Poly(hydroxycarboxylate) — ihre Herstellung und ihre Eigenschaften als Komplexbildner mit Metallionen

Zusammenfassung An Acrolein—Acrylsäure-Copolymerisaten ist bereits in wäßr. MediumCannizzaro-Reaktion zu Poly(hydroxycarboxylaten) möglich; dabei sind an bestimmten Typen sogar Reaktionsabläufe bis zum praktisch vollständigen, stöchiometrischen Umsatz erreichbar. Auf diesem Wege wurden Polyelektrolyte vom Typ der Poly(hydroxycarbonsäuren) bzw. deren Alkalisalzen hergestellt. Die Produkte bilden Komplexe mit Metallionen, deren Stabilität vom Zahlenverhältnis Carboxylat-: Hydroxyl-Gruppen sowie von der herstellungsbedingten Struktur der Polymeren abhängt. Eingehendere Messungen an den Ca⁺⁺-Komplexen zeigen, daß mit steigendem Verhältnis Carboxylat: Hydroxyl Maxima der Komplexstabilitätskonstanten durchlaufen werden.

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Polyhydroxycarboxylates, preparation and properties as sequestering agents for metal ions

Salts of acrolein—acrylic acid copolymers undergoCannizzaro reaction already in aqueous medium; under these conditions, for certain types of them it is possible to reach almost complete reaction. Using this reaction, polyelectrolytes of the group of poly(hydroxycarboxylic-acids) and their alcali salts respectively, were prepared. The products act as sequestering agents for metal ions. Depending on the carboxylate: hydroxyl-number ratio and on the chemical structure as a consequence of the production process, the polymers form metal ion complexes of different stability. As to the complexes with Ca⁺⁺-ions, more detailed investigations show the stability constants of these complexes going through maxima with rising values of the carboxylate: hydroxyl-ratio.

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Mit 4 Abbildungen

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Herrn Prof. Dr.H. Nowotny gewidmet.     

Polymer complexes. XVI

Polymer complexes of 5-vinylsalicylidene aniline with some transition metal salts were prepared and characterised by elemental analyses, IR, electronic spectroscopy and magnetic moment measurements. Thermal stabilities of the polymer complexes were compared with poly(5-vinylsalicylidene) aniline homopolymer, and the order of stabilities of the complexes was given. The activation energies of the polymer complexes were calculated.

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Zusammenfassung Polymerkomplexe von 5-Vinylsalizylidenanilin mit einigen Übergangsmetallsalzen wurden dargestellt und mittels Elementaranalyse, IR, Elektronenspektroskopie und magnetischen Momentmessungen charakterisiert. Die thermische Stabilität der Polymerkomplexe wurde mit der des Homopolymers Poly(5-Vinylsalizyliden)-anilin verglichen. Die Aktivierungsenergien der Polymerkomplexe wurden berechnet.

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Part XV, Poly. Deg. Stab., 29 (1990) 271.     

Eisen-, Kobalt- und Nickel-Cyanokomplexe mit bifunktionellen Phosphonium-Kationen Phosphororganische Derivate von Übergangsmetall-Cyanokomplexen, 2. Mitt

Zusammenfassung Es wurden die Derivate von Eisen-, Kobalt- und Nickel-Cyanokomplexen mit bifunktionellen Phosphonium-Kationen dargestellt und untersucht. Bei Eisen und Kobalt sind neben Phosphonium-Komplexen auch Phosphonium—Wasserstoff-Verbindungen zu erhalten. Thermische Untersuchungen ermöglichten die Aufklärung der Zersetzungsprozesse dieser Derivate. Die vermessenen _CN- und _NO-Valenzschwingungen wurden mit denen der Alkalisalze bzw. freien Säuren verglichen. Die Thermolyse der Phosphonium—Wasserstoff-Komplexe führt zu koordinativ ungesättigten isolierbaren Zwischenstufen.

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Organophosphorus derivatives of transition metal complex cyanides

The derivatives of cyano complex compounds of iron, cobalt and nickel with bifunctional phosphonium-cations were prepared and investigated. In the case of iron and cobalt the phosphonium—hydrogen derivatives can be produced too beside those of the phosphonium-complexes. The thermal decomposition of the compounds was examined by the derivatographic method. The _CN and _NO stretching frequencies of the complexes were compared with the similar frequencies in those of the alkaline cyano complexes and their corresponding free acids. The thermal decomposition of phosphonium—hydrogen—cyanometallates leads to coordinatively unsaturated intermediates which can be prepared.

