Studies on the germination specific α-amylase and its inhibitor of rye (Secale cereale) 3. Estimation of a-amylase inhibitor activity

Summary A method is presented for estimating the -amylase II inhibitor activity in rye and isolated preparations (inhibition of germination-specific -amylase II from germinated rye). It was established that the residual activity of -amylase activity did not decrease linearly but was retarded in dependence on the inhibitor concentration. A plot of the reciprocal of the-amylase II residual activity in dependence on the inhibitor/-amylase II mass ratio showed linearity up to 50% residual activity. From this, an estimation method has been derived. Further, a computer program has been developed to calculate the results. Finally a simplified procedure (two-point method) is proposed in order to rationalize the application. The formation of the enzyme-inhibitor complex is complete after 10 min at 35° C and a preincubation time of no more than 15 min is needed before determining the inhibitor activity. The method has been found to be convenient for the inhibitor analysis of the cereal grain, flour and purified fractions and the characterization of the -amylase II inhibitor.

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Untersuchungen zur keimungsspezifischen -Amylase und deren Inhibitor im Roggen (Secale cereale) 3. Bestimmung der -Amylase-Inhibitor-Aktivität

Zusammenfassung Es wird eine Methode zur Bestimmung der -Amylase-II-Inhibitor-Aktivität in Roggen sowie daraus isolierten Präparaten (Hemmung der keimungsspezifischen -Amylase-II aus gekeimtem Roggen) vorgestellt. Bei den Untersuchungen wird festgestellt, daß die -Amylase-II-Restaktivität mit steigendem Inhibitorzusatz nicht linear, sondern von Anfang an verzögert abnimmt. Bei reziproker Darstellung der -Amylase-II-Restaktivität gegen das Inhibitor--Amylase-II-Verhältnis besteht bis etwa 50% Restaktivität Linearität. Hieraus wird ein Bestimmungsverfahren abgeleitet. Die Berechnung erfolgt über ein speziell entwickeltes Computerprogramm. Ferner wird ein vereinfachtes Verfahren (Zwei-Punkt-Methode) vorgeschlagen, um seine Anwendung zu rationalisieren. Die Ausbildung eines stabilen Enzym-Inhibitor-Komplexes ist bei 35 °C bereits nach 10 min abgeschlossen, so daß vor der Bestimmung der Inhibitor-Aktivität eine Präinkubationszeit von 15 min ausreicht. Das Verfahren hat sich bei Untersuchungen zur Reinigung und Charakterisierung von -Amylase-II-Inhibitoren aus Roggen bewährt (vgl. 2. Mitt.).

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Explanation of symbols used for calculation A -amylase II activity (U/g) without inhibitor addition;A=1/Y - A(I) -amylase II activity in the presence of inhibitor (U/g);A (I)=O(I)·F·D/(C·t·0.1) - AI -amylase II inhibitor activity (IU/g);AI=0.5·A/X - B regression coefficient [(g amylase/U)/(g inhibitor/g amylase];B=Y/X - C -amylase II mass (g) - D -amylase II dilution (ml); volume to whichC was diluted - E -amylase II in test volume (g/0.1 ml);E=C·0.1/D - F factor for calculating maltose equivalents from the calibration curve (mol maltose) - I designation of measured values (no.) - IU inhibitor unit - J(I) inhibitor mass (g) - K(I) inhibitor dilution (ml); volume to whichJ (I) was diluted - L(I) inhibitor in test volume (g/0.1 ml);L(I)=J(I)·0.1/K(I) - N number of measured values - O(I) absorbance at 530 nm in 1-cm cell - P(I) -amylase II activity (%), relative toA(I)=-amylase II activity without inhibitor addition=100%;P(I)=A (I)·100/A(I) - R correlation coefficient - t incubation time (min); t=15 min - U -amylase II activity unit - X inhibitor/-amylase II mass ratio at 50% residual activity;X=Y/B - X(I) inhibitor/-amylase II mass ratio;X(I)=L(I)/E - Y reciprocal -amylase II activity (g/U) without inhibitor addition, calculated from the regression equation;Y(I)=Y+B·X(I);Y=1/A - Y(I) reciprocal -amylase II activity;Y (I)=1/A(I)=C·t·0.1/[O(I)·F·D]     

Carotenoid pigments in acerola fruits (<Emphasis Type="Italic">Malpighia emarginata</Emphasis> DC.) and derived products

