Partial structure elucidation of the most abundant octa and nonachlorotoxaphene congeners in marine mammals by using conventional electron ionization mass spectrometry and mass spectrometry/mass spectrometry

Summary Conventional electron ionization (EI) mass spectrometry (MS) and MS/MS techniques were applied to the analysis of two abundant octa and nonachlorobornanes isolated from seals of the Baltic sea and originating from technical toxaphene. The exact sterical structures of the two compounds were previously determined using nuclear magnetic resonance (NMR) spectroscopy by two independent research groups. The MS and MS/MS data generated in this study allowed partial structure elucidation of these polychlorobornanes, in particular revealing the distribution of the Cl substituents between the six-membered carbon ring, the bridge and the bridgehead in the parent bornane structure. Fragmentation of the six-membered carbon ring and the bridge by retro-Diels-Alder (RDA) and related mechanisms was discovered by studying specific parent/daughter ion transitions. The detailed fragmentation pathways formulated may be applicable to the structure elucidation of other toxaphene congeners and the monitoring of strategic transitions is highly selective for the detection of these compounds in technical toxaphene and in environmental samples.     

Local Entropy Conditions in Transonic Potential Flow Problems

The transonic potential flow problem is handled as a variational problem over a closed convex set which is given by a bound for the gas velocity and by a local entropy condition. It can be shown that the minimum problem has a solution though the functional need not be convex and the given set is not compact. Furthermore, the convergence of an approximation method (KATCHANOV'S method) for the solution to the corresponding variational inequality is proved.     

Preparation of micro- and nanopatterns of polymer chains grafted onto flexible polymer substrates

In this work a simple novel method for preparing micro- and nanoscale patterns of polymer chains grafted onto flexible polymer substrates is described. A combination of the two techniques of radiation grafting and "grafting-from" has been made. This combination makes it possible to prepare grafted structures having micro- or nanoscale lateral dimensions that are determined by the electron beam or X-ray irradiation patterns used. The height of the grafted features can be controlled by the irradiation dose or such grafting reaction conditions as time, temperature, or monomer concentration. Our first results for nanopatterned samples demonstrate resolution comparable to those of other polymer-based lithography processes.     

Tetrakis (methylidene)cyclobutane (‘[4]Radialene’): Electronic states of the molecular ion

The photoelectron spectrum of tetrakis (methylidene)cyclobutane ( 1 , ‘[4]radialene’) is reported. The electronic states of 1 ⁺ are assigned on the basis of model calculations and with reference to related systems. Jahn-Teller activity in the degenerate states is discussed. A failure of the simple LCBO-model for the π(e_g)-orbital of 1 is noted and traced to the fact that this orbital, though having a symmetry-equivalent π*-counterpart, does not interact with it. This feature is confined to [4n]radialenes; their total π-energies are therefore higher than those of the other members. It is shown that radialenes, in principle, do not constitute a class analogous to that of the linear polyenes as inferred earlier.     

Rhodium and palladium β-diketonate determination with on-line supercritical fluid extraction-high performance liquid chromatography via solid phase extraction

 An on-line system of supercritical fluid extraction (SFE) and high performance liquid chromatography (HPLC) via solid phase extraction (SPE) is described for the determination of palladium and rhodium 2,2,6,6-tetramethyl-3,5-heptanedione-(thd) as well as rhodium-acetylacetonate-(acac) and benzylacetonate-(bzac) chelates. The chelates were extracted with supercritical CO₂ from sand and humic acid, concentrated on SPE cartridges and analysed with HPLC. Two cartridge materials were tested and compared to off-line trapping. The percentage of the breakthrough and cartridge retained material were measured in liquid dichloromethane. The SFE conditions could be optimized to separate metal chelates during the extraction. The supercritical fluid (SF) behaviour of different ligands on rhodium were investigated. Received: 19 July 1996/Revised: 11 December 1996/Accepted: 14 December 1996     

