Extraktion von 3d-Metallionen mit zweizähligen Sulfonamiden. I. Liganden mit Schwefel bzw. heterocyclisch gebundenem Stickstoff als zweitem Haftatom

Extraction of 3d-Metal Ions by Bidendate Sulfonamides. I. Ligands with Sulfur or Heterocyclic Nitrogen as a Second Donor Atom The properties of 2-acetylpyridine-p-toluensulfonylhydrazone (APSH - H), arensulfonylthioureas (I), and the esters of arensulfonylmonothiocarbamic acid (II) or arensulfonyldithiocarbamic acid (III) as extractants for the late 3d-metal ions are proved. APSH-H is comparable to the proprietary extractant LIX 34. But, because of the special structure of the corresponding 1,2-chelates, the pH_1/2-values of nickel(II) and cobalt(II) are ≈2 units lower. The pK_s-values, measured in dioxane-water mixtures (75 per cent v/v), increase in the order III < II < I. In aqueous solutions compounds of type III are acids of medium strength. In the case of compounds of type I the substituents of the non-sulfonated nitrogen have a strong influence on the pK_s-values (ΔpK_s = 4.6). Among the late 3d-elements, the ligands II and III extract only copper(II) (pH_1/2 ～2.7 or ～1.6), the ligands I extract zinc(II), cobalt(II), and nickel(II) as well, but not iron(II) and iron(III). The reasons of this unique behaviour are discussed.     

Photocycloaddition of Cyclohex‐2‐enones to Penta‐1,2,4‐triene

Dihydrothiinone 9a undergoes photocycloaddition regioselectively to all three C?C bonds of penta‐1,2,4‐triene ( 10 ), the relative stabilities of the biradical intermediates determining the product distribution. In contrast, cyclohexenone 9b and dihydropyranone 9c afford more complex mixtures of bicyclo[4.2.0]octanones, which also turn out to be less stable on chromatographic workup, reflecting the higher strain due to the shorter bond lengths (C? O and C? C vs. C? S) in the six‐membered rings, respectively.     

Metallorganische verbindungen der lanthanoide CVIII. Synthese und strukturaufklärung monomerer organolanthanoidacetate

LnCl₃ reacts with Na(C₅Me₄¹Bu) in THF to form the organolanthanoid chlorides [(C₅Me₄¹Bu)₂LnCl(THF)] (Ln = La (1a), Lu (1b)). Compounds 1a and 1b yield in reaction with NaO₂CCH₃ the monomeric organolanthanoid acetates [(C₅Me₄¹Bu)₂LnO₂CCH₃] (Ln = La (2a), Lu (2b)). The single crystal X-ray structure analysis of 2b as well as the cryoscopic molecular weight investigation of 2a verify the monomeric structure of these complexes.     

In-capillary micro solid-phase extraction and capillary electrophoresis separation of heterocyclic aromatic amines with nanospray mass spectrometric detection

A miniaturised technique to analyse and detect heterocyclic aromatic amines (HAs) using micro solid-phase extraction (SPE) coupled on-line (in-capillary) to capillary electrophoresis (CE) separation with nanospray (nESI) mass spectrometry (MS) detection has been developed. HAs are mutagenic and carcinogenic compounds formed at low levels in protein-rich food during cooking. Due to the low concentrations of HAs and the high complexity of the matrix in which they exist, sensitive and selective analytical methods are required for quantification. SPE was performed on a packed bed of C₁₈ particles inside the CE capillary, which minimised the dead volume. The on-line coupling of SPE, CE and nESI-MS reduced the time for extraction and identification to less than half an hour, which will allow for screening of several samples per day. The new technique provides short analysis time, low sample and solvent consumption, and HAs in standard solutions were easily detected at 12–17 fmol injections, and in spiked urine samples at 750–810 fmol injections.     

Intercalation materials for lithium rechargeable batteries

An overview is given of intercalation materials for both the negative and the positive electrodes of lithium batteries, including the results of our own research. As well as lithium metal as a negative electrode, we consider insertion materials based on aluminium alloys. In the case of the positive electrode metal-oxides based on manganese, nickel and cobalt are discussed. Received: 27 May 1997 / Accepted: 30 July 1997     

UHF-CI studies of energy barriers for the abstraction and exchange reactions in the system H + CH4

UHF and CI calculations, using the direct CI method, and double-zeta plus polarization functions basis sets, have been performed on the more important parts of the energy hypersurface for CH₅. The abstraction H + CH₄ → H₂ + CH₃ and the inversion substitution reaction H′ + CH₄ → CH₃H′ + H have been studied in detail. The predicted barriers for these two reactions are 13.5 and 36.6 kcal/mol, respectively. The abstraction reaction is, in agreement with experiment, found to be almost thermo-neutral with a heat of reaction of 1.5 kcal/mol.     

