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QUATERNARY AMMONIUM SALTS

QUATERNARY AMMONIUM SALTS. Stanis l aw WITEK Wroc l aw University of Technology E-mail: stanislaw.witek@pwr.wroc.pl. QAS - GENERAL PROPERTIES. Synthetic QAS – large group of chemical compounds of different application: Cationic surfaktants Catalyst in chemical reactions

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QUATERNARY AMMONIUM SALTS

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  1. QUATERNARY AMMONIUM SALTS • Stanislaw WITEK • Wroclaw University of Technology • E-mail: stanislaw.witek@pwr.wroc.pl

  2. QAS - GENERAL PROPERTIES • Synthetic QAS – large group of chemical compounds of different application: • Cationic surfaktants • Catalyst in chemical reactions • Biocides (bactericides, fungicides, plant growth regulators)

  3. QAS - GENERAL PROPERTIES • About 100 QAS compounds found in the • nature and isolated from the living • systems, among them well known QAS as choline and glycinebetaine

  4. RETARDANTS chlormequate chloride (CCC) retardant for wheat (shortening ca 26%)

  5. RETARDANTS N,N-dimethylmorpholinium chloride (RW-3)

  6. RETARDANTS Synthesis of N,N-dimethyl-2-oxo-morpholinium chloride (RW-13)

  7. RETARDANTS • RW-3 has a very good retardants activity (shortening of wheat steam ca.26 % like chlormequate chloride) and also a good activity as growth stimulant of leguminous plants • RW-3 was applied as growth stimulant for flax (elongation of flax steam ca. twice and enhancing of seed yeld up to 50%)

  8. NITROVINYL QAS GENERAL FORMULA

  9. NITROVINYL QASSTARTING COMPOUNDS • R=H (B1) R=H (C1) R=H (D1) • R= Me (B2) R=Me (C2) R=Me (D2)

  10. NITROVINYL QASSTARTING COMPOUNDS • Transformation of p-tolunitryl into p-chloromethyl benzaldehyde

  11. NITROVINYL QASSTARTING COMPOUNDS • Chloromethylation of salicylaldehyde

  12. NITROVINYL QASSTARTING COMPOUNDS synthesis of nitrovinyl derivatives

  13. NITROVINYL QAS • Quaternization of tertiary amines

  14. NITROVINYL QAS

  15. NITROVINYL QAS • J.Kołodyński, S.Ułaszewski, D.Grobelny, R.Witkowska, S.Witek, T.Lachowicz, Acta Microbiol. Polon., 1984, 33, 119

  16. NITROVINYL QAS - resume • β- nitrovinyl salts are unstable, β-methyl- β-nitrovinyl compounds are more stable • Nitrovinyl QAS have high fungicidal activity against Botritis cinerea and Alternaria tenuis, especially C12-C14 alkyl and morpholinium derivatives • Nitrovinyl salts are very active biocides against slimes in water cooling systems (M.Rucka at.al, Environ.Protec.Eng.,1983.9.25) • Nitrovinyl substituent enhanced biological activity, interaction with biological membranes and transport of Ca+2 ions through those membranes

  17. NITROVINYL QAS - resume • In relativelu low concentration eflux of internal aminoacids from the yeast cells is observed and next disruption of the cell membrane (J.Kołodyński,at.al, Acta Microbiol. Polon., 1984, 33, 119) • An essential role in those processes play a nitrovinyl substituent and aromatic ring which together give a planar system with delocalized electrons and are probably responsible for deeper penetration of long chain alkyl into the membrane bilayer

  18. ALKOXYMETHYL QAS R-OH + (CH2O)x + HCl -------- R-O-CH2-Cl

  19. ALKOXYMETHYL QAS

  20. ALKOXYMETHYL QAS -resume • Simple synthesis and relatively stable products • C12-C14 alkyl morpholinium and piperidinium salts are of highest activity against B.cinerea and A.tenuis and also as biocides for water cooling systems (B.Rucka at.al., Environ.Protec.Eng., 1981,7,45) • Dodecyl morpholinium salts was proofed for protection of apple trees against Venturia inaequalis in field experiment; in concentration 500 ppm a full defoliation was observed. Using a compound as ionic pair with SDS give no better results

  21. GLYCINE DERIVATIVES • mono and bis QAS of glycine esters

  22. GLYCINE DERIVATIVES -resume • Glycine monosalts were less active in pesticide screening-test than two previous presented groups. Also their interaction with membranes was smaler; details of this will be present in the next lecture • It was found a good activity of monosalts against Salmonella sp. and a good activity against slimes in cooling systems • Gemini salts were more active than monosalts;, maximum of activity in the test of inhibition of yeast growth was at C8 alkyl chains

