Über definierte Polyoxyäthylenderivate. V. [1] Stickstoffhaltige Polyoxyäthylene

On Defined Polyethylene Oxide Adducts. V. Nitrogen Containing Polyethylene Oxide Adducts The authors report on the synthesis and properties of longchain α-hydro-ω-N-alkylamino-polyoxyethylenes, there methylethers, and of α-hydro-ω-N-dodecylacetamidopolyoxyethylenes. Special surface properties as solubility, surface activity and micel formation are discussed.     

Spinmarkierte Oligopeptide als substratanaloge Inhibitoren der Leucinaminopeptidase

Spin Labeled Oligopeptides as Substrate Analogous Inhibitors of Leucine Aminopeptidase The synthesis of L-Thr(Bu^t)-(L-Phe)_n-SL peptides C-terminal labeled with the nitroxide spin label 2,2,5,5-tetramethyl-3-amino-pyrrolidin-1-oxyl, is described and e.s.r. parameters of the labeled compounds are presented. As shown by e.s.r. spectroscopy studies Thr(Bu^t)-Phe-SL is a competitive inhibitor of the leucine aminopeptidase and is bound by the enzyme with high affinity.     

Flavonolglykoside der Pflaumen der Species Prunus domestica L. und Prunus salicina Lindley

Zusammenfassung Blätter wie Früchte von 6 SortenPrunus domestica-Pflaumen enthalten hauptsächlich 3-Rutinoside, in geringerer Konzentration 3-Glucoside und 3-Galaktoside von Kämpferol und Quercetin Bowie Quercetin-3-rhamnosid. Dagegen weisen Pflaumen vonPrunus salicina (2 untersuchte Sorten) Kämpferol-3,7-bisrhamnosid und Kämpferol-3-arabinosyl-7-rhamnosid als Hauptflavonole auf. Hierdurch ist eine Unterscheidung beider Arten leicht and sicher mög-lich. Weiterhin konnten inSalicina-Pflaumen Kämpfe-rol-3-rutinosid sowie Quercetin-3-rhamnosid, -xylosid,-glucosid, -galaktosid, --l-arabinofuranosid and -rutinosid, auch Quercetin-7-rhamnosid and Kämpferol-7-glucosid nachgewiesen werden.Die Gesamtgehalte an Flavonolglykosiden lagen bei den untersuchten Pflaumensorten vonPrunus domestica (P. salicina) bei 2500–3340 (7170, 10350) ppm in Blättern and 20–52 (8, 24) in Früchten, jeweils bezogen auf Frischgewicht.

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Flavonol glycosides of plums of the species Prunus domestica L. and Prunus salicina lindley12. Phenolics of fruits

Summary Leaves and fruits from 6 cultivars ofPrunus domestica plums contain mainly 3-rutinosides; in smaller concentrations the 3-glycosides and 3-galactosides of kaempferol and quercetin as well as quercetin-3-rhamnoside are present. On the other hand, in plums ofPrunus salicina (2 examined cultivars) main flavonols are kaempferol-3,7-bisrhamnoside and kaempferol-3arabinosyl-7-rhamnoside. Due to the difference in composition, differentiation of these species will be easy and reliable. Additionally kaempferol-3-rutinoside and quercetin-3-rhamnoside, -xyloside,-glucoside, -galactoside, --l-arabinofuranoside and-rutinoside, and also quercetin-7-rhamnoside and kaempferol-7-glucoside could be detected inP. salicina plums. The total content of flavonol glycosides in the investigated plums ofPrunus domestica (P. salicina) were based on fresh weight about 2500–3340 (7170, 10350) ppm in the leaves and 20–52 (8, 24) ppm in the fruits.

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11. Mitt.: Henning W, Herrmann K (1980) Z Lebensm Unters Forsch 170:433–444

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Auszug aus der Promotionsarbeit von W. Henning: Bestimmung der in Pflaumen, Kirschen, Pfirsichen and Aprikosen vorkommenden Flavonolglykoside unter Anwendung der Hochdruckflüssigkeitschromatographie. Diss. Univ. Hannover 1980     

Litter fall, litter stocks and decomposition rates in rainforest and agroforestry sites in central Amazonia