Macrophage-targeting oligopeptides from Mortierella alpina

The realm of natural products of early diverging fungi such as Mortierella species is largely unexplored. Herein, the nonribosomal peptide synthetase (NRPS) MalA catalysing the biosynthesis of the surface-active biosurfactants, malpinins, has been identified and biochemically characterised. The investigation of the substrate specificity of respective adenylation (A) domains indicated a substrate-tolerant enzyme with an unusual, inactive C-terminal NRPS module. Specificity-based precursor-directed biosynthesis yielded 20 new congeners produced by a single enzyme. Moreover, MalA incorporates artificial, click-functionalised amino acids which allowed postbiosynthetic coupling to a fluorophore. The fluorescent malpinin conjugate penetrates mammalian cell membranes via an phagocytosis-mediated mechanism, suggesting Mortierella oligopeptides as carrier peptides for directed cell targeting. The current study demonstrates substrate-specificity testing as a powerful tool to identify flexible NRPS modules and highlights basal fungi as reservoir for chemically tractable compounds in pharmaceutical applications.

Specificity profiling of a nonribosomal peptide synthetase of an early diverging fungus revealed high substrate flexibility. Feeding studies with click-functionalised amino acids enabled the production of fluorescent peptides targeting macrophages.     

Heterotrimeric liquid crystalline thiadiazole derivatives

Abstract

Various trimeric co-oligomers combining 2-phenyl-1,3,4-thiadiazole mesogenic moieties with a biphenyl mesogenic moiety were synthesized and their mesomorphic behaviour investigated by polarizing microscopy, calorimetry and X-ray scattering. Such co-oligomeric structures provide an opportunity to combine different mesogenic units. Thus readily accessible homochiral biphenyl mesogenic units were connected with thiadiazole mesogenic units leading to an oligomeric liquid crystal material with ferroelectric properties.     

Aus der Praxis Erste Ergebnisse zur On-line-Schnellextraktion mit Kronenethern bei kernchemischen Experimenten

Im Zusammenhang mit on-line-Bestrahlungsexperimenten har sich vor allem die He-Jet-Technik einen festen Platz erobert [1- 5], der nicht in Frage gestellt werden soll. Unge- uchtet dessen erseheint es zweekmäßig, ergänzend Techniken zu entwickeln, die ausschließlich auf Verwendung von flüsigen Phasen basieren. Das erlaubt es, die vielfältigen Möglichkeiten zu nutzen, welehe die Chemie in Lösungen für Trenn- und Anreicherungsaufgaben bietet. Dabei wird von der Grundannahme ausgegangen, daß bezüglich der Transportgeschwindigkeit die entsprechenden Parameter der Gas-Jet-Technik durch rein flüssige Varianten bestenfalls erreicht jedoch kaum übertroffen werden können. In der zur Verfügung stehenden Literatur wurde lediglich von Aronsson u. a. 1973 ein System beschrieben, wo in einer n, γ-Reaktion eine Lösung direkt bestrahlt wird [6], dieses findet sich jedoch in der späteren Literatur nicht wieder.

Die hier darzulegenden Ergebnisse stellen erste Experimente zur direkten Bestrablung einer Lösung mit beschleunigten Ionen dar. Sie sollen in letzter Konsequenz der Erarbeitung einer Experimentiervariante     

Detection of laser induced dielectric breakdown in water using a laser doppler vibrometer

This study is focused on exploring the feasibility of an all-optic surface scanning method in determining the size and position of a submerged, laser generated, optoacoustic (OA) source. The optoacoustic effect in this case was generated when the absorption of a short electromagnetic pulse in matter caused a dielectric breakdown, a plasma emission flash and a subsequent acoustic wave. In the experiment, a laser pulse with λ = 1064 nm and 12 ns pulse length was aimed at a volume of deionized water. When the laser beam was focused by a f = 16 mm lens, a single dielectric breakdown spot occurred. When a f = 40 mm was used several breakdowns in a row were induced. The breakdowns were photographed using a double shutter camera. The acoustic wave generated by the dielectric breakdowns were detected at a point on the water surface using a laser Doppler vibrometer (LDV). First, the LDV signal was used to calculate the speed of sound with an accuracy of 10 m/s. Secondly, the location and length of the dielectric breakdown was calculated with an accuracy of 1 mm. The calculated position matched the breakdown location recorded by a camera. The results show that it is possible to use LDV surface measurements from a single spot to determine both the position and length of the OA source as well as the speed of sound in the medium. Furthermore, the LDV measurements also show a secondary peak that originates from the OA source. To unravel the origin and properties of this interesting feature, further investigations are necessary