Carotenoid composition has been investigated in acerola fruits (Malpighia emarginata DC. syn. Malpighia glabra L.) and derived products. In the ripe fruit, four major carotenoids were identified (-carotene, -cryptoxanthin, lutein, and violaxanthin) together with other minor carotenoids (neoxanthin, antheraxanthin, neochrome, luteoxanthin, auroxanthin, -cryptoxanthin-5,6-epoxide, -cryptoxanthin-5,8-epoxide, cis--carotene, and cis-lutein). An average composition for the ripe fruit has been estimated as follows: -carotene (536.55 g/100 g fw), -cryptoxanthin (417.46 g/100 g fw), lutein (99.21 g/100 g fw), violaxanthin (395.33 g/100 g fw), and total minor carotenoids (197.33 g/100 g fw). Vitamin A values are similar to those described in tomatoes and some tropical fruits such as guava and papaya. After juice-making, including a pasteurization stage as thermal processing, decreases in carotenoid content were observed as well as progress of cis-isomers and structural rearrangement of xanthophylls containing 5,6 epoxide groups. The occurrence of such modifications affected the nutritional value of fruits as well as their antioxidant capability, properties that could be used as a measurement of processing quality.     

An influence of cooking on fatty acid composition in three varieties of common beans and in lentil

The fatty acid composition of three raw and cooked freeze-dried common bean varieties (Phaseolus vulgaris), namely enjevec, Semenarna 22 and Cipro, and of the lentil (Lens esculenta), var. Anicia, was determined and the influence of storage on their composition was studied. Analyses of fatty acid composition were conducted by in situ transesterification and capillary column gas-liquid chromatography. In raw milled beans average values of about 16% saturated fatty acids (SAT), 6% monosaturated fatty acids (MUFA) and 78% polyunsaturated fatty acids (PUFA) were found. Somewhat different values of 15% of SAT, 25% MUFA and 60% PUFA were found in lentil. In cooked beans the content of all fatty acids was slightly decreased. In cooked lentil the decrease was almost 50%, but the ratios of SAT, MUFA and PUFA in both cases were practically the same. After two years of storage at 4 °C the fatty acid content in raw milled beans was unchanged, but altered in cooked ones. The amounts of linoleic (18:2, n-6) and -linolenic (18:3, n-3) acid decreased, but myristic (14:0), margaric (17:0) and arachidic (20:0) acids increased. It was found that freeze-dried cooked beans, prepared from raw seed beans, kept 2.5 years at 10 °C, have practically the same fatty acid composition as freeze-dried cooked beans 0.5 year after harvesting.     

Organochlorine pesticides and polychlorinated biphenyls in flatfish from the southern Baltic, 1983

Summary Hexachlorobenzene (HCB),-,-,- and-benzenehexachloride (BHC; HCH),p,p-DDE,o,p-DDD,o,p-DDT,o,p-DDD andp,p-DDT ( DDT) and polychlorinated biphenyls (PCBs) levels have been determined in muscle tissue of 37 turbotsPsetta maxima, 27 plaicesPleuronectes platessa and 106 floundersPlatichthys flesus netted during 1983 in a different regions in the southern part of the Baltic Sea. The mean levels found for flatfish muscle tissue related to wet weight were: 0.7, 0.88 and 1.1 g/kg HCB; 1.3, 2.6 and 3.0 g/kg-BHC; 11, 10 and 11 g/kg-BHC; 4.4, 4.9 and 5.5 g/kg-BHC;-BHC remained undetected; 17, 18 and 20 g/kg BHC; 5.1, 5.2 and 8.7 g/kg p,p-DDE; o,p-DDD remained undetected; o,p-DDT was detected in 10 of 106 samples of the muscle tissue of flounder at the mean level of 17 g/kg; 4.6, 5.0 and 7.6 g/kgp,p-DDD; 3.1, 4.0 and 11 g/kgp,p-DDT; 13, 14 and 29 g/kg DDT and 71, 66 and 94 g/kg PCBs for turbot, plaice and flounder, respectively. Generally, the levels of organochlorine pesticides and PCBs in wet muscle tissue of fish followed the increased lipids content of muscles. Some local differences in pollution pattern of organochlorines have occurred. The results are compared with levels found in flatfish collected in a different regions of the Baltic Sea during 1966–1981, and reported previously by other authors.