Characteristic behavior of macro-, semimicro- and microelectrodes in voltammetric and chronoamperometric measurements

The advantages of microelectrodes such as the improvement of signal-to-noise ratio, the ability to perform electrochemical measurements in high resistive solutions and small RC-time constants give the possibility of an extended use for voltammetric and chronoamperometric techniques in analytical chemistry. In this comparative study, the microelectrode properties of three selected electrodes were examined. The characterization of a RAM-microarray electrode, an epoxy-impregnated carbon electrode and a conventional glassy carbon macroelectrode was performed by cyclic voltammetry at different scan rates, by DP-voltammetric measurements using different concentrations of supporting electrolyte and by transient measurements. It could be shown, that in comparison to the microarray electrode and to the glassy carbon macroelectrode, respectively, the results obtained by using the epoxy-impregnated carbon electrode are caused by its semimicroelectrode character.     

Triangulations and moduli spaces of Riemann surfaces with group actions

Summary We study that subset of the moduli space of stable genusg,g>1, Riemann surfaces which consists of such stable Riemann surfaces on which a given finite groupF acts. We show first that this subset is compact. It turns out that, for general finite groupsF, the above subset is not connected. We show, however, that for ℤ₂ actions this subsetis connected. Finally, we show that even in the moduli space ofsmooth genusg Riemann surfaces, the subset of those Riemann surfaces on which ℤ₂ actsis connected. In view of deliberations of Klein ([8]), this was somewhat surprising. These results are based on new coordinates for moduli spaces. These coordinates are obtained by certainregular triangulations of Riemann surfaces. These triangulations play an important role also elsewhere, for instance in approximating eigenfunctions of the Laplace operator numerically. This work has been supported by the European Communities Science Plan Project No SCI^*-CT91 (TSTS) “Computational Methods in the Theory of Riemann Surfaces and Algebraic Curves,” by Academy of Finland and by the Swiss National Science Foundation Grant 20-34099.92. We thank M. C. Petrus for providing excellent motivation for this work. This article was processed by the author using the LATEX style filecljourl from Springer-Verlag.     

Series representation for semistable laws and their domains of semistable attraction

If the centered and normalized partial sums of an i.i.d. sequence of random variables converge in distribution to a nondegenerate limit then we say that this sequence belongs to the domain of attraction of the necessarily stable limit. If we consider only the partial sums which terminate atk _n wherek _n+1 ck _n then the sequence belongs to the domain of semistable attraction of the necessarily semistable limit. In this paper, we consider the case where the limiting distribution is nonnormal. We obtain a series representation for the partial sums which converges almost surely. This representation is based on the order statistics, and utilizes the Poisson process. Almost sure convergence is a useful technical device, as we illustrate with a number of applications.This research was supported by a research scholarship from the Deutsche Forschungsgemeinschaft (DFG).     

Synthesis and absolute configuration of clemastine and its isomers (author's transl)]

Synthesis and Absolute Configuration of Clemastine and its Isomers. Condensation of 4-chloro-α-methylbenzhydrylalkohol ( 1 ) with 2-(2-chloroethyl)-1-methylpyrrolidine ( 2 ) gave an isomeric mixture of 2-[2-(p-chloro-α-methyl-=-phenylbenzyloxy)ethyl]-1-methylpyrrolidine ( 3 ) and 4-(p-chloro-=-phenylbenzyloxy)-1-methyl-hexahydroazepin ( 4 ). The separation of the four possible optically active isomers of 3 is described and their absolute configuration established by degradation to (R)- and (S)-1-methyl-2-pyrrolidineethanol ( 6 ), respectively, and by an X-ray cristallographic analysis of the quarternary methiodide of the isomer 3-A . Clemastine (3-A) is (+)-(2R)-2-[2-((αR)-(p-chloro-α-methyl-α-phenylbenzyloxy)ethyl)]-1-methylpyrrolidine.