tetragonal distortion induced by vacant oxygen sites. As Zr substitutes for Ti, the tetragonal distortion decreases, and Zr coordination increases from 6 to 8. The migration of oxygen ions from 48f or 8b sites to vacant 8a sites compensate for the increased Zr coordination, thereby reducing the number of vacant 8a sites, which further reduces the tetragonal distortion and introduces more disorder around Ti. This is evidence for simultaneous cation disorder with anion migration.     

Coulometric titration of some phenolic steroids with bromine based on thin-layer hydrodynamic biamperometric end-point detection

Four phenolic steroids were titrated coulometrically with bromine in a methanol—water solvent containing hydrochloric acid and sodium bromide. End-point detection was achieved with a twin electrode thin-layer cell placed in a flow loop connected to the titration vessel. Linear-segmented biamperometric titration curves were recorded. Concentrations of 17-β-estradiol were determined in the range from 442 ppb to 8.84 ppm with relative inaccuracies of -1.3% and +2.2%, respectively. Part-per-million solutions of estrone and estriol were titrated with good accuracy and precision. Somewhat poorer precision and accuracy was found for the determination of 17-α-ethynyl estradiol.     

Two concomitant polymorphs of 3,3′,4,4′-tetrakis(phenylethynyl)-1,1′-[2,2,2,-trifluoro- 1-(trifluromethyl)ethanediyl]bisbenzene

A representative compound of bis-ortho-diynyl arene (BODA), with a general formula [(m,p)R₂–Ph]₂ –X, where R: –C≡C–Ph and X: >C(CF₃)₂ has been structurally characterized. The compound is being investigated as a monomer for high-performance polyarylene networks and glassy carbon precursors. The bis(trifluoromethyl) derivative crystallizes in two concomitant polymorphic forms. The two polymorphs form a monotropic system with melting points of 436 and 463 K. The metastable form yields monoclinic crystals (P2₁/n, Z=4). a=12.677(3) ?, b=11.677(2) ?, c=24.026(5) ?, β=93.79(3)°. The thermodynamically stable form is monoclinic as well (P2₁/c, Z=8), a=10.7983(6) ?, b=30.628(2) ?, c=21.648(1) ?, β=94.737(1)° with small voids indicating less efficient packing. The two polymorphs contain different conformers of the rotationally flexible molecule.