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Organochlorpesticide und polychlorierte Biphenyle in Plattfischen aus der südlichen Ostsee,1983

Zusammenfassung Der Gehalt von Hexachlorbenzol (HCB)-,-,- and-Benzolhexachlorid (BHC; HCH), p,p-DDE, o,p-DDD, o,p-DDT, p,p-DDD und p,p-DDT ( DDT) und polychlorierte Biphenyle (PCB) wurde in Muskelgewebe von 37 SteinbuttsPsetta maxima, 27 SchollenPleuronectes platessa und 106 FlundernPlatichthys flesus bestimmt, die 1983 in verschiedenen Regionen der südlichen Ostsee mit Netz gefangen wurden. Der mittlere Gehalt für obige Plattfische, bezogen auf das Naßgewicht, betrug: 0,7, 0,88 und 1.1 g/kg HCB; 1,3, 2,6 und 3,0 g/kg-BHC; 11, 10 and ll /kg-BHC; 4,4, 4,9 and 5,5 g/kg-BHC; -BHC blieb unentdeckt; 17, 18 and 20 g/kg BHC; 5,1, 5,2 und 8,7 g/kg p,p-DDE; o,p-DDD blieb unentdeckt; o,p-DDT konnte in 10 von 106 Proben von Flundern mit einem mittleren Gehalt von 17 g/kg nachgewiesen werden; 4,6, 5,0 und 7,6 g/kg p,p-DDD; 3,1, 4;0 and 11 g/kg p,p-DDT; 13,14 und 29 g/kg DDT and 71, 66 and g/kg PCB waren die Werte für Steinbutt, Schollen and Flunder.

     

Organochlorine pesticides and polychlorinated biphenyls in livers of cod from the southern Baltic, 1983

Summary Hexachlorobenzene (HCB), -, -, - and -benzenehexachloride (BHC; HCH),p,p-DDE,o,p-DDD,o,p-DDT,p,p-DDD andp,p-DDT (DDT) and polychlorinated biphenyls (PCB) levels have been determined in livers of 210 cod (Gadus morhua) netted during 1983 in a different regions in the southern part of the Baltic Sea. The mean levels found for cod livers related to wet weight (mg/kg) were: 0.096 HCB, 0.15 -BHC, -BHC was found in trace amounts, 0.098 -BHC, -BHC remained undetected, 0.26 BHC, 1.1p,p-DDE,o,p-DDD ando,p-DDT remained undetected, 1.1p,p-DDD, 0.39p,p-DDT, 2.6 DDT and 7.2 PCB. The levels of DDT, BHC and HCB found are comparable with those noted in livers taken from cod of the same length class and netted in 1981, whilst-for PCB somewhat lower levels were found. Because of heavy contamination with PCBs, DDT, BHC and HCB the livers of cod caught in Baltic Sea still remain insuitable for human consumption.

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Organochlorpesticide und polychlorierte Biphenyle in der Kabeljauleber aus der südlichen Ostsee, 1983

Zusammenfassung Hexachlorbenzol (HCB), -, -, -und -Benzolhexachlorid (BHC; HCH), p,p,p-DDE,o,p-DDD,o,p-DDT,p,p-DDD undp,p-DDT (DDT) und polychlorierte Biphenyle (PCB) wurde in der Leber von 210 Kabeljaus (Gadus morhua), im Netz 1983 in verschiedenen Regionen der südlichen Ostsee gefangen, bestimmt. Die mittleren gefundenen Werte für die Kabeljauleber, bezogen auf das Frischgewicht, betrugen: 0.096 mg/kg HCB, 0,15 mg/kg -BHC, -BHC wurden in Spurenmengen gefunden, 0.098 mg/kg -BHC, -BHC blieb unentdeckt, 0,26 mg/kg BHC, 1,1 mg/kgp,p-DDE,o,p-DDD undo,p-DDT blieb unentdeckt, 1,1 mg/kgp,p-DDD, 0,39 mg/kgp,p-DDT, 2,6 mg/kg DDT und 7,2 mg/kg PCB. Die gefundenen Mengen von DDT, BHC und HCB sind mit denen in der Kabeljauleber der Werte von 1981 vergleichbar, während die für PCB etwas niedriger gefunden wurde. Die schwere Kontamination mit PCB, DDT, BHC und HCB in der Leber, der in der Ostsee gefangenen Kabeljaus, läßt einen Verzehr für den Menschen nicht zu.

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Partially with financial support under grant PR-4 (Sea Fisheries Institute)     

Organochlorine pesticides and polychlorinated biphenyls in cod from the southern Baltic, 1983

Summary Hexachlorobenzene (HCB), -, -, - and -benzenehexachloride (BHC; HCH),p,p-DDE,o,p-DDD,o,p-DDT,p,p-DDD and p,p-DDT (DDT) and polychlorinated biphenyls (PCB) levels have been determined in muscle tissue of 207 cod (Gadus morhua) netted during 1983 in different regions in the southern part of the Baltic Sea. The mean levels found for cod muscle tissue (g/kg) related to wet weight were: 0.65 HCB, 1.2 -BHC, 9.0 -BHC, 2.8 -BHC, -BHC remained undetected, 13 BHC, 4.4p,p-DDE,o,p-DDD ando,p-DDT remained undetected, 4.0p,p-DDD, 1.8p,p-DDT, 10 DDT and 55 PCBs. The results are compared with levels found in cod caught in different regions of the Baltic Sea during 1967–1983, and reported previously by other authors.

