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4-Phenylphenoxazinones were isolated after biomimetic oxidation, using diphenoloxidases of insect cuticle, mushroom tyrosinase, or after autoxidation of N-acetyldopamine (Image ) in the presence of β-alanine, β-alanine methyl ester or N-acetyl-L-lysine. They are formed presumably by addition of 2-aminoalkyl-5-alkylphenols to the o-quinone of biphenyltetrol which, in turn, arises from oxidative coupling of. The structures of present the first examples for the assembly of reasonably stable intermediates in the rather complex process of chemical modifications of aliphatic amino acid residues by o-quinones.
Amphiphilic derivatives of octadiene and docosadiene were investigated in monolayers and Langmuir-Blodgett multilayers, with respect to their self-organization and their polymerization behavior. All amphiphiles investigated form monolayers. However, only acid and alcohol derivatives were able to build up multilayers. Those multilayers are rapidly photopolymerized in the layers via a two-step process: Irradiation with long-wavelength UV light yields soluble polymers, whereas additional irradiation with sfiort-wavelength UV light produces insoluble and presumably cross-linked polymers. The reaction meclianism is discussed according to the polymer characterization by UV spectroscopy, small-angle X-ray scattering, NMR spectroscopy, and gel permeation chromatography. All multilayers undergo structural changes during the polymerization; substantial changes result in defects in the polymerized layers as observed by scanning electron microscopy. In contrast to the acids and alcohols, the deposition of monolayers of the aldehyde derivatives did not yield well-ordered multilayers, but rather amorphous films. In this different film structure, the photopolymerization process differs from the one observed in multilayers.
Aus dem Inhalt: Die Juvenilhormone 1a-c werden im Blut von Insekten enzymatisch zu den biologisch inaktiven Sluren hydrolysiert. Bei der Hydrolyse von racemischem 1c im Blut der Wanderheuschrecke Locusta migratoria wird ein Umsatz von 40-60% erreicht. Das unumgesetzte Edukt enthällt einen Überschuß an natürlich konfiguriertem (10R)-1c (e.e. 47.2%). Wir konnten zeigen, daß das in der Hämolymphe vorhandene Hormon-Bindungsprotein bevorzugt mit (10R)- 1c assoziiert.
The topography of first-order catchments in a region of western Amazonia was found to exhibit distinctive, recurrent features: a steep, straight lower side slope, a flat or nearly flat terrace at an intermediate elevation between valley floor and interfluve, and an upper side slope connecting interfluve and intermediate terrace. A detailed survey of soil-saturated hydraulic conductivity (K sat)-depth relationships, involving 740 undisturbed soil cores, was conducted in a 0.75-ha first-order catchment. The sampling approach was stratified with respect to the above slope units. Exploratory data analysis suggested fourth-root transformation of batches from the 0–0.1 m depth interval, log transformation of batches from the subsequent 0.1 m depth increments, and the use of robust estimators of location and scale. The K sat of the steep lower side slope decreased from 46 to 0.1 mm/h over the overall sampling depth of 0.4 m. The corresponding decrease was from 46 to 0.1 mm/h on the intermediate terrace, from 335 to 0.01 mm/h on the upper side slope, and from 550 to 0.015 mm/h on the interfluve. A depthwise comparison of these slope units led to the formulation of several hypotheses concerning the link between K sat and topography.
Rainfall erosivities as defined by the R factor from the universal soil loss equation were determined for all events during a two-year period at the station La Cuenca in western Amazonia. Three methods based on a power relationship between rainfall amount and erosivity were then applied to estimate event and daily rainfall erosivities from the respective rainfall amounts. A test of the resulting regression equations against an independent data set proved all three methods equally adequate in predicting rainfall erosivity from daily rainfall amount. We recommend the Richardson model for testing in the Amazon Basin, and its use with the coefficient from La Cuenca in western Amazonia.
