Accurate mass measurement by matrix‐assisted laser desorption/ionisation time‐of‐flight mass spectrometry. I. Measurement of positive radical ions using porphyrin standard reference materials

A method for the accurate mass measurement of positive radical ions by matrix‐assisted laser desorption/ionisation time‐of‐flight mass spectrometry (MALDI‐TOFMS) is described. Initial use of a conjugated oligomeric calibration material was rejected in favour of a series of meso‐tetraalkyl/tetraalkylaryl‐functionalised porphyrins, from which the two calibrants required for a particular accurate mass measurement were chosen. While all measurements of monoisotopic species were within ±5 ppm, and the method was rigorously validated using chemometrics, mean values of five measurements were used for extra confidence in the generation of potential elemental formulae. Potential difficulties encountered when measuring compounds containing multi‐isotopic elements are discussed, where the monoisotopic peak is no longer the lowest mass peak, and a simple mass‐correction solution can be applied. The method requires no significant expertise to implement, but care and attention is required to obtain valid measurements. The method is operationally simple and will prove useful to the analytical chemistry community. Copyright © 2010 John Wiley & Sons, Ltd.     

Photosensitive gelatin

Employing photodestructible surfactants in gelatin-based aqueous gels presents novel possibilities for controlling colloidal and aggregation properties of surfactant gelatin complexes. Light-triggered breakdown of the gelatin-bound photosurfactant aggregates causes dramatic changes in viscosity and aggregation.     

Investigation into accurate mass capability of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, with respect to radical ion species

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) has been shown to be an effective technique for the characterization of organometallic, coordination, and highly conjugated compounds. The preferred matrix is 2-[(2E)-3-(4-tert-butylphenyl)-2-methylprop-2-enylidene]malononitrile (DCTB), with radical ions observed. However, MALDI-TOFMS is generally not favored for accurate mass measurement. A specific method had to be developed for such compounds to assure the quality of our accurate mass results. Therefore, in this preliminary study, two methods of data acquisition, and both even-electron (EE+) ion and odd-electron (OE+.) radical ion mass calibration standards, have been investigated to establish the basic measurement technique. The benefit of this technique is demonstrated for a copper compound for which ions were observed by MALDI, but not by electrospray (ESI) or liquid secondary ion mass spectrometry (LSIMS); a mean mass accuracy error of -1.2 ppm was obtained.     

Potentiometrie

Ohne Zusammenfassung     

Spatial evolution of pulses of low-energy phonons in liquid He

The system of equations that describes the temporal and spatial evolution of low-energy phonons (l-phonons) is obtained for the cases of plane and axial symmetry. From the solutions of these equations, we discuss the time-resolved measurements of the angular distribution of l-phonons. These show a rather unusual mesa shape with a flat top in the direction normal to the heater. We consider that the flat top is due to the creation of high-energy phonons (h-phonons).     

Drag reduction effectiveness of dilute and entangled xanthan in turbulent pipe flow

The ability to reduce the frictional drag in turbulent flow in pipes and channels by addition of a small amount of a high molecular weight polymer has application in myriad industries and processes. Here, the drag reduction properties of the polyelectrolyte xanthan are explored in differing solvent environments (salt free versus salt solution) and delivery configurations (homogeneous versus stock solution dilution). Drag reduction effectiveness increases when an entangled xanthan solution is diluted compared to solutions prepared in the dilute regime. Based on dynamic rheological measurements of the elastic modulus, residual entanglements and network structure are hypothesized to account for the observed change in drag reduction effectiveness. Drag reduction effectiveness is unchanged by the presence of salt when the stock solution concentration is sufficiently above the critical concentration c_D. Finally, the drag reduction effectiveness decreases with time when diluted from an entangled stock solution but remains greater than the homogeneous case after more than 24 h.     

Vectorial phase retrieval for linear characterization of attosecond pulses

The waveforms of attosecond pulses produced by high-harmonic generation carry information on the electronic structure and dynamics in atomic and molecular systems. Current methods for the temporal characterization of such pulses have limited sensitivity and impose significant experimental complexity. We propose a new linear and all-optical method inspired by widely used multidimensional phase retrieval algorithms. Our new scheme is based on the spectral measurement of two attosecond sources and their interference. As an example, we focus on the case of spectral polarization measurements of attosecond pulses, relying on their most fundamental property-being well confined in time. We demonstrate this method numerically by reconstructing the temporal profiles of attosecond pulses generated from aligned CO(2) molecules.