The sustainability of agroforestry systems in Amazonia was assessed from their litter dynamics and decomposition. Litter fall and litter stocks were determined from July 1997 to March 1999 in four sites in central Amazonia: a primary rainforest, a 13-year-old secondary forest, and two sites of a polyculture forestry system which consisted of four planted tree species of commercial use amidst upcoming secondary growth. The average annual litter fall in the undisturbed primary rainforest (FLO) was 8.4 t ha^–1 year^–1, which is within the range of litter fall in other rainforests in the region. It was similar in one of the two polyculture sites (8.3 t ha^–1 year^–1), but lower in the secondary forest and in the second polyculture site. In the litter fall in secondary forest and agroforestry sites, the leaf portion was higher (76–82% of total litter fall) than in FLO, due to reduced fine matter and wood fall. Leaf litter fall variability was much lower in the plantation sites than in the forests, which is explained by the much more homogeneous stand structure of the plantations. The quality of the produced litter, measured as C/N ratio, differed significantly between the primary forest site and one polyculture and the secondary forest site. The cumulative input of nitrogen through litter fall was 144 kg ha^–1 year^–1 in FLO, and 91–112 kg ha^–1 year^–1 in the polycultures and the secondary forest. Litter fall was not correlated with soil parameters, but had a significant linear regression with canopy closure. For the primary rainforest, litter fall was also (inversely) correlated with monthly rainfall. Litter fall was higher in the first year (1997–1998; an El Niño period) than in 1998–1999. Litter stocks on the forest floor were highest in the secondary forest (24.7 t ha^–1), and much lower in the polyculture sites (15.1–16.2 t ha^–1) and the primary forest (12.0 t ha^–1). There were no differences in the relative N content (C/N ratio) of the litter stocks between the sites, but the larger stocks led to higher absolute N contents in the litter layer in the secondary forest. From the monthly values of litter stocks (S) and litter fall (P), the decomposition coefficient k _e=P/S was calculated, which was, on average, highest for the primary forest (0.059), followed by the polyculture systems (0.040–0.042), and by the secondary forest (0.024). Thus, due to low decomposition rates, the secondary forest site showed large litter accumulations in spite of a relatively low litter fall. In contrast, the primary forest showed high litter fall but low stocks, due to high decomposition rates. The decomposition coefficients of the polyculture systems ranged between the primary and the secondary forest. The reduced decomposition rates in the man-managed agroecosystems indicate quantitative and/or qualitative changes in the decomposer communities of these systems that lead to a higher build-up of litter stocks on the forest floor. However, the decomposer systems in the polyculture sites still were more functional than in the site of non-managed secondary growth. Thus, from a soil biological viewpoint, ecologically sustainable low-input agroforestry in Amazonia will benefit from the application of these polyculture systems.     

Rapid On-Resin N-Formylation of Peptides as One-Pot Reaction

N-formylation is a common pre- and post-translational modification of the N-terminus or the lysine side chain of peptides and proteins that plays a role in the initiation of immune responses, gene expression, or epigenetics. Despite its high biological relevance, protocols for the chemical N-formylation of synthetic peptides are scarce. The few available methods are elaborate in their execution and the yields are highly sequence-dependent. We present a rapid, easy-to-use one-pot procedure that runs at room temperature and can be used to formylate protected peptides at both the N-terminus and the lysine side chain on the resin in near-quantitative yields. Only insensitive, storage-stable standard chemicals – formic acid, acetic anhydride, pyridine and DMF – are used. Formylation works for both short and long peptides of up to 34 amino acids and over the spectrum of canonical amino acids.     

13C‐NMR, 13C‐13C gCOSY,and ESI‐MS characterization of ether‐bridged condensation products in N,N′‐dimethylurea‐formaldehyde systems

The reaction of urea with formaldehyde is the basis for the production of urea‐formaldehyde (UF) resins which are widely applied in the wood industry. The presence of ether‐bridged condensation products in the UF resin reaction system is an open question in the literature. It is addressed in the present work. The N,N′‐dimethylurea‐formaldehyde model system was studied since it is chemically similar to the UF resin reaction system but allows for a simple elucidation of all reaction products. It was analyzed by ¹³C‐NMR spectroscopy and ESI‐MS. In corresponding NMR and MS spectra, peaks due to methoxymethylenebis(dimethyl)urea and its hemiformal were observed. ¹³C‐¹³C gCOSY analysis was conducted using labeled ¹³C‐formaldehyde. The correlation spectra showed evidence for an ether‐bridged compound and mass spectra exhibited peaks agreeing with labeled methoxymethylenebis(dimethyl)urea and its hemiformal. Methoxymethylenebis(dimethyl)urea was characterized in N,N′‐dimethylurea‐formaldehyde systems in acidic and slightly basic media. As urea is very similar to N,N′‐dimethylurea, the results of this work strengthen the assumption that ether‐bridged condensation products are likely to form in UF resins. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dielectric relaxation of high-k oxides

Frequency dispersion of high-k dielectrics was observed and classified into two parts: extrinsic cause and intrinsic cause. Frequency dependence of dielectric constant (dielectric relaxation), that is the intrinsic frequency dispersion, could not be characterized before considering the effects of extrinsic frequency dispersion. Several mathematical models were discussed to describe the dielectric relaxation of high-k dielectrics. For the physical mechanism, dielectric relaxation was found to be related to the degree of polarization, which depended on the structure of the high-k material. It was attributed to the enhancement of the correlations among polar nanodomain. The effect of grain size for the high-k materials'' structure mainly originated from higher surface stress in smaller grain due to its higher concentration of grain boundary.