Fragmentation during the formic acid/formaldehyde (eschweiler-clarke) methylation of polyamines

Eschweiler-Clarke methylations of both acyclic and cyclic polyamines can lead to methylation products of fragments of the original polyamine; thus 1,5,9,13-tetra-azatridecane yields 1,1,3,3-tetramethylpropanediamine exclusively and 1,5,9-triazacyclododecane gives 45% 1,5,9-trimethyl-1,5,9-triazacyclodecane and 45% 2,6,10-trimethyl-2,6,10-triazaundecane.     

On Linear-Time Algorithms for the Continuous Quadratic Knapsack Problem

We give a linear time algorithm for the continuous quadratic knapsack problem which is simpler than existing methods and competitive in practice. Encouraging computational results are presented for large-scale problems. The author thanks the Associate Editor and an anonymous referee for their helpful comments.     

Impact of two mass scale oscillations on the analysis of atmospheric and reactor neutrino data

We study the stability of the results of the three-neutrino oscillation analysis of atmospheric and reactor neutrino data under departures of the one dominant mass scale approximation. In order to do so we perform the analysis of atmospheric and reactor neutrino data in terms of three-neutrino oscillations where the effect of both mass differences is explicitly considered. We study the allowed parameter space resulting from this analysis as a function of the mass splitting hierarchy parameter which parameterizes the departure from the one dominant mass scale approximation. We consider schemes with both direct and inverted mass ordering. Our results show that in the analysis of the atmospheric data the derived range of the largest mass splitting, , is stable, while the allowed ranges of mixing angles and are wider than those obtained in the one dominant mass scale approximation. Inclusion of the CHOOZ reactor data in the analysis results in the reduction of the parameter space in particular for the mixing angles. As a consequence the final allowed ranges of the parameters from the combined analysis are only slightly broader than when obtained in the one dominant mass scale approximation. Received: 31 May 2002 / Revised version: 10 July 2002 / Published online: 31 October 2002     

Realisation and metrological characterisation of thickness standards below 100 nm

High-accuracy film thickness measurements in the range below 100 nm can be made by various complex methods like spectral ellipsometry (SE), scanning force microscopy (SFM), grazing incidence X-ray reflectometry (GIXR), or X-ray fluorescence analysis (XRF). The measurement results achieved with these methods are based on different interactions between the film and the probe. A key question in nanotechnology is how to achieve consistent results on a level of uncertainty below one nanometre with different techniques.Two different types of thickness standards are realised. Metal film standards for X-ray techniques in the thickness range 10 to 50 nm are calibrated by GIXR with monochromatised synchrotron radiation of 8048 eV. The results obtained at four different facilities show excellent agreement. SiO₂ on Si standards for SE and SFM in the thickness range 6 to 1000 nm are calibrated by GIXR with monochromatised synchrotron radiation of 1841 eV and with a metrological SFM. Consistent results within the combined uncertainties are obtained with the two methods. Surfaces and interfaces of both types of standards are additionally investigated by transmission electron microscopy (TEM). PACS 61.10.Kw; 68.55.Jk; 06.20.Fn; 06.60.Mr; 07.79.Lh     

Mass spectral analysis and imaging of tissue by ToF-SIMS—The role of buckminsterfullerene, C60, primary ions

Recent developments in desorption/ionisation mass spectrometry techniques have made their application to biological analysis a realistic and successful proposition. Developments in primary ion source technology, mainly through the advent of polyatomic ion beams, have meant that the technique of secondary ion mass spectrometry (SIMS) can now access the depths of information required to allow biological imaging to be a viable option.Here the role of the primary ion C₆₀⁺ is assessed with regard to molecular imaging of lipids and pharmaceuticals within tissue sections. High secondary ion yields and low surface damage accumulation are demonstrated on both model and real biological samples, indicating the high secondary ion efficiency afforded to the analyst by this primary ion when compared to other cluster ion beams used in imaging. The newly developed 40 keV C₆₀⁺ ion source allows the beam to be focused such that high resolution imaging is demonstrated on a tissue sample, and the greater yields allow the molecular signal from the drug raclopride to be imaged within tissue section following in vivo dosing.The localisation shown for this drug alludes to issues regarding the chemical environment affecting the ionisation probability of the molecule; the importance of this effect is demonstrated with model systems and the possibility of using laser post-ionisation as a method for reducing this consequence of bio-sample complexity is demonstrated and discussed.