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Als 1. Mitt. gilt:S. Papp, S. Kovács undI. Liszi, J. inorg. nucl. Chem.34, 3111 (1972).     

Synthesis,spectroscopy, thermal and biological aspect of novel six‐coordinated dimeric iron(III) mixed‐ligand complexes

The mixed‐ligand complexes of iron(III) with 1‐cyclopropyl‐6‐fluoro‐4‐oxo‐7‐piperazin‐1‐yl‐1,4‐dihydroquinoline‐3‐carboxylic acid and various neutral bidentate Schiff base ligands were prepared. The structure of mixed‐ligand complexes was investigated using spectral, physicochemical and elemental analyses. Biocidal activity was determined using agar plate technique against Staphylococcus aureus, Bacillus subtilis, Bacillus cereus, Salmonella typhi, Escherichia coli and Serratia marcescens . The result showed a significant increase in a biocidal activity compared with parent ligands, metal salts and standard drugs (ofloxacin, levofloxacin). DNA binding and cleavage studies were carried out using absorption titration and gel electrophoresis techniques, respectively. The binding constant of Fe(III) complexes was obtained in the range 2.5–4.0 × 10⁴ M ^?1. The DNA binding and cleavage efficacy were raised in mixed‐ligand complexes as compared with parental ligands and metal salts. Copyright © 2008 John Wiley & Sons, Ltd.     

Die Reaktion der Ferrisalze mit der Isonitroso-thioglykolsäure

Zusammenfassung Die Farbreaktion der Ferrisalze mit der Isonitroso-thioglykolsäure wurde durch die Isolierung dreier basischer innerer Komplexsalze mit 1 bzw. 2 Mol der Säure aufgeklärt (I, II, III). Das Eisen bindet mit der Hauptvalenz das Schwefelatom, mit der Nebenvalenz den Sauerstoff der Carbonylgruppe. Erfassungsgrenze der blauen Färbung 3 Eisen bei der Grenzkonzentration 1:7333000.

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Summary The colour reaction of the ferric salts with the isonitrosothioglycolic acid was enlightened by the insulation of three basic inner complex salts with 1, respectively 2 moles of the acid (I, II, III). The iron is fixed by the principal valency to the sulphur atom, by the secondary valency to the oxygen of the carbonyl group. Limit of identification of the blue colour 3 Fe; concentration limit 1:7333000.

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Résumé (W) Le réaction colorée des sels ferriques avec l'acide isonitrosothioglycolique a été expliquée en isolant trois sels complexes internes basiques, avec respectivement une ou deux molécules d'acide (I. II, III). Le fer avec valence principale, se lie à l'atome de soufre, tandis qu'avec une valence secondaire, il se lie à l'oxygène du groupe carbonyle. Limite de perceptibilité: 3 de fer, avec une limite de dilution: 1:7333000.

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(Experimentell ausgeführt vonB. Mareth.)

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XVI. Mitteilung: Chem. Listy34, 307 (1940)     

Effect of the Alkali-Metal Cations On the Protonation Constants of Myo-Inositol Hexakis(Phosphate)

Abstract

Values for the protonation constants of myo-inositol hexakis(phosphate) have been determined at 25°C and 0.1 M ionic strength by potentiometry in media containing two different concentrations of Li⁺, Na⁺, K⁺ and Cs⁺ salts.

The Alog K_yHM values, which correspond to the differences between the constants obtained with and without alkali-metal cations, are considered as being related to the binding ability of the ligand towards these cations.

Their relative behaviour is then analysed and some conclusions are drawn about the conformations which might be adopted by the complexes in different pH regions.     

New terpyridine derivatives of thiacalix[4]arenes in solution and at the water-air interface

New di- and tetrasubstituted thiacalix[4]arenes in cone and 1,3-alternate configurations containing terpyridine and triazole fragments at the lower rim of the macrocycle, as well as model triazole-terpyridine, are synthesized. The structures and purity of the compounds are confirmed by NMR spectroscopy and high-resolution MALDI mass spectrometry. The compounds form luminescent complexes with lanthanide cations (europium and terbium) in a chloroform-methanol (10: 1) system during fluorimetric titration. The possibility of antenna ef ect during fluorescence sensitization in lanthanides by the thiacalixarene ligands is demonstrated. Successful immobilization of the terpyridine receptors on a solid substrate makes it possible to consider the Langmuir-Blodgett films on the basis of these receptors as promising adsorbents of lanthanide from nonaqueous media or organic salts and also provides new opportunities for the investigation of the luminescence characteristics of lanthanide complexes in thin films.

