Mass spectrometric investigations of water extracts of the river Elbe for the determination of potential inputs of pollutants into the North Sea

A non-target screening by gas chromatography-mass spectrometry has been carried out on water extracts of the river Elbe in order to obtain an overview of organic compounds being dissolved or bound to suspended matter in the Elbe. Samples of 1001 volume were taken at the freshwater border at Stade and extracted by liquid-liquid extraction with pentane. Before GC-MS analysis, the water extracts were fractionated into 15 subsamples by HPLC on an SiO₂ column. A sensitivity of ca. 50 to 250 pg/l was reached for the GC-MC analysis. Several hundreds of natural and anthropogenic compounds could be identified or at least grouped into a compound class. The presence of a number of compounds could be verified from earlier investigations, in addition a great number of anthropogenic compounds were described which have previously not been reported for the river Elbe.     

18C6-Kronenkomplex der Amidoschwefelsäure

18C6 Crown Complex of Amidosulfuric Acid The title compound ( 3 ) has been obtained from reaction of the crown ether 18C6 ( 1 ) with amidosulfuric acid ( 2 ) in water, methanol, and ethanol. The structure of the substance was elucidated with X-ray diffraction and IR data. The two constituents of 3 are connected through three oxygen-hydrogen bridges. 3 is ideally suited for the isolation and recovery of 1 from aqueous solutions.     

Ozonolyse von Olefinen,III: Säurekatalysierte Ozonolyse von 3-Hexen-1,6-und 2-Penten-1,5-dicarbonylderivaten

Summary The ozonolysis of mono-unsaturated compounds containing the structural element =CH-CH₂-R [R=COOH, COOCH₃, CH(OCH₃)₂] was investigated. Reductive ozonolysis of (E)-3-hexene-1,6-dioic acid gives methyl 3,3-dimethoxypropanoate (2), whereas ozonolysis of dimethyl (E)-3-hexene-1,6-dioate (1a) and (Z)-1,1,6,6-tetramethoxy-3-hexene (1b) in a methanolic solution of HCl leads to a mixture of2, dimethyl malonate (3 a) and 1,1,3,3-tetramethoxypropane (3 b). The homologuos derivatives, dimethyl glutaconate (4 a) and 1,1,5,5-tetramethoxy-2-pentene (4 b), were ozonized to give mixtures of2, 3, dimethyl oxalate (5), methyl 2,2-dimethoxyacetate (6 a), and 1,1,2,2-tetramethoxyethane (6 b). The ratios of the various reaction products were determined by gas chromatography. In each case the formation of the bifunctional derivatives2 and6 a was favoured.

     

Beiträge zur Chemie der Pyrrolpigmente, 42. Mitt. Kraftfeldrechnungen an Gallenfarbstoffen: Die Energiehyperfläche rubinoider Pigmente

The energy hypersurface of rubinoid bile pigments is calculated using a force field model previously described. Two cases are observed. I: The pigment is substituted symmetrically or unsymmetrically by apolar groups. This results in a very shallow energy valley containing several enantiomeric conformers of approximately equal energies. II: Substitution by polar groups, especially in position 8 and 12 of the rubin skeleton, (e.g.–CH₂–CH₂–COOH) is followed by a lock in bonding between such groups and the lactam ring functions. Thereby only two enantiomeric conformers, which are energetically stabilized, are possible. The barrier between these species amounts to about 40 kJ/mol. These results are compared with the experimental facts available so far. An analysis of the corresponding energy hypersurfaces of the diastereomeric forms of (Z,Z)-, (E,Z)-, (Z,E)- and (E,E)-configurations is given as well.

41. Mitt.:Falk H., Müller N., Mh. Chem.112, 791 (1981).     

Analysis of N-acylhomoserine lactones after alkaline hydrolysis and anion-exchange solid-phase extraction by capillary zone electrophoresis-mass spectrometry

A quantitative, specific, and sensitive method for the determination of N-acylhomoserine lactones (HSLs - a group of bacterial semiochemicals) in the form of their hydrolysis products (N-acylhomoserines, HSs) is presented. Real samples were analyzed by capillary zone electrophoresis-mass spectrometry (CZE-MS) after alkaline lactonolysis and extraction by mixed-mode anion-exchange solid-phase extraction. The presented cleanup significantly speeds up the HSL extraction procedure, strongly reduces sample consumption, and is more selective compared to the commonly used liquid/liquid extraction. Completeness of the hydrolysis reaction was examined by nuclear magnetic resonance spectroscopy. This CZE-MS method complements recently published capillary separation techniques (nano liquid chromatography-MS, partial-filling micellar electrokinetic chromatography-MS, gas chromatography-MS) and provides a possibility to differentiate quantitatively between the homoserines (as naturally occurring degradation products) besides the intact homoserine lactones. The method was found to be quantitative down to a concentration of 0.05 microg/mL (limit of quantification), while the limit of detection was determined with 0.01 microg/mL - sufficient for the analysis of culture supernatants.     