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Organochlorpesticide und polychlorierte Biphenyle in Kabeljau aus der südlichen Ostsee,1983

Zusammenfassung Die Werte für Hexachlorbenzol (HCB), -, , -, und -Benzolhexachlorid (BHC; HCH),p,p-DDE,o,p-DDD,o,p-DDT,p,p-DDD undp,pDDT (DDT) und polychlorierte Biphenyle (PCB) wurden im Muskelgewebe von 207 Kabeljaus (Gadus morhua), mit Netz in verschiedenen Regionen der südlichen Ostsee 1983 gefangen, bestimmt. Die mittleren Werte, bezogen auf das Frischgewicht, waren: 0,65 g/kg HCB, 1,2 g/kg -BHC, 9,0 g/kg -BHC, 2,8 g/kg -BCH, -BHC blieben unbestimmt, 13 g/kg BHC, 4,4 g/kgp,p-DDE,o,p-DDD undo,p-DDT blieben unbestimmt, 4,0p,p-DDD, 1,8p,p-DDT, 10 g/kg DDT und 55 g/kg PCB. Die Ergebnisse wurden mit den Werten früherer Jahre von 1967–1983 und mit denen anderer Autoren verglichen.

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Partially with financial support under grant PR-4 (Sea Fisheries Institute)     

Effect of α- and δ-tocopherol on the oxidative stability of a mixed hydrogenated fat under frying conditions

Information on the antioxidative potential of -tocopherol is scanty, in particular for frying conditions. This study was aimed at assessing the antioxidative effects and degradation of - and -tocopherol between 0.01 and 0.1% on the oxidation of a commercial frying fat at 160 °C. Oxidation experiments were performed by assessing every 15 or 30 min the peroxide value and conjugated dienes as primary oxidation products, p-anisidine reactive products and hexanal as secondary oxidation products, as well as the stability of tocopherols. The fatty acid composition was determined after 6 h. The fat samples enriched with -tocopherol were considerably less resistant to oxidation compared to those with -tocopherol. Both primary and secondary oxidation parameters increased their speed of formation with -tocopherol but not with -tocopherol. The latter observation is confirmed for the total amount of oxidation and also for the first stage, showing a lag phase only for -tocopherol. These antioxidative effects can be due to the higher stability of -tocopherol compared to -tocopherol, which is oxidized faster into tocopheryl radicals, which can participate in side reactions that result in an acceleration of the oxidation speed. Neither -tocopherol nor -tocopherol influenced the fatty acid pattern. The investigation showed that during mild frying conditions the tocopherol homologues displayed various antioxidant activities. The less effective homologue, -tocopherol, underwent disintegration more quickly than -tocopherol.     

Organochlorine pesticides and polychlorinated biphenyls in herring from the southern Baltic, 1983

Summary Hexachlorobenzene (HCB), -, -, - and -benzenehexachloride (BHC, HCH),p,p-DDE,o,p-DDD,o,p-DDT,p,p-DDD andp,p-DDT (DDT) and polychlorinated biphenyls (PCB) levels have been determined in muscle tissue of 187 herring (Clupea harengus) netted during 1983 in a different regions in the southern part of the Baltic Sea. The mean levels found for herring muscle tissue related to wet weight (g/kg) were: 14 HCB, 18 -BHC, 23 -BHC, 14 -BHC, -BHC remained undetected, 56 BHC, 115p,p-DDE,o,p-DDD ando,p-DDT remained undetected, 84p,p-DDD, 51p,p-DDT, 250 DDT and 530 PCB. The levels of organochlorine pesticides determined in wet muscles or extractable lipids of her ring are nearly 2–3 times as high as those noted in fish sampled in the same area in two years before, whilst for PCBs the wet weight levels were comparable, and when based on a lipid weight are somewhat higher. The results are compared with levels found in herring collected in different regions of the Baltic Sea during 1965–1983, and reported previously by other authors.

