Determining a 'safe' high-mass limit in matrix-assisted laser desorption/ionisation time-of-flight mass spectra of coal derived materials with reference to instrument noise

Three methods for determining a 'safe' estimate for high-mass limits of MALDI spectra of coal derived liquids were explored, using a sample of coal-tar pitch and its pyridine-insoluble fraction. Co-addition of increasing numbers of single-shot spectra (10, 30, 50 and 100 pulses) showed visually observable reductions in noise levels, consistent with robust and statistically meaningful signals. Three separate types of post-acquisition calculation were used to identify high-mass limits of the spectra. (i) A literature method indicated high-mass limits similar to those observed visually-as a shift from baseline at the highest masses, nearly 350 000 u for the coal tar pitch and about 390 000 u for its pyridine insoluble fraction. (ii) Comparing instrument signal with pre-selected multiples of the standard deviation, upper mass estimates of between 40-60 000 u for the coal-tar pitch and about 95 000 u for its pyridine-insoluble fraction were found. (iii) Calculation of the slope was used to identify 'lift-off' of the spectrum from baseline. The angle between the smoothed spectrum and the baseline was matched to a pre-selected value (e.g. 0.5 degrees and 1 degrees ). However, the arbitrary specification of the key parameter did not establish this last method on a firm basis. The choice of a criterion for estimating high-mass limits of MALDI spectra remains a semi-quantitative procedure; a reasonably conservative high-mass limit may be estimated by comparison of signal with five times the standard deviation. However, evaluation of size exclusion chromatograms of the present samples using polystyrene standards suggests that molecular mass distributions of pitch samples arrived at by MALDI mass spectrometry are, at least partly, determined by the limitations of available instruments. Copyright 1999 John Wiley & Sons, Ltd.     

Adsorption properties and surface chemistry of MgO

The adsorption properties of MgO, which is used as a sorbent and catalyst support, were studied using gas chromatography. The test absorbents used were n-alkanes (which show only nonspecific dispersion interactions when physisorbed on any adsorbent) and adsorbates whose molecules are capable of specific interactions with the surface reactive sites of MgO. Adsorption isotherms were measured for CHCl₃, CH₃NO₂, CH₃CN, (CH₃)₂CO, CH₃COOC₂H₅, and (C₂H₅)₂O on MgO at 50–100°C. Differential molar enthalpy changes (?ΔH), equal to molar heats of adsorption, were determined. For polar adsorbates, contributions from dispersive and specific interactions into ?ΔH were determined. The electron-acceptor and electron-donor abilities of the MgO surface were estimated.     

Octave phase matching for optical parametric amplification of single-cycle pulses in the mid-infrared range

Analysis of optical properties of mid-infrared-transparent nonlinear crystals reveals octave phase matching for a highly efficient optical parametric amplification of single-cycle electromagnetic field waveforms within the 3- to 12-μm wavelength range, recently demonstrated in experiments.     

Adsorption properties of aluminium oxide modified with palladium,gold, and cerium oxide nanoparticles

The adsorption properties of nanocomposites based on γ-Al₂O₃ modified with CeO_x, Au/CeO_x, and Pd/CeO_x nanoparticles with contents of deposited metals ranging from 0.07 to 1.71 wt % are investigated by means of dynamic sorption method. n-Alkanes (C₆–C₈), acetonitrile, diethyl ether, tetrahydrofuran, and dioxane are used as test adsorbates. Adsorption isotherms are measured, and the isosteric heats of adsorption of a number of test adsorbates are calculated. Electron-donor and electron-acceptor characteristics of the surfaces of γ-Al₂O₃-based nanocomposites are estimated. It is shown that Au(0.1%)/CeO_x(0.07%)/γ-Al₂O₃ nanocomposite, which has the lowest content of nanoparticles of the deposited metals, has the highest adsorption activity.     

Quantum-chemical study of the effect of oxygen on the formation of active sites of silver clusters during the selective adsorption of hydrocarbons

Density functional theory (PBE with a modified Dirac-Coulomb-Breit Hamiltonian) is used to simulate the adsorption of hydrocarbons (C₂H₂, C₂H₄, C₂H₆) on the surface of a sorbent containing Ag⁰, Ag^δ+, and AgO sites. The dynamics of change in the structural characteristics of Ag _n (n ≤ 10) is analyzed and the adsorption of oxygen on Ag₈ and Ag₁₀ is studied to select the adsorption site model. Studying the interaction of hydrocarbons with Ag₈, Ag₁₀, Ag ₁₀ ⁺ , Ag₁₀O, and Ag₁₀O₂ clusters reveals that the presence of oxygen leads to an increase in the activation of unsaturated hydrocarbons, and the adsorption energy of C₂H₂ increases tenfold. It is found that the role of adsorbed oxygen is not only to form adsorption sites of hydrocarbons (Ag^δ+) but also to bind C₂H₂ and C₂H₄ directly to the sorbent’s surface.     

Adsorption of chlorobenzenes on ultrafine diamond modified with palladium and nickel nanoparticles

Dynamic sorption is used to study the adsorption properties of palladium and nickel nanoparticles immobilized on a surface of ultrafine diamond (UFD). The test adsorbates are n-alkanes (C₆-C₈), benzene, chloroform, diethyl ether, chlorobenzene, and o-dichlorobenzene. For each adsorbate, the adsorption isotherms are measured, the isosteric heats of adsorption and contributions to them from the energies of dispersion Q _disp and specific (donor-acceptor) Q _spec interactions are calculated, and the electron-donor and electron-acceptor characteristics of the surface of the original UFD and the UFDs with immobilized metal nanoparticles are estimated. It is shown that chlorobenzene is sorbed by the physical adsorption mechanisms on the original support and on a sample modified with nickel nanoparticles, and is chemisorbed on a support modified with palladium nanoparticles. The highest heats of chemisorption are obtained on UFD modified with Pd nanoclusters; a surface of UFD modified with Ni nanoclusters is less active with respect to these chlorobenzenes than a surface of unmodified UFD. Benzene, chloroform, and diethyl ether are sorbed on unmodified and modified UFDs by a physical adsorption mechanism; the highest and lowest values of Q _spec for these materials are obtained on UFDs modified with Pd and Ni nanoclusters, respectively.     

Commensurability oscillations in NdBa2Cu3Oy single crystals

Commensurability between inter-vortex distance and crystal lattice constant is investigated by angular dependent magnetization in very pure twinned and twin-free NdBa₂ Cu₃ O_y single crystals. With increasing temperature the incommensurate states split up and become finally commensurate with half the vortex distance. These new commensurate states are related to a substructure of the intrinsic pinning potential within the unit cell and discussed with respect to temperature, field, anisotropy, and twin structure.     

Electron band structure detection by high-order optical harmonic generation in solids

As the threshold field strength for the breakdown in air significantly exceeds the maximum measured thundercloud strength 3 kV/cm/atm, the problem of lightning initiation remains unclear. According to the popular idea, lightning can be initiated from streamer discharges developed in the enhanced electric field in a vicinity of hydrometeors. To test the idea, we carry out numerical simulations of positive streamer development around charged water drops at air pressure typical at thundercloud altitudes and at different background fields, drop sizes and charges. With real drop sizes and charges, the electric field required for the streamer formation is stronger than the measured fields; therefore, second mechanism is required to amplify the local field.