Morphological and elemental characterisation with the high-energy ion-nanoprobe LIPSION

This contribution deals with the morphological and elemental characterisation with high-energy (MeV) focused ion beams (in particular protons) with special emphasis on high spatial resolution in the sub-micrometer regime and very low minimum detection limits (sub-ppm) in trace element analysis. The most important methods like particle induced X-ray emission (PIXE), Rutherford backscattering spectrometry (RBS), as well as scanning transmission ion microscopy (STIM) and STIM-tomography will be illustrated by examples from material and life sciences.     

Low energy excitations in KMnO4 with 1 eV<=ΔE<=10 eV from electron-energy loss spectroscopy

Electron-energy loss spectra of potassium permanganate (KMnO₄) with primary electron energies 25 eV<=E₀<=500 eV show 7 peaks in the energy-loss range 1 eV<=ΔE<=10eV and are successfully analysed with a superposition of 7 independent Gaussians. The intensity of these lines follow roughly a power-law dependence on the primary energy I∝E ₀ ^-α . There are two groups of lines, the first with an exponent α≈0.5, while the lines in the second group decay much stronger with increasingE ₀ corresponding to a value 0.9<=α<=1.3. The 4 lines in the first group are identified as dipole allowed transitions by comparison to recent first principle molecular-orbital calculations for the (MnO₄) molecule by H. Nakai et al. The dipole-allowed excitation spectrum obtained from this analysis agrees very well with these first principle calculations.     

On the Hydrolytic Stability of Organic Ligands in Al-, Ti- and Zr-Alkoxide Complexes

The complexation degrees of Al-, Ti- and Zr-butoxide (M) with unsaturated and saturated -diketones (3-allylpentane-2.4-dione-APD, acetylacetone-ACAC) and -ketoesters (methacryloxyethyl-acetoacetate-MEAA, allylacetoacetate-AAA, ethylacetoacetate-EAA) as organic ligands (L) were examined by IR and ¹³ C NMR spectroscopy and were found to be L:M 1.5. The hydrolytic stability of the ligands of the metal alkoxide complexes (L:M = 1) during hydrolysis/condensation reactions at the molar ratio h (H₂O : OR) = 0.5–2.0 decreases with increasing H$$₂O:complex ratio. Furthermore, the ligand stability depends on the type of metal in the complexes and decreases in the order Al- > Zr- > Ti-butoxide complexes at h=1. The ACAC ligand likewise shows in the Al-, Ti- and Zr-butoxide complexes a high hydrolytic stability (95–100%) at h=1 within 7 days. The Ti- and Zr-butoxide complexes with -ketoesters as ligand show at h=1> a release to a different extent e.g., up to 60% in the case of the MEAA-ligand in the Ti-butoxide complex after 2 days. In general, the hydrolytic stability of the ligands in the Ti-butoxide complexes (L:M = 1, h=1) decreases in the order ACAC > APD > AAA > EAA MEAA. The hydrolysis/condensation reaction of complexes having a weak ligand stability leads to larger particle sizes in the sols than those with stable ACAC ligands. The results contribute to a more controlled synthesis of sols and of new inorganic-organic hybrid polymers via the sol-gel process.     

Electron-hole correlation effects in core-level spectroscopy probed by the resonant inelastic soft x-ray scattering map of C60

We have employed a unique spectroscopic approach, a resonant inelastic soft x-ray scattering (RIXS) map, to identify and separate electron-hole correlation effects in core-level spectroscopy. With this approach, we are able to derive a comprehensive picture of the electronic structure, separating ground state properties (such as the HOMO-LUMO separation) from excited state properties (such as the C 1s core-exciton binding energy of C(60)). In particular, our approach allows us to determine the difference between core- and valence exciton binding energies in C(60) [0.5 (±0.2) eV]. Furthermore, the RIXS map gives detailed insight into the symmetries of the intermediate and final states of the RIXS process.     