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Organochlorpesticide und polychlorierte Biphenyle in Hering aus der südlichen Ostsee, 1983

Zusammenfassung Hexachlorbenzol (HCB), -, -, -und -Benzolhexachlorid (BHC, HCH),p,p-DDE,o,p-DDD,o,p-DDT,p,p-DDD undp,p-DDT (DDT) und polychlorierte Biphenyle (PCB) wurde im Muskelgewebe von 187 Heringen (Clupea harengus) 1983 in verschiedenen Regionen der südlichen Ostsee mit Netz gefangen, bestimmt. Die mittleren gefundenen Mengen für das Muskelgewebe von Heringen, bezogen auf das Frischgewicht waren: 14 g/kg HCB, 18 g/kg -BHC, 23 g/kg -BHC, 14 g/kg -BHC, -BHC blieb unentdeckt, 56 g/kg -BHC, 115 g/kg p,p-DDE,o,p-DDD undo,p-DDT blieb unentdeckt, 84 gmg/kgp,p-DDD, 51 g/kgp,p-DDT, 250 g/kg -DDT und 530 gmg/kg PCB. Die Mengen für Organo-chlorpesticide in frischen Muscheln oder in den extrahierten Lipiden waren zwei- bis dreimal höher als die in den Jahren zuvor bestimmten, während die für PCB vergleichbar gewesen sind, und wenn sie auf die Fettmenge bezogen wurden, lagen sie etwas höher. Die Ergebnisse wurden verglichen mit den gefundenen in anderen Regionen der Ostsee während der Jahre 1965–1983 und mit denen anderer Autoren.

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Partially with financial support under grant PR-4 (Sea Fisheries Institute)     

Primary structures of proteinase inhibitors fromPhaseolus vulgaris var.nanus (cv. Borlotto)

The primary structures of two trypsin-chymotrypsininhibitors fromPhaseolus vulgaris var.nanus (bush bean, cv. Borlotto), PVI-3₂ und PVI-4, were derived from automated Edman degradation data, amino acid composition and manual Edman degradation results of enzymatic fragments and homology with other Bowman-Birk type proteinase inhibitors. The highest degrees of homology were observed between PVI-3₂ or PVI-4 and the trypsin-chymotrypsin inhibitors from lima beans (LBI I, IV and IV, 86%), black-eyed peas (BTCI, 81%), and, in part, adzuki beans (ABI I, II and II, 74–77%). Similarly, the primary structure of the trypsin-elastase inhibitor from the same source, PVI-3₁, was deduced which showed highest homology with that of the trypsin-elastase inhibitor GBI II from garden beans (92%), followed by GBI II from garden beans (86%) and C-II from soybeans (71%). In contrast, homology between PVI-3₂ and PVI-4 on the one hand and PVI-3₁ on the other was relatively low (61%).

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Primärstrukturen einiger Proteinaseinhibitoren ausPhaseolus vulgaris var.nanus (cv. Borlotto)

Zusammenfassung Die Primärstrukturen zweier Trypsin-Chymotrypsin-Inhibitoren ausPhaseolus vulgaris var.nanus (Buschbohne, cv. Borlotto), PVI-3₂ und PVI-4, wurden aus den Ergebnissen des automatischen Edman-Abbaus, der Aminosäurezusammensetzung und dem manuellen Edman-Abbau enzymatischer Fragmente sowie der Homologie zu anderen Proteinase-Inhibitoren der Bowman-Birk-Familie ermittelt. Die höchsten Homologiegrade wurden zwischen PVI-3₂ bzw. PVI-4 und den Trypsin-Chymotrypsin-Inhibitoren aus Limabohnen (LBII, IV und IV, 86%), Augenbohnen (BTCI, 81%) und, teilweise, Adzukibohnen (ABI I, II und II, 74–77%) beobachtet. Analog wurde die Primärstruktur des Trypsin-Elastase-Inhibitors aus diesen Buschbohnen, PVI-3₁ abgeleitet. Diese zeigte die höchste Homologie zu der des Trypsin-Elastase-Inhibitors GBI II aus Gartenbohnen (92%), gefolgt von GBI II aus Gartenbohnen (86%) und C-II aus Sojabohnen (71%). Die Homologie zwischen PVI-3₂ und PVI-4 auf der einen und PVI-3₁ auf der anderen Seite war dagegen relativ niedrig (61%).

     

Stereoisomeric flavour substances

Summary Racemic mixtures of 5-hydroxyalkanoic acid-isopropylesters were converted into the diastereomers (5R), (5S)-[(R)-2-phenylpropionyloxy]-alkanoic acid-isopropylesters (11 · 11'-16 · 16) and (5R),(5S)-[(S)-Tetrahydro-5-oxo-furancarbonyloxy]-alkanoic acid-isopropylesters (22 · 22-26 · 26), respectively. These were then separated by liquid chromatography. The absolute configurations of11-16 and11–16 were derived from¹H-NMR studies and the optical activity of the lactones,1-6 and1–6 could be estimated after hydrolysis and recyclization. The optically pure stereoisomers of2-6, 2–6 have been obtained from22-26 and22–26 on a preparative scale. The sensoric characteristics of the optically pure -lactones are given.