     

Synthese und kernresonanzspektroskopische Untersuchung von Hexahydro-oxazolopurinen

Zusammenfassung Bei der Umsetzung von 8-Chlor- und 8-Brom-theophyllin oder deren Kaliumsalzen mit 3-Chlor-1,2-epoxypropan oder 3-Brom-1,2-epoxypropan entstehen halogenmethyl-substituierte Hexahydro-oxazolopurine. Die Struktur der auf diese Weise synthetisierten Verbindungen sowie von Epoxypropyl-theobrominen und-theophyllin wird kernresonanzspektroskopisch untersucht.

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Synthesis and NMR studies on hexahydro-oxazolopurines

The reaction of 8-chloro- and 8-bromo-theophylline or the potassium salts of these compounds with 3-chloro-1,2-epoxypropane or 3-bromo-1,2-epoxypropane affords halogenmethyl-substituted hexahydro-oxazolopurines. The structure of the compounds synthesized in this way and of epoxypropyltheobromines and-theophylline were studied by¹H-NMR-spectroscopy.

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Aus der DissertationK. H. Kleine, Freiburg i. Br. 1969.     

Dinuclear trivalent chromium,manganese, iron and cobalt complexes bridged by aromatic diamines

Summary Trivalent chromium, manganese, iron and cobalt salts react withm-phenylenediamine and acetylacetone to give complexes of the type [M(C₁₆H₁₈N₂O₂)X]: X = Cl, Br, NO₃ or NCS for M = chromium(III) and iron(III); X = Cl, Br, OAc or NCS for manganese(III); and X = OH for cobalt(III). Conductance measurements show the complexes to be nonelectrolytes. Molecular weights determined cryoscopically, show the iron complexes to be dinuclear. Magnetic measurements above 85 K reveal the presence of slight antiferromagnetic interactions. The complexes are dimeric five-coordinate square-pyramidal withm-phenylenediamine residues acting as bridges. The electronic spectra are interpreted in terms of the Normalised Spherical Harmonic Hamiltonian Theory and the DT/DQ values which indicate that chromium complexes are slightly distorted, whereas those of manganese are severely distorted.     

Über Metallkomplexe der Heteroarylformazane

Two new heteroarylformazans with two complex forming carboxy groups in the ortho position relative to the formazan chain have been synthesized. These compounds form complexes with uranyl, cobalt and nickel ions. The ratio metal/formazan of these complexes has been investigated.

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Teil der Dissertation,. Kaban, Univ. Istanbul 1975.     

Untersuchungen zur adsorptiven Anreicherung von Elementspuren an Adsorberharzen

Summary The adsorbability of metalhalogenocomplexes of 18 elements from hydrochloric or hydrobromic acid solutions on activated carbon, Amberlite XAD-4 and XAD-7 resins was examined. Only few of the complexes are selectively adsorbed with high adsorption rates. The preconcentrated elements can easily be eluated from the resins by 1 mol/l HCl in acetone and subsequently be determined by AAS. By addition of basic dyes, quaternary ammonium and tetraphenylphosphonium salts the adsorption rates of metallogenocomplexes are generally enhanced. The adsorption behaviour of the complexes is similar to that of corresponding solvent extraction systems.

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Teil I: Fresenius Z Anal Chem (1987) 327:179     

Über Kobalt- und Nickelkomplexe der heterocyclisch substituierten Azomethine

The cobalt and nickel complexes of some heterocyclic substituted azomethins have been synthesized. Metal/azomethine ratio of these complexes has been studied.

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Teil der Dissertation,. Kaban, Univ. Istanbul 1975.     

Trennung schwefelhältiger und schwefelfreier organischer verbindungen mit Hilfe von Quecksilbersalzen

Zusammenfassung Durch Ausschütteln mit verschiedenen Quecksilbersalz-lösungen und nachfolgende Regenerierung konnten bestimmte organische Schwefelverbindungen, wie sie in stark schwefelhältigen Schieferölen vorkommen, voneinander und von schwefelfreien Substanzen getrennt werden.

