Vibrational modes and structure of (AgI)x (GeS1.5)100−x chalcohalide glasses

We report a structural investigation of bulk Ge-rich Ge–S–AgI chalcohalide glasses. A vibrational spectroscopic study of the quaternary system (AgI)_x (GeS_1.5)_100−x (0  x_AgI  20) has been undertaken using infrared spectroscopy and Fourier transform Raman scattering. It was found that the GeS_1.5 Raman spectrum is compatible with a glass structure composed of corner- and edge-sharing mixed GeS_nGe_4−n (n = 0–4) tetrahedra where units with n = 2–4 dominate, whilst the fraction of corner-sharing units are significantly lower than the corresponding fraction in the stoichiometric GeS₂ glass. The addition of AgI has revealed a subtle but systematic effect in the structure of the Ge-rich glass matrix, manifested by mild decrease of the ES units and the concomitant increase of complex GeS_nI_4−n or GeS_nGe_mI_4-n−m tetrahedra whose vibrational modes form a continuum at low frequencies. Although, AgI seems to cause subtle structural changes due to the formation of Ge–I bonds, it is also evident that AgI does not act as a real modifier that would depolymerize appreciably the Ge–S network structure.     

Characterization of the light scattering by ensembles of randomly distributed soot aggregates

Soot particles formed in combustion processes commonly exist in the form of ensembles of randomly distributed aggregates of small, nearly spherical monomers. In this paper, these randomly distributed aggregates are numerically generated using a combination of the cluster–cluster aggregation algorithm with the Monte Carlo method. Moreover, an efficient and accurate numerical method is presented for characterizing the light scattering by these complex soot particles illuminated by plane wave and Gaussian beam. This method exploits the unique features of the hybrid finite element-boundary integral method and, more importantly, the unique features of soot aggregates. It is designed in such a manner that it first decomposes the original problem into many sub-regions, where each primary particle is regarded as a sub-region, and then it employs the edge-based finite element method to deal with each sub-region. The sub-regions communicate through the near-field Green’s function. To reduce computational burdens, an iterative domain decomposition method in combination with parallel conjugate gradient method is adopted to solve the coupling system of equations. As an illustration, we present some of our preliminary numerical results. The results are expected to provide useful insights into the optical properties of soot particles formed in combustion processes.     

Resonance light scattering technique used for biochemical and pharmaceutical analysis

By coupling and scanning simultaneously excitation and the emission monochromators of a common spectrofluorometer, enhanced resonance light scattering (RLS) signals could be obtained. The enhanced RLS signals could be used for designating bio-assemblies, aggregation species, and analytical purposes. Herein, we review the reports since the year of 2000 concerning the biochemical and pharmaceutical analysis with the RLS measurements, and discuss the possible developments of this technique.     

Correlation of counterions with rodlike macroions as assessed by anomalous small-angle X-ray scattering

We consider the analysis of a rodlike synthetic polyelectrolyte in solution by anomalous small-angle X-ray scattering (ASAXS) in order to elucidate the correlation of the counterions with the highly charged macroion. ASAXS can be applied to these systems because the absorption edge of typical counterions, for example, bromine or iodine ions can be attained by synchrotron radiation. Model calculations using the Poisson–Boltzmann cell model show that ASAXS furnishes two terms caused by the anomalous dispersion of the counterions. The leading terms is a cross-term between the ordinary scattering amplitude of the polyelectrolyte and the real part of the scattering length f ′ of the counterions. A second term refers solely to the anomalous contribution of the counterions, i.e., to f ′ and f ′′ ( f ′′: imaginary part of scattering length). Preliminary data obtained from rodlike synthetic macroions having iodine counterions corroborate the theoretical deductions. They demonstrate that ASAXS is capable of furnishing information that is not available by the ordinary SAXS experiment. Received: 11 December 2000/Accepted: 22 February 2001     

Effect of silver doping on the structure and phase separation of sulfur-rich As–S glasses: Raman and SEM studies

We report on the structural details and microphase separation of the bulk glasses Ag_x·(As₃₃S₆₇)_100-x for 0x25. Glass–glass phase separation occurs over a wide range of Ag content, i.e. 4x20. An off-resonant polarized Raman spectroscopic study has been carried out to elucidate structural aspects at the short- and medium-range structural order of the glasses. Analysis of Raman spectra revealed quantitative changes of the sulfur-rich microenvironments that reduce upon adding Ag. Scanning electron microscopy combined with X-rays microanalysis have been utilized to examine the type and extent of phase separation, and to provide quantitative details on the atomic concentrations in the Ag-poor and Ag-rich phases. It has been shown that at 7 at.% Ag the Ag-rich phase percolates through the structure; this effect can be associated with an ionic-to-superionic behavior of these glasses in accordance with similar studies on the stoichiometric arsenic sulfide glass; although the phase separation observed in the present glasses is qualitatively different.     