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Stereoisomere AromastoffeXXIII. S-Lacton Aromakomponenten-Struktur und Eigenschaften der Enantiomeren

Zusammenfassung Racemische 5-Hydroxyalkansäu-re-isopropylester werden in diastereomere (5R),(5S) [(R)-2-Phenylpropionyloxy]-alkansäure-isopropyl-ester (11 · 11-16 · 16) bzw. in diastereomere (5R),(5S)[(S)-Tetrahydro-5-oxo-2-furancarbonyloxy]-alkansäsure-isopropylester (22 · 22-26 · 26) überführt und flüssigchromatographisch getrennt. Die absoluten Konfigurationen werden aus den¹H-NMR Daten abgeleitet und nach Hydrolyse und Recyclisierung der Drehsinn der optisch aktiven -Lactone1-16 und1–6 bestimmt. Aus den optisch reinen Stereoisomeren22-26 und22–26 werden die optisch reinen -Lactone2-6 und2-6 im präparativen Maßstab erhalten. Die sensorischen Eigenschaften der optisch reinen -Lactone werden mitgeteilt.

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Dedicated to Professor Dr. C. H. Brieskorn, Würzburg, FRG, on the occasion of his 75th birthday     

Organochlorine pesticides and polychlorinated biphenyls in cod from the Southern Baltic, 1981

Summary 98 samples of muscle tissue of cod ranging form 51 to 60 cm in total length and netted in 1981 in the southern part of the Baltic Sea were analysed for polychlorinated biphenyls (PCBs), DDT and its metabolites (DDE and DDD), hexachlorobenzene (HCB), and isomers of benzenehexachloride (-, -, -and -BHC). Mean values obtained related to wet weight for cod muscle tissue were: 0.77 g kg/HCB, 0.71 g kg/-BHC, 3.8 g kg/-BHC, 5.2 g kg/p,p-DDe, 2.6 g kg/p,p-DDD, 2.6 Vg kg/p,p-DDT, 10 g kg/ DDT and 180 g kg/PCB; -BHC was detectable in trace amounts and -BHC was undetected. Generally residue levels of organochlorine pesticides and PCBs found in the muscles were low, and substantial decrease of DDT and less of PCB levels in recent years when compared with data noted in 1969–1970 and 1972–1974 is noticable.

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Organochlorpesticide und polychlorierte Biphenyle im Kabeljau der südlichen Ostsee 1981

Zusammenfassung 98 Proben von Kabeljau mit einer Gesamtlänge von 51–60 cm, mit Netz in der südlichen Ostsee gefangen, wurden auf PCB, DDT und seine Metaboliten DDE und DDD, HCB und die Isomeren von -, -, - und -BHC untersucht. Die mittleren Werte, bezogen auf das Frischgewicht, waren: 0,77 g kg/HCB, 0,71 g kg/-BHC, 3,8 g kg/-BHC, 5,2 g kg/p,p-DDE, 2,6 g kg/p,p-DDD, 2,6 g kg/p,p-DDT, 10 g kg/ DDT und 180 g kg/PCB; -BHC wurde nur in Speisen mit -BHC nicht nachgewiesen. Im allgemeinen waren die Werte für die Organochlorpesticide und PCB niedrig und eine Abnahme, verglichen mit denen der Jahre 1969–1970 und 1972–1974, ist festzustellen.

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Financial support under grant PR-4 (7.1/1).     

Online determination of <Superscript>2</Superscript>H/<Superscript>1</Superscript>H and <Superscript>13</Superscript>C/<Superscript>12</Superscript>C isotope ratios of cinnamaldehyde from different sources using gas chromatography isotope ratio mass spectrometry

