Investigation of the stability of metal species with respect to liquid chromatographic separations

Summary For accurate speciation analyses it is important to know the stability of the respective species, especially in the case of metal complexes. Factors affecting the chromatographic stability of such metal species are investigated. By using thermodynamic models for complex formation and chromatographic retention equilibria the influence of species concentration, stoichiometry and excess of ligand is calculated and compared with experimental results for iron complexes (lactate, gluconate and citrate species). Iron citrate is the only species, that is chromatographed as 1:2 complex (metal: ligand), while iron lactate and gluconate are transformed to 1:1 species. Problems resulting from the coelution of different species are discussed.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

TLC-screening of important pharmaceutical substances using fluorescence detection

Summary Observation of fluorescence reactions on TLC plates is a valuable additional tool within the scope of screening procedures for many toxicologically relevant substances commonly encountered in clinical- and forensic-toxicological analysis. The reactions are based on native fluorescence without any treatment and on reactions obtained with an approved derivatization procedure. Due to the enormous sensitivity of the fluorescence detection, the method is also applicable to very low concentrations and small amounts of biological materials. The procedures described in this article have proven their high pragmatic usefulness in many practical cases.Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Structure of thin block copolymer films studied by X-ray reflectivity

Summary X-ray reflectivity may be used to determine the internal structure of thin polymer films. An electron density difference of 10% for polystyrene and polyisoprene is sufficient to distinguish between a random distribution of lamellae, complete orientation parallel to the substrate surface and a surface induced formation of lamellae. The disappearance of the lamellar Bragg-peaks, with heating of the film, shows the transition into the disordered state.     

Contributions to the synthesis of some ferrocene-containing antibiotics

This Review discusses the synthesis and characterization by our Group of new antibiotics belonging to the class of penicillins, cephalosporins and rifamycins with ferrocenyl and 1, 1′-ferrocenilene residues in the molecule. As reactants for 6-aminopenicillanic acid (6-APA) and 7-aminocephalosporanic acid (7-ACA) the following were used: 1, 1-bis(chlorocarbonyl)ferrocene, ferrocenyl sulfochloride, 1, 1′-ferrocenylenedisulfochloride and thioglycolic acids S-modified with ferrocene. In the synthesis of rifamycins, the hydrazides of the thioglycolic acids, S-modified with ferrocene, were employed as nucleophilic agents. The synthesized intermediates were characterized by elemental analysis, TLC, IR, UV and ¹H NMR spectra. The characterization of new antibiotics was made by TLC, IR and UV spectral analysis. Biological activity was tested on Gram-negative and Gram-positive bacteria. Good activity is reported towards Gram-positive bacteria in the case of derivatives containing residues of thioglycolic acid S-modified with ferrocene, the antibacterial activity being similar to that of amoxicillin, carbenicillin and cephalothin. All compounds are inactive towards Gram-negative bacteria.     

Molecular electric field mapping of some anions and cations of 2- aminopurine and 6- thioguanine

Electric fields of the anions, cations and neutral forms of 2-aminopurine and 6-thioguanine have been mapped. Certain important features of the maps are similar to those found earlier in the neutral and ionic forms of adenine and guanine. The computed electric field patterns satisfactorily explain reactive sites and biological activity of the molecules.     

Liquid crystal properties of some substituted pyrazines

A number of biphenyl, terphenyl analogues and ethynes which contain a pyrazine ring have been made and their liquid crystal transition temperatures, together with examples of birefringence measurements, are reported. All the 2,5-disubstituted pyrazine systems are liquid crystalline showing high birefringence values for the biphenyl and terphenyl analogues, whereas the 1,5-disubstituted systems are not liquid crystalline. The pyrazine ethyne systems exhibit very high birefringence values. X-ray diffraction has been used to identify the liquid crystal phases of 2-n-nonyloxy-5-(4'-propylbiphenyl-4-yl)pyrazine.     

Plant polysaccharides I. Polysaccharides ofLagochilus and their biological activity

Institute of the Chemistry of Plant Substances, Academy of Sciences of the Republic of Uzbekistan, Tashkent, fax (3712) 89 14 75. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 313–314, March–April, 1995. Original article submitted November 7, 1994.     

On the Causes and Effects of Contaminations during rf Diode Deposition of Cr-Si Alloys

Investigations to the causes and effects of contaminants at the rf diode deposition of CrSi films in a non-heated high vacuum apparatus were carried out comparing an oxygen-free fusion target with an oxygen-containing cermet target. The films of the fusion target contained considerable amounts of oxygen; analogously the oxygen concentration in the films was increased in the case of the cermet target. Moreover, hydrogen was found. The concentration of the contaminants decreased with the sputtering power, however the rate of incorporation increased. For high sputtering rates the contamination process was reproducible and independent of the plant conditioning; the deposited films were depth-homogeneous. The reasons for this behaviour lie in water sources which are activated first of all by the discharge itself. The electrical properties found are explained by the contaminants and the deposition conditions.     

Complexes in polymers IV. FTIR microscopic characterization of thin organic polymer films containing embedded transition-metal carbonyl complexes

Thin films of polystyrene (PS), poly(methyl methacrylate) (PMMA) and polystyrene-polyacrylonitrile copolymer (PS-AN), containing various embedded transition-metal complexes, have been studied by FTIR microscopy. The spatial distributions of the transition-metal carbonyl complexes throughout the thin organic polymer films have been determined by a two-dimensional IR mapping procedure. The spectral variations observed in the distribution of the metal carbonyls throughout the different polymer films are discussed. The IR data show that the technique used to prepare the organometallic-embedded thin films (viz. freeze-drying of solutions followed by hot mechanical pressing of the residues) does in general lead to homogeneous films which may eventually find industrial application, e.g. as membrane sensors for small molecules.