X-ray diffraction measurements on PE 2000 between 10 K and 300

Summary It was possible to obtain film exposures of the WAXS-diagram (2 50°) of a PE-fraction in the temperature range from 10 K to 300 K by using a special low temperature Guinier-chamber. The crystallographica-,b-andc-axis has been calculated from the positions of all reflexions. The different behaviour of their expansion coefficients can be explained by activation of rotational- and torsional-vibrations. If we take the number of net planes as constant and consider a temperature-independent part resulting from paracrystalline disorder (built up during crystallization), we can describe the linear increasing of the integral widths of the reflexions with decreasing temperature (10 ... 100%) with building up of inherent stresses inside the crystals.

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Zusammenfassung Eine spezielle Tieftemperatur-Guinier-Kammer ermöglichte es, Filmaufnahmen der Röntgenweitwinkelstreukurve (2 50°) einer hochkristallinen Polyäthylen-Fraktion im Bereich von ca. 10 K bis 300 K zu erhalten. Das unterschiedliche Temperaturverhalten der Ausdehnungskoeffizienten der kristallographischena-,b- undc-Achse, berechnet aus der Lage aller auswertbaren Reflexe, kann durch Anregung von Torsions- und Rotationsschwingungen erklärt werden. Unter der Annahme konstanter Kristallitgrößen sowie eines temperaturunabhängigen parakristallinen Gitterstörungsanteils (hervorgerufen durch Defekteinbau bei der Kristallisation), kann die starke Zunahme der integralen Breiten der Reflexe (bis ca. 100%) zu tiefen Temperaturen auf Eigenspannungen in den Kristalliten zurückgeführt werden.

     

Small-angle neutron-scattering study of concentrated nonionic-amphiphile solutions

The structure of aqueous solutions of two polyoxyethylene non-ionic amphiphiles, C₁₀E₅ and C₈E₄, is studied by small-angle neutron-scattering along isothermal paths crossing the isotropic single-phase region from 0% to 100% amphiphile volume fractions. The scattered intensityI(k) shows a peak at a valuek _m , which grows monotonically as the amphiphile volume fraction increases. The interpretation of the scattering data lead to the following conclusion: as increases the micellar structure becomes less and less sharp, but some orientational correlations between neighboring amphiphile molecules are preserved even in the pure amphiphile phase.     

Characterization of proteins separated by displacement chromatography using low angle laser light scattering photometry

Summary -Lactoglobulin A and B (-LACT) were separated by displacement chromatography (DSC) on an ionexchange column using dextran sulfate as the displacer. A LALLS photometer and a UV detector, in series, were used to determine the molecular weight (MW) of the proteins, on-line. The results indicate that both, -LACT A and B, were present as dimers in the buffer used for the mobile phase. The MWs of the proteins were about 6–8% higher than the theoretical MW of a dimer (37,000). Additional control studies have shown the presence of a high molecular weight species in both the proteins, which could possibly be an aggregate. This species was observed in the LALLS signal but was nearly absent in the UV signal. Our work has demonstrated the feasibility of interfacing LALLS with displacement chromatography for detecting impurities or aggregates which may be difficult to detect by conventional detectors used for chromatography.     

Direct Hydrogenation of Dinitrogen and Dioxygen via Eley–Rideal Reactions

Most Eley–Rideal abstraction reactions involve an energetic gas‐phase atom reacting directly with a surface adsorbate to form a molecular product. Molecular projectiles are generally less reactive, may dissociate upon collision with the surface, and thus more difficult to prove that they can participate intact in abstraction reactions. Here we provide experimental evidence for direct reactions occurring between molecular N₂⁺ and O₂⁺ projectiles and surface‐adsorbed D atoms in two steps: first, the two atoms of the diatomic molecule undergo consecutive collisions with a metal surface atom without bond rupture; and second, the rebounding molecule abstracts a surface D atom to form N₂D and O₂D intermediates, respectively, detected as ions. The kinematics of the collisional interaction confirms product formation by an Eley–Rideal reaction mechanism and accounts for inelastic energy losses commensurate with surface re‐ionization. Such energetic hydrogenation of dinitrogen may provide facile activation of its triple bond as a first step towards bond cleavage.     

The sphere-rod transition of micelles of dodecyldimethylammonium bromide in aqueous NaBr solutions,and the effects of counterion binding on the micelle size,shape and structure

Micelle size and shape of dodecyldimethylammonium bromide have been determined by measurement of light scattering from its aqueous NaBr solutions. In water and in the presence of NaBr up to 0.07 M, the Debye plots give straight lines with positive slopes, and spherical micelles having molecular weight less than 30 000 are formed. At higher NaBr concentrations, the Debye plots decrease with increasing micelle concentration, indicating the aggregation of the primary spherical micelles into larger secondary micelles. The molecular weight and the radius of gyration of the secondary micelles increase with increasing NaBr concentration, and the relation between molecular weight and radius of gyration suggests that they are rodlike and flexible. Linear logarithmic relations between micelle molecular weight and ionic strength hold for spherical and rodlike micelles, respectively, and the threshold concentration of NaBr for the sphere-rod transition is located at 0.07 M. The spherical micelle of dodecyldimethylammonium ions has a size more than 20 surfactant ions larger in NaBr solutions than in NaCl solutions, and their rodlike micelle has a shorter length in NaBr solutions than in NaCl solutions, when compared at an identical aggregation number, indicating 2 more surfactant ions in its cross-section.