The combination of gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS) and gas chromatography-pyrolysis-isotope ratio mass spectrometry (GC-P-IRMS) is applied to the authenticity assessment of cinnamaldehyde from various sources. For that reason, cinnamon oils were self-prepared by steam distillation from three different varieties of cinnamon bark on the market, C. ceylanicum (ceylon), C. cassia (cassia) and C. burmanii (cassia vera). Furthermore, the so-called wood cinnamon was investigated, which is produced from the outer bark of older branches of cinnamon of minor quality. Self-prepared oils were analysed from commercial cinnamon powder. In addition several commercial samples of cinnamon oil and cinnamaldehyde, some of them declared to be natural, were investigated. ²_V-SMOW and ¹³C_V-PDB values of cinnamaldehyde were determined and characteristic authenticity ranges were deduced, allowing the differentiation between synthetic and natural samples. By correlation of both the ²_V-SMOW and ¹³C_V-PDB values, characteristic authenticity ranges were defined for ceylon, cassia and wood cinnamon. The ²_V-SMOW and ¹³C_V-PDB values of cassia vera samples are in the range of cassia. By comparing the ²_V-SMOW values of different self-prepared samples (ground bark, distillate) of cinnamon determined by TC/EA-IRMS with the corresponding GC-IRMS values, online GC-IRMS methods are proved to be essential in the authentication of complex natural products.     

St?chiometrische Zusammensetzung des Caseins in Abh?ngigkeit von Rasse, Standort und Jahreszeit

Zusammenfassung Durch Untersuchungen mit der freien Elektrophorese nachTiselius und durch Bestimmung der -Caseinanteils über den NPN-Gehalt und den Neuraminsäuregehalt der Proben wurde der Komponentenaufbau quantitativ festgestellt. Die mittlere stöchiometrische Zusammensetzung des Caseins entspricht der Bruttoformel ₉ ^s _{4 1 3}. Das einfachste Verhaltnis ist ₃ ^s ₁] _{0 1}. Von der Durchschnittszusammensetzung, die auf etwa 200 elektrophoretische Prüfungen aufgebaut ist, werden in einzelnen Fällen erhebliche Abweichungen gefunden. Sie entsprechen den Bruttoformeln ₁₂ ^s _{4 1 3} bis ₆ ^s _{1 1 3}. Auf der Basis von elektronenoptischen Aufnahmen und Mikrotomschnitten durch Caseinmicellen und unter Berücksichtigung anderer experimenteller Ergebnisse werden Vorstellungen über ein Raummodell der kleinsten Caseinpartikeln entwickelt, das aus annähernd kugeligen Elementarzellen von _s -, -, - und - Caseinteilchen besteht.FräuleinMonika Draxler danke ich für technische Assistenz bei der Durchführung der Versuche.Auszug aus der Habilitationsschrift von Dr. rer. nat.Otto Kirchmeier: Konstitution und Eigenschaften des Molekulkomplexes Casein. Habilitation Technische Hochschule München 1967.     

Untersuchungen zum Abbau von Maillard-Reaktionsprodukten durch amylolytische Enzyme

Zusammenfassung Es wird der Einfluß von Amadori-Verbindungen (Fructosyl-, Maltulosyl- und Maltotriulosylglycin) auf die Aktivität der Enzyme -Glucosidase (ausSaccharomyces cerevisiae), Glucoamylase (ausAspergillus niger) und -Amylase (aus Schweinepankreas) untersucht. Fructosylglycin wird durch alle drei Enzyme nicht hydrolysiert. -Glucosidase hydrolysiert Maltulosylglycin um den Faktor 10 langsamer als Maltotriulosylglycin. Glucoamylase und -Amylase katalysieren dagegen nur die Spaltung von Maltotriulosylglycin, wobei Glucose und Maltulosylglycin gebildet werden. Die Aktivitäten der -Glucosidase und Glucoamylase werden durch die Amadori-Verbindungen Fructosyl- und Maltulosylglycin gehemmt. Diese Amadori-Verbindungen haben auf die -Amylaseaktivität keinen Einfluß. Für die Hemmung können elektronische Effekte bzw. Wechselwirkungen zwischen der sekundären Aminofunktion der Amadori-Verbindungen und der Carboxyl- bzw. der Carboxylatgruppe des aktiven Zentrums verantwortlich sein.

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Studies on the degradation of Maillard reaction products by amylolytic enzymes. 1. Reversible inhibition of - and glucoamylase as well as -glucosidase by oligosaccharide-Amadori-compounds

The influence of Amadori-compounds (fructosyl-, maltulosyl- and maltotriulosylglycin) on the activity of the enzymes -glucosidase (fromSaccharomyces cerevisiae), glucoamyläse (fromAspergillus niger) and -amylase (from porcine pancreas) was studied. Fructosylglycin was not hydrolyzed by all three enzymes. -Glucosidase hydrolyzes maltulosylglycin 10 times slower than maltotriulosylglycin. Glucoamylase and -amylase catalyze only the cleavage of maltotriulosylglycin to form glucose and maltulosylglycin. The activities of -glucosidase and glucoamyläse are inhibited through the Amadori-compounds fructosyl- and maltulosylglycin. These Amadori-compounds don't influence the activity of -amylase. Electronic effects or interactions between the secondary amino function of Amadori-compounds and the carboxyl- or carboxylate groups of active centres could be responsible for such an inhibition.