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Certain sulfur compounds whose occurence is characteristic of shale oils of high sulfur content were separated from each other and from sulfur-free substances by extraction with solutions of different mercury salts.

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Herrn Prof. Dr.H. Bretschneider zum 60. Geburtstag gewidmet.     

Transition metal complexes of α-aminophosphonates part II: Synthesis,spectroscopic characterization,and in vitro anticancer activity of copper(II) complexes of α-aminophosphonates

Abstract

A one pot procedure was used to synthesize two new derivatives of α-aminophosphonates. Novel copper(II) complexes of α-aminophosphonates were synthesized by coordinating different copper salts with the newly synthesized α-aminophosphonates. Their structures were characterized by different spectral and analytical techniques. Evaluation of the metal-free ligands HL1, HL², and their Cu(II) complexes against human colon carcinoma HT-29 cell lines was performed, using cisplatin as a reference drug. The results indicated that the complexes of the ligand HL¹ exhibited enhanced anticancer activity, while ligand HL² complexes showed decreased anticancer activity.     

Neue rhodanilatähnliche Verbindungen mit Morpholin

Substitution reactions of K₃[Cr(NCS)₆] with morpholine were studied. The formula of the complex anion, [Cr(NCS)₄(morph)₂]^–, was established.23 new complex compounds of these types have been prepared from the hydrochlorides of some aliphatic or heterocyclic amines, alkaloids and cobalt(III)ammine bases resp.Their thermal behaviour and the mechanism of pyrolysis of these salts was studied by derivatographic methodes. From UV and IR spectra some structural problems are resolved and discussed.

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Mit 3 Abbildungen     

Trennung chemisch sehr nahe verwandter Elemente durch Fällung unter Dekomplexierung mittels Austausch-und Verdrängungsreaktionen (Displacement)

Zusammenfassung Durch einen gekoppelten Komplex-Dissoziations-Assoziationsvorgang derSE-ÄDTE-Komplexe mit Co-, Cu- oder Ni-Salzlösungen werden dieSE-Kationen beliebig langsam entwickelt und bei Anwesenheit von Fällungsmitteln dieSE-Ionen nach den Bedingungen der Fällung im homogenen Medium selektiv gefällt. Es werden wirkungsame Trennungen bzw. Reinstdarstellung der Ceriterden und insbesondere die Reindarstellung von Pr und Nd beschrieben.

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Separation of very closely related elements by precipitation and simultaneous decomplexation accompanied by exchange and displacement reactions.

Rare earth ions were found to be released from theirEDTA complexes at arbitrary rates in acoupled dissociation-association reaction with Co-, Cu- and Ni-salts, respectively. In the presence of precipiting in agents the rare earth ions are selectively precipitated in homogeneous media. Highly effective separations, preparation of ultra-pure samples of the cerite metals and the preparation of pure samples of Pr and Nd are described.

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Palladium(II) N-heterocyclic carbene complexes: synthesis,structures and cytotoxicity potential studies against breast cancer cell line

Abstract

Mononuclear trans-Pd(II)–NHC complexes (where NHC?=?N-heterocyclic carbene) bearing asymmetrically substituted NHC-ligand have been synthesized via transmetalation reaction between Ag(I)–NHC complexes and [Pd(NCCH₃)₂Cl₂]. The NHC precursors are accessible in two steps by N-n-alkyl reactions of benzimidazole. The resultant benzimidazolium salts were deprotonated with Ag₂O by in situ deprotonation to facilitate the formation of mononuclear Ag(I)–NHC complexes. Single-crystal structural study for Pd(II)–NHC shows that the palladium(II) ion exhibits a square-planar geometry of two NHC ligands and two chloride ions. The cytotoxicity study was investigated against breast cancer cell line (MCF-7). The Ag(I)–NHC complexes exhibit better activities than their corresponding Pd(II)–NHC complexes, whereas all benzimidazolium salts are inactive toward MCF-7 cancer cell line.     