  23. PHENOLIC ANTIOXIDANTSRESEARCH PROGRAMME • design and synthesis of QAS with antioxidant fragment which are able to be incorporated into a membrane with localization of the antioxidant part under or on the surface of the membrane • Proof of QAS application for inhibition of lipids oxidation as a tool for protection of membranes, cells and food against oxidative destruction

  24. PHENOLIC ANTIOXIDANTS • Synthesis of starting methyl cinnamate

  25. PHENOLIC ANTIOXIDANTS

  26. PHENOLIC ANTIOXIDANTS ABREVIATIONS

  27. PHENOLIC ANTIOXIDANTS

  28. PHENOLIC ANTIOXIDANTS

  29. PHENOLIC ANTIOXIDANTS

  30. PHENOLIC ANTIOXIDANTS

  31. PHENOLIC ANTIOXIDANTS

  32. PHENOLIC ANTIOXIDANTS • Phenolic antioxidants (PhA) have low activity as inhibitors of yeast S.cerevisiae growth. • PhA were tested for their activity as inhibitors of oxidation (autoxidation) on erythrocytes membranes and erythrocyte membrane lipids (ghosts) as well as highly unsaturated olive oil and and on oxidant-sensitive yeast species (Schizosaccharomyces pombe, S.cerevisiae and Rhodotorula glutinis)

  33. PHENOLIC ANTIOXIDANTS • PhA have very high inhibitory activity at extrimely low concentrations (in some cases < 10μM) • Erythrocytes membranes are fully protected at concentration 2 – 3 order lower than hemolytic concentration. • PhA protect olive oil at concentrations lower ca 2 order than commonly use antioxidant BHT

  34. PHENOLIC ANTIOXIDANTS • Przestalski S at.al: Interaction between model membranes and a new class of surfactants with antioxidant function, Biophys. J. 1996, 70, 2203-2211 • Kleszczyńska H.at.al : Inhibition of lipid peroxidation in the erythrocyte membrane by quaternary morpholinium salts with antioxidant function, Z. Nat.forsch., C 1998, 53, 425-430 • Krasowska A.at.al: New phenolic antioxidants of PYA and PYE class increase the resistance S.cerevisiae strain SP4, its SOD- and catalase-deficient mutants to lipophilic oxidants, Folia Microbiol. 1999, 44, 657-662

  35. PHENOLIC ANTIOXIDANTS • Kleszczyńska H.at.al : Protective effect of quaternary piperidinum salts on lipid oxidation in the erythrocyte membrane.. Z. Nat.forsch., C J. Biosci. 1999, 54, 424-428 • Kleszczyńska H.at.al: Antioxidative activity of pirolidinium salts in erythrocyte membrane. Pol. J. Environ. Stud. 2000, 9, 475-478, • Krasowska A. at.al: The antioxidant activity of the BHT and new phenolic compounds PYA and PPA measured by chemiluminescence, Cell. Mol. Biol. Lett. 2001, 6,71-81 • Witek S. i wsp.: Środek do ochrony tłuszczów przed oksydacyjmą destrukcją, patent polski, Nr 195707( 2007)

  36. PHENOLIC ANTIOXIDANTS • Krasowska A.at al.: Suppresion of Radical-Induced Lipid Peroxidation in a model system by alkyl esterd os cinnamate quaternary ammonium salts, Z.Naturforsch.2001, 56C • Krasowska A. at.al: Spontaneous and radical-induced plasma membrane lipid peroxidation in differently oxidant-sensitive yeast species and its suppresion by antioxidants, Folia Microbiol.,2000,45,509-514 • Kleszczynska H. at al..: Inhibition of lipid peroxidation in the erythrocyte membrane by quaternary morpholinium salts with antioxidant function,Z.Naturforsch.,1998,53C,425-430

  37. RESEARCH TEAM • University of Wroclaw: • prof. T. M. Lachowicz, prof. S.Ułaszewski, dr E, Obłąk,dr A. Krasowska, dr M. Bień, dr J.Piątkowski • Wroclaw University of Natural Sciences: • prof. S. Przestalski, prof. J. Kuczera, prof. H. Kleszczyńska, prof. J. Gabrielska, dr J. Sarapuk • Wroclaw University of Technology: • Dr D. Grobelny, dr M. Oświęcimska, dr J. Łuczyński, mgr B. Rutkowski, inż. A. Kołodziejczyk, J. Radwańska

  38. RESEARCH TEAM Catholic University, Louvain-la-Neuve, Belgium prof. Andre Goffeau, dr Marcin Kołaczkowski, dr Anna Kołaczkowska, Józef Nader. Institute of Microbiology Czech Akademy of Sciences, Praha: prof. Karel Sigler

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