     

Quantitative Analyse von Autoxidationsprodukten des Cholesterols in tierischen Lebensmitteln Quantitative Analysis of the Autoxidation Products of Cholesterol in Foods of Animal Origin

Zusammenfassung Nach Extraktion mit Methylenchlorid und Isolierung der unverseifbaren Lipid-Fraktion wurden die Oxycholesterole über zwei säulenchromatographische Schritte angereichert und dann als Trimethylsilylether gaschromatographisch an Dünnfilmcapillaren getrennt und massenspektrometrisch identifiziert. Als Hauptprodukte wurden Cholest-5-en-3,7-(I) und 7-diol(II) sowie das 5,6-Epoxy-cholestan-3-ol(III) und in einigen Proben Spuren von Cholestan-3,5,6-triol und Cholest-5-en-3,25-diol identifiziert. Quantitative Analysen wurden nach Zusatz von Cholest-5-en-3,19-diol als interner Standard durchgeführt.Sprühgetrocknete Eipulver enthielten die höchsten Konzentrationen von I-III (insgesamt 15-60 g/g). Im Parmesankäse, Butterschmalz und bei Wurst proben lagen die Konzentrationen von I-III wesentlich niedriger (insgesamt 0,1-2,6 gg/g). Wurde Butterschmalz oder Talg unter Luftzutritt auf 170 °C längere Zeit erhitzt, so nahmen I-III stark zu.[/p]

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Summary After extraction with methylene chloride, isolation of the unsaponifiable lipid fraction and enrichment by two-step column chromatography, the oxycholesterols were gas chromatographically separated in the form of their trimethylsilyl ethers on a thin film capillary and identified by mass spectrometry. The three major products of cholesterol autoxidation were cholest-5-en-3,7-diol(I) its 7-epimer(II) and 5,6-epoxy-cholestan-3-ol(III). In addition, traces of cholestan-3,5,6-triol and cholest-5en-3,25-diol were detected in some samples. Quantitative analysis was performed with cholest-5-en-3,19-diol as internal standard. The highest concentrations of I-III were found in spray dried egg powders (total amount 15–60 g/g). Parmesan cheese, butter oil and sausages contained significantly lower levels of I-III (total amount 0.1–2.6 /g/g). The concentrations of I-III increased strongly when butter oil and beef tallow were heated at 170 °C in the presence of air for a longer period.[/p]

     

Proteolytic and lipolytic activities of mould strains isolated from Spanish dry fermented sausages

Proteolytic and lipolytic activities of ninePenicillium strain and oneMucor strain previously isolated from Spanish dry fermented sausages have been studied.P. camemberti STCC 2267 andAspergillus oryzae ATCC 9362 were also used. Myofibrillar and sarcoplasmic proteins as well as fat extracted from pork meat and -naphthyl acetate, -naphthyl caprilate and -naphthyl laurate were used as substrates. Mould strains were grown in an enrichment medium prepared at pH 5.5 and 7.0 and malt extract broth. Strains were incubated at 18°C and 22°C. Myofibrillar proteins and -naphthyl caprilate were the most hydrolysed substrates. The greater enzymatic activities were observed at a pH 7.0 and 22°C. However, five mould strains showed considerable enzymatic activities under conditions similar to those used for ripening dry fermented sausages. These strains can be assayed as potential starter cultures for industrial sausage production.     

Antioxidative activity of<Emphasis Type="Italic"> Geranium macrorrhizum</Emphasis>

The composition of radical-scavenging compounds from Geranium macrorrhizum leaves was analyzed and the antioxidative activities of various extracts was determined. Seven compounds, namely gallic acid, ellagic acid, 4-galloyl quinic acid, the flavonoid quercetin and three of its glycosides, quercetin-3--glucopyranoside, quercetin-3--galactopyranoside and quercetin-4--glucopyranoside were isolated and identified in the various fractions. The radical-scavenging activity of the isolated compounds was measured using DPPH^· and ABTS^·+ scavenging assays and compared with the activity of rosmarinic acid. Quercetin-3-glucopyranoside and quercetin-3-galactopyranoside showed the highest antioxidative capacities. Antioxidative activities of all plant fractions were assessed by model system tests (superoxide anion and hydrogen peroxide scavenging) and by oxidation tests (-carotene bleaching, peroxide value, UV absorbance and headspace-gas chromatography hexanal determination). The ethanol-butanol fraction of the plant possessed the highest activity in most of the tests.