Optische Rotationsdispersion und Circulardichroismus bei Jod-Polysaccharid-Komplexen

Zusammenfassung Die wäßrigen Lösungen der Jodkomplexe von Stärke, verschiedenen Amylosen und Amylopektinen zeigen im Bereich der betreffenden Absorptionsmaxima einen induzierten positiven Cotton-Effekt. Die Drehwerte hängen in der gleichen Weise vom Jod-Amylose-Verhältnis ab wie die Extinktionen bei 660 und 445 m. Die Drehwerte einiger Jod-Polysaccharid-Komplexe nehmen mit der Zeit stark zu, obwohl die Extinktion konstant bleibt. Maßnahmen, durch welche die Struktur der Jod-Einschlußverbindung verändert wird (Erwärmung, Zusatz von Salzen, Lösungsmitteln, Harnstoff, Netzmitteln) haben einen starken Einfluß auf den induzierten Cotton-Effekt.

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Summary Aqueous solutions of iodine complexes with starch, different samples of amylose or amylopectin show an induced positive Cotton effect in the region of the absorption maximum. The rotatory power and the extinction at 660 and 445 m depends upon iodine amylose ratio. The optical of some complexes increases with time, whereas the absorption remains constant. Experimental conditions which change the structure of the channel complexe (heating, addition of salts, solvents, urea or detergents) influence the induced Cotton effect.

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Mit 8 Abbildungen in 9 Einzeldarstellungen und 1 Tabelle

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2. Mitt. J. macromol. Sci. Chem.A2 im Druck; 1. Mitt.R. Wolf undR. C. Schulz, Tetrahedron Letters1967, 1799.

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Vortrag anläßlich der 23. Arbeitstagung der Kolloid-Gesellschaft in Bad Oeynhausen 27. 10. 1967.

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Auszug aus der Dissertation vonH. Mayerhöfer, Mainz 1967, D. 77.     

Dehydratisierung von Butanolen an Hartstoffcarbiden

The dehydration of 1-butanol and 2-butanol was studied in a microcatalytic reactor over refractory carbides (except Hf and Cr) in a temperature range between 40 and 500°C. The activity was comparable with that of oxides and salts. Varying the pulse size, the surface coverage — and the amount of reaction products—was found to be in good correlation with aLangmuir adsorption isotherm. Heats of adsorption and activation energies were calculated from experiments at different temperatures, the activation energies, using two different methods with good agreement. The activity of the refractory carbides increased in the periodic table of the elements from the left to the right and from bottom to top, as observed with salt-catalysts.

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Auszugsweise vorgetragen bei der 75. Hauptversammlung der Deutschen Bunsengesellschaft für Physikalische Chemie in Saarbrücken, 26. bis 29. Mai 1976.     

Photochemische Synthese von Eisencarbonylclustern

Zusammenfassung Die UV-spektroskopische Analyse der Spektren wäßrigäthanol. Lösungen von Pentacarbonyleisen während der Bestrahlung zeigt das Auftreten des Ions Hydrogen-undecacarbonyltriferrat [HFe₃(CO)₁₁]^–. Aus Tetraarylphosphoniumbromiden und Pentacarbonyleisen in Äthanol können bei 10–15°C photochemisch Salze des Typs [PR₄]⁺[HFe₃(CO)₁₁]^– hergestellt werden. Die Röntgenphotoelektronenspektren (ESCA-Spektren) des Eisenclusters [HFe₃(CO)₁₁]^– enthalten für dasL _III-Niveau (2p_3/2) des Eisens zwei Emissionsmaxima, deren Auftreten im Einklang steht mit dem aus den Röntgenstrukturanalysen undMößbauerspektren abzuleitenden Vorhandensein zweier chemisch nicht äquivalenter Arten von Eisenatomen in diesen Fe₃-Einheiten.

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Photochemical synthesis of iron-carbonyl clusters

The UV-spectroscopic analyses of the spectra of aqueousethanolic solutions of pentacarbonyl iron during irradiation show the appearance of the ion of hydrogen-undecacarbonyltri-ferrate [HFe₃(CO)₁₁]^–. From tetraarylphosphonium bromides and pentacarbonyl iron in ethanol salts of the type [PR₄]⁺[HFe₃(CO)₁₁]^– were prepared photochemically within the temperature of 10–15°C. The X-ray photoelectron spectra (ESCA-spectra) of the cluster [HFe₃(CO)₁₁]^– contains two maxima of emission from theL _III-level (2p_3/2) of iron. The appearance of these maxima confirm the existence of two chemically different kind of iron atoms in the Fe₃-unit of these clusters. A fact, which is known from X-ray analysis andMößbauer spectroscopy.

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Herrn Prof. Dr.F. Asinger zum 65. Geburtstag gewidmet.