Georg Manecke

Oxidation-reduction polymers

ABSTRACT This review summarizes our work on the synthesis and redox properties of polymers with various quinone–hydroquinone systems. Information is given on our attempts to increase the chemical stability of the redox resins by suitable substitution and by other methods. The redox properties were thoroughly investigated (e.g. redox potentials, redox capacity, rate of the redox reaction). A theoretical treatment is given for the redox behaviour of tetra- and hexa-valent redox systems. Redox resins can be used as insoluble, regenerable oxidants or reductants. By means of these resins some organic substrates could be dehydrogenated and several metal ions could be reduced or deposited.

On some reactive polymers and immobilized enzymes

Abstract New reactive polymer carriers with ionic or neutral hvdrophilic matrices have been synthesized. Effective were the copolymers of 3− or 4-isothiocyanato styrene and acrylic acid, copolymers of 1-vinyl-2-pyrrolidone and maleic anhydride or acrylic acid but also with acrylic acid/styrene modified with maleimide groups. As effective reactive carriers were also used polyethyleneimine, polyethyleneimine carbonic acids, poly-(allyl alcohol), polyvinylethers and various carriers of different polymer combinations containing poly(vinyl alcohol) in form of crosslinked gels, coated tubes and synthetic pulp. The ability of these individual carriers to bind enzymes was studied. Various Darameters which affect the immobilization reaction and the properties of the immobilized enzymes were investigated.

Über einige neue Aziridinverbindungen, III

Durch Addition von Aziridin an Mono- und Divinyl-p-chinone werden N-substituierte Aziridinverbindungen 2, 5, 6, 9, 11 erhalten, die zur Darstellung von Redoxharzen und im Hinblick auf ihre cytostatische Wirkung von Interesse sein Konnen. n n n nSome New Aziridine Compounds, III n n n nAddition of aziridine to mono- and divinyl-substituted p-quinones results in N-substituted aziridinyl compounds 2, 5, 6, 9, 11, which are of special interest with regard to the synthesis of redox resins and their possible cytostatic action.

Some New Nitrogen-Containing Redox Polymers

Abstract Synthesis of some new N-substituted aziridinyl compounds by the addition of aziridine to monovinyl- and divinyl-substituted p-quinones is described. The redox potentials of the monomers, their polymerization behavior, and the properties of redox polymers derived from them were investigated. Different polymerizable monosubstituted and disubstituted vinyl-4,7-indazolequinones were prepared by 1,3-dipolar addition of vinyldiazomethane to 1,4-benzoquinones. By copolymerization of 5,6-dichloro-3-vinyl-indazolehydro-quinone triacetate with 5,6-dichloro-l,3-divinyl-indazole-hydroquinone diacetate as a crosslinking agent, followed by hydrolysis and sulfalkylation of the resulting copolymer with propane sultone, chemically stable redox resins were obtained.

ON SOME REACTIVE POLYMERS AND IMMOBILIZED ENZYMES

New reactive polymer carriers with ionic or neutral hvdrophilic matrices have been synthesized. Effective were the copolymers of 3− or 4-isothiocyanato styrene and acrylic acid, copolymers of 1-vinyl-2-pyrrolidone and maleic anhydride or acrylic acid but also with acrylic acid/styrene modified with maleimide groups. As effective reactive carriers were also used polyethyleneimine, polyethyleneimine carbonic acids, poly-(allyl alcohol), polyvinylethers and various carriers of different polymer combinations containing poly(vinyl alcohol) in form of crosslinked gels, coated tubes and synthetic pulp. The ability of these individual carriers to bind enzymes was studied. Various Darameters which affect the immobilization reaction and the properties of the immobilized enzymes were investigated.

Separation of Enantiomers with Insoluble Optically Active Polymers

Crosslinked optically active polymers (OAP) were synthesized starting from optically inactive polymeric reactive carriers (e.g. sulfochlorinated or chloromethylated polystyrene) and low-molecular weight optically active amino compounds (e.g. D-α-phenylethylamine, D-ephedrine, L-alanine, L-phenylalanine, L-alanine methylester). The OAP were used as specific adsorbants for the chromatographic resolution of racemic mixtures. The influence of various substituents at both the chiral centres of the OAP and the racemic mixtures was investigated systematically. An exchange of the carbonyl group for a methyl group at both the chiral centres of the polymers or the racemic mixtures decreased the resolution efficiency. The replacement of a benzyl or methyl group by a phenyl group in the racemic mixtures influenced the resolution more than that in the polymer. A —SO2 NH— bridge between the polymeric matrix and the optically active centres was more adventageous than a —CH2 NH— bridge