The electronic structure of KMnO4 investigated by resonant photoemission

The valence band of potassium permanganate (KMnO₄) was investigated by means of resonant photoemission spectroscopy (ResPES) at the Mn2p, Mn3p and O1s edge. These data confirm the previous conclusions of a strong deviation from a purely ionic charge distribution in this compound. The ResPES data are in agreement with previous results about the character of the individual valence band states. A simple cluster model is used to explain qualitatively the different structures seen in the valence band spectra and their dependence on the photon energy.     

Polydispersitäts- und formeinfluß and diffusionskonstanten und svedberg-molekulargewichte insbesondere bei DNS

Zusammenfassung Ein allgemeiner Zusammenhang zwischen Sedimentationskonstanten verteilung und Diffusionskonstantenverteilung wird angegeben. Darauf aufbauend werden für polydisperse Proben linearer Makromoleküle Beziehungen zwischen den verschiedenen Mittelwerten der Diffusionskonstante abgeleitet. Analoge Zusammenhänge werden angegeben zwischen verschiedenen mittleren Molekulargewichten nach derSvedberg-Gleichung einerseits und dem GewichtsmittelM _w oder dem MolekulargewichtM ⁺ einer monodispersen Subfraktion mit der vorgegebenen Sedimentationskonstantes ⁰=s ⁰⁺ andererseits.Die Ergebnisse sind für eine beliebige Form der Verteilung formuliert. Sie sind dargestellt als Funktion des Gestaltsparameters und der MomenteI ^(v) der reduzierten Sedimentationskonstantenverteilung. Letztere sind leicht bestimmbar im Falle sehr hochmolekularer Proben und sehr empfindlicher Nachweismethoden. Bei Benutzung einer speziellen einparametrigen Näherung für die reduzierten Sedimentationskonstantenverteilung ist oft eine einfache Abschätzung des Polydispersitätseinflusses möglich.Weiterhin wird eine Möglichkeit für die Berechnung des Einflusses von Gestaltsänderungen auf das Verhältnis o. g. Mittelwerte angegeben. In Umkehrung des Verfahrens ist man in der Lage, die mit Konformationsänderungen verbundenen Veränderungen des Parametersa _s durch Messung der Änderung der reduzierten Sedimentationskonstantenverteilung einer Probe anzugeben.

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Summary A general relation between sedimentation constant distribution and diffusion constant distribution is presented. Based on it equations combining different mean values of diffusion constant are derived for polydisperse samples of linear macromolecules. Analogous relations are formulated between different average molecular weights according to theSvedberg equation on the one hand and the weight averageM _w or the molecular weightM ⁺ of the monodisperse subfraction with an arbitrary sedimentation constants ⁰=s ⁰⁺ on the other hand.The results are formulated for an arbitrary form of the distribution. They are expressed in terms of the shape parameter and the momentsI ^(v) of the reduced sedimentation constant distribution which may be easily determined in the case of very high molecular weight samples and very sensitive detection methods. By use of a special single parameter approximation for the reduced sedimentation constant distribution a simple estimation of the polydispersity effect may often be possible.Furthermore a possibility is demonstrated for the calculation of the influence of changes in shape on the ratio of given mean values. Converting the procedure we are able to calculate the variation of the parametera _s accompanying a conformational change by measuring the change of the reduced sedimentation constant distribution.

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Mit 5 Abbildungen und 3 Tabellen

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Mitteilung über Polydispersität und Konformation.     

Total Variation Distance for Poisson Subset Numbers

Let n be an integer and A₀,..., A_k random subsets of {1,..., n} of fixed sizes a₀,..., a_k, respectively chosen independently and uniformly. We provide an explicit and easily computable total variation bound between the distance from the random variable , the size of the intersection of the random sets, to a Poisson random variable Z with intensity λ = EW. In particular, the bound tends to zero when λ converges and for all j = 0,..., k, showing that W has an asymptotic Poisson distribution in this regime. Received February 24, 2005     

Chemosensor for the optical detection of aliphatic amines and diamines

Two new chemosensor dyes with either one or two trifluoroacetophenone recognition moieties have been investigated in terms of reversibly interacting with amines and diamines.