Previous hydrometric studies demonstrated the prevalence of overland flow as a hydrological pathway in the tropical rain forest catchment of South Creek, northeast Queensland. The purpose of this study was to consider this information in a mixing analysis with the aim of identifying sources of, and of estimating their contribution to, storm flow during two events in February 1993. K and acid-neutralizing capacity (ANC) were used as tracers because they provided the best separation of the potential sources, saturation overland flow, soil water from depths of 0.3, 0.6, and 1.2 m, and hillslope groundwater in a two-dimensional mixing plot. It was necessary to distinguish between saturation overland flow, generated at the soil surface and following unchanneled pathways, and overland flow in incised pathways. This latter type of overland flow was a mixture of saturation overland flow (event water) with high concentrations of K and a low ANC, soil water (preevent water) with low concentrations of K and a low ANC, and groundwater (preevent water) with low concentrations of K and a high ANC. The same sources explained the streamwater chemistry during the two events with strongly differing rainfall and antecedent moisture conditions. The contribution of saturation overland flow dominated the storm flow during the first, high-intensity, 178-mm event, while the contribution of soil water reached 50% during peak flow of the second, low-intensity, 44-mm event 5 days later. This latter result is remarkably similar to soil water contributions to storm flow in mountainous forested catchments of the southeastern United States. In terms of event and preevent water the storm flow hydrograph of the high-intensity event is dominated by event water and that of the low-intensity event by preevent water. This study highlights the problems of applying mixing analyses to overland flow-dominated catchments and soil environments with a poorly developed vertical chemical zonation and emphasizes the need for independent hydrometric information for a complete characterization of watershed hydrology and chemistry.
Chemical fingerprints of hydrological compartments and flow paths at La Cuenca, western Amazonia
(1995)
A forested first-order catchment in western Amazonia was monitored for 2 years to determine the chemical fingerprints of precipitation, throughfall, overland flow, pipe flow, soil water, groundwater, and streamflow. We used five tracers (hydrogen, calcium, magnesium, potassium, and silica) to distinguish “fast” flow paths mainly influenced by the biological subsystem from “slow” flow paths in the geochemical subsystem. The former comprise throughfall, overland flow, and pipe flow and are characterized by a high potassium/silica ratio; the latter are represented by soil water and groundwater, which have a low potassium/silica ratio. Soil water and groundwater differ with respect to calcium and magnesium. The groundwater-controlled streamflow chemistry is strongly modified by contributions from fast flow paths during precipitation events. The high potassium/silica ratio of these flow paths suggests that the storm flow response at La Cuenca is dominated by event water.
Earlier investigations at South Creek in northeastern Queensland established the importance of overland flow as a hydrologic pathway in this tropical rainforest environment. Since this pathway is ‘fast’, transmitting presumably ‘new’ water, its importance should be reflected in the stormflow chemistry of South Creek: the greater the volumentric contribution to the stormflow hydrograph, the more similarity between the chemical composition of streamwater and of overland flow is to be expected. Water samples were taken during two storm events in an ephemeral gully (gully A), an intermittent gully (gully B) and at the South Creek catchment outlet; additional spot checks were made in several poorly defined rills. The chemical composition of ‘old’ water was determined from 45 baseflow samples collected throughout February. The two events differed considerably in their magnitudes, intensities and antecedent moisture conditions. In both events, the stormflow chemistry in South Creek was characterized by a sharp decrease in Ca, Mg, Na, Si, Cl, EC, ANC, alkalinity and total inorganic carbon. pH remained nearly constant with discharge, whereas K increased sharply, as did sulfate in an ill-defined manner. In event 1, this South Creek stormflow pattern was closely matched by the pattern in gully A, implying a dominant contribution of ‘new’ water. This match was confirmed by the spot samples from rills. Gully B behaved like South Creek itself, but with a dampened ‘new’ water signal, indicating less overland flow generation in its subcatchment. In event 2, which occurred five days later, the initial ‘new’ water signal in gully A was rapidly overwhelmed by a different signal which is attributed to rapid drainage from a perched water table. This study shows that stormflow in this rainforest catchment consists predominantly of ‘new’ water which reaches the stream channel via ‘fast’ pathways. Where the ephemeral gullies delivering overland flow are incised deeply enough to intersect a perched water table, a delayed, ‘old’ water-like signal may be transmitted.
Just and Carpenter (1980) presented a theory of reading based on eye fixations wherein their "psycholinguistic" variables accounted for 72% of the variance in word gaze durations. This comment raises some statistical and theoretical problems with their use of simultaneous regression analysis of gaze duration measures and with the resulting theory of reading. A major problem was the confounding of perceptual with psycholinguistic factors. New eye fixation data are presented to support these criticisms. Analysis of fixations within words revealed that most gaze duration variance was contributed by number of fixations rather than by fixation duration.
The synthesis of galactose clusters that are linked to a steroid moiety by a peptide-like spacer unit is described. The galactose cluster is obtained by Koenigs-Knorr glycosylation of TRIS-Gly-Fmoc (2b) under Helferich conditions. Peptide and ester bonds are formed after activation of carboxylic acids as diphenylthiophene dioxide (TDO) esters. 6a is synthesized in a convergent way by coupling of (Ac4Gal)3-TRIS-Gly (3e) with cholesteryl TDO succinate (5b). Coupling of (Ac4Gal)3-TRIS-Gly hydrogen succinate (3f) with Gly-O-Chol (