Structural study of highly halogenated dihydropyridine derivatives as potential calcium channel modulators

Two dihydropyridines endowed with fluorine atoms ( 3 ) and fluorine and chlorine atoms ( 4 ) have been synthesized and structurally characterized by experimental X‐ray analyses and theoretical calculations at the semiempirical (AMI) and ab initio (HF/6–31G*) levels. The results show that these compounds meet the required criteria to act as potential calcium channel modulators.     

Chemical force microscopy study of adhesive properties of polypropylene films: influence of surface polarity and medium

The adhesive properties of untreated and corona treated polypropylene (PP) films were studied in polar (water) and nonpolar (hexadecane) liquid medium by using chemical force microscopy. A gold-coated colloidal probe was sequentially modified with self-assembled monolayers (SAMs) of omega-functionalized alkanethiols. The same colloidal probe was used for the force measurements, to avoid influence of determination accuracy of the spring constant and sphere radius on the obtained results. The thermodynamic work of adhesion was determined from the measured pull-off force using the Johnson-Kendall-Roberts (JKR) adhesion theory. Rabinovich's model was applied for the consideration of an effect of roughness when calculating the work of adhesion. It was found that the work of adhesion correlates with the hydrophilic properties of the PP surface and SAMs as well as with the polarity of the liquid medium. The observed correlations agree well with those found for the work of adhesion calculated from contact angle measurement.     

Synthese und struktur von dicyclopentadienyl(trimethylsilyl)titanchlorid

Dicyclopentadienyl(trimethylsilyl)titanium chloride, a stable trimethylsilyltitanium compound, is synthesized by reaction of dicyclopentadienyltitanium dichloride and tris(trimethylsilyl)aluminium, coordinated with diethyl ether, or lithium tetarakis(trimethylsilyl)aluminate. The IR and NMR spectra are reported. The crystal structure of the title compound has been determined. It shows a distorted tetrahedral surrounding of the titanium atom; the Ti–Si distance is 267 pm.     

Pragmatic Studies on Protein-Resistant Self-Assembled Monolayers

Summary. The present study describes new synthetic routes to oligo(ethylene glycol)-terminated alkanethiols (OEG-ATs), starting from α,ω-dibromoalkanes, which are reacted either with OEG or with trityl mercaptan in the first step. In addition to these ether conjugates of OEG and AT, analogous ester and amide conjugates were prepared by established procedures. All thiols were used to form self-assembled monolayers (SAMs) on cleaned gold surfaces and these were stored for 1–2 weeks under water at 4°C before the extent of nonspecific protein adsorption was tested with IgG, BSA, and lysozyme at 1 mg cm⁻³ protein concentration in phosphate-buffered saline. Under these practice-oriented testing conditions, SAMs with tri(ethylene glycol) chains (EG ₃) exhibited nonsatisfactory protein resistance, in sharp contrast to EG ₄ or longer OEG chains. The effectiveness of EG ₃ was partially restored when they were linked to a long acyl chain (16-mercaptohexadecanoic acid) instead of 12-mercaptododecane or 11-mercaptoundecane. Furthermore it was found that (i) SAM formation at 20 μM thiol versus 500 μM OEG-AT gave identical results, (ii) gel-filtered proteins were much less adsorbed than the unpurified commercial products, and (iii) the method for gold-precleaning was very critical. In conclusion, this study offers convenient synthetic routes to OEG-AT and helps to choose molecules and procedures for reliable preparation of protein-resitant SAMs with prolonged stability during storage.     

Synthesis of flavone-3-sulfonylureas

The synthesis of new flavone-3-sulfonylurea derivatives is hereby described. The influence of a phenyl group in the 2-position and an acetate group in the 8-position at the chromone nucleus on the activity was studied. Only weak cytostatic activity of the new compounds was found.