Hexanal, 2-heptenal, and nonanal were identified as relevant reaction products formed in the course of the lipid peroxidation of heated peanut oil. For the identification of potential amino acid side chain adducts, kinetic studies between N(α)-benzoylglycyl-l-lysine as a model for protein-bound lysine and trans-2-heptenal were performed, showing a strong decrease of the lysine-derivative whereupon the loss of trans-2-heptenal was moderate. Following acid hydrolysis of the incubation mixture of N(α)-acetyl-l-lysine and trans-2-heptenal, two UV-active major lipation products were observed, isolated and identified as isomeric pyridinium-derivatives, namely (Z)- and (E)-1-(5-amino-5-carboxypentyl)-4-butyl-3-(pent-1-en-1-yl)pyridin-1-ium (cis- and trans-BPP-lysine). After heating of a native peanut protein extract with trans-2-heptenal, both derivatives were quantitated by LC-ESI-MS/MS after acid hydrolysis and the modification of lysine was measured by amino acid analysis. At low, "food-relevant", concentrations of trans-2-heptenal, up to 80% of the lysine modification could be explained by the formation of cis- and trans-BPP-lysine, showing that these two lipation derivatives represent good markers for a protein modification by the lipid peroxidation product trans-2-heptenal.
Professor Dr. Josef Schurz zum 65. Geburtstag gewidmet Es werden Aussagen zu den Wechselwirkungen zwischen N-Methylmorpholin-N-oxid und einer zweiten protischen oder aprotischen Losungsmittelkomponente fur Cellulose getroffen. Als Untcrsuchungsmethoden dienten DSC-, 'H-NMR-, FTIR-und RWWS-Messungen. Um den Celluloselosemechanismus zu erklaren, wurden einige Modellsubstanzen rnit OH-Gruppen in binaren Systemen rnit NMMNO untersucht. Die hier und in fruheren Mitteilungen erhaltenen experimentellen Ergebnisse werden hinsichtlich der Losewirkung von Mischungen aus NMMNO .I H,O und unterschiedlichen Zweitkomponenten gegenuber Cellulose zusammenfassend diskutiert. mccneaoeanu pacmeopenus ~e~znwn03b~ 8 6unapnaix anpomuuecmx cucmeaax. 3 . C00624. Nccnedoeanm eaaumoaefic m e u mmcay ornaefibnacau komnonenmuu pacmeopumeneii an8 yennwnoaac u 06 yaicaenm o mexanuaae pacmeopenm PaCCMaTpHBaeTCH B3aWMOAe&CTBHe MeHtAY N -M e T H J I M O p~O J I H H -N -O K C~A O M (NMMNO) H BTOPHM IIPOTHYeCKHM HJIH aIIpOTHYeCKHM KOMIIOHeHTOM PaCTBOpllTeJIH AJIH UeJIJIIoJI03E.I. MCCJIeAOBaHHH IIpOBOAHJIHCb C lXOMOLQbI0 ACH, 'H-HMP, @T~~-CIIeKTpOCKOIIHH I4 MeTOAOM PaCCeHHElH PeHTreHOBCHHX JIyYei H a 6 o n b r u~x YrJIaX. q~0 6 b 1 BPHCHHTb MeXaHH3M PaCTBOPeHHH qeJIJIIOJI03bI HCCJIeAOBaJIH HeKOTOpbIe MOAeJIbHbIe BeLQeCTBa C OH-rpynnaME B ~IIHIPHUX CHCTeMaX C NMMNO. nOJIyYeHHbIe B A a H H O i W B IIpeAbIAyQHX patjo~ax pe3yJIbTaTbI 0 6 c y x f l a 1 0~c~ OTHOCHTeJIbHO paCTBOpFIIOQe2f CnOCO6HOCTH AJIH qeJIJIIoJI03bI CMeCefi NMMNO * 1 HzO C paaJIH'4HbIMki KOMIIOHeHTaMH. Investigation of the solution of cellulose in binary aprotic systems. 3rd Comm. Study of the interaction between the individual solvent components and discussion of the solution mechanismInteractions between N-methylmorpholine-N-oxide and a second protic or aprotic solvent component for cellulose are considered. For the experimental investigations DSC, lH-NMR spectroscopy, FTIR spectroscopy, and WAXS were employed. To obtain informations on the mechanism of cellulose dissolution, some model compounds containing OHgroups were investigated in the appropriate binary solvent systems. The results obtained here and in our previous publications are discussed with regard to the solvent action of binary systems with NMMNO.1 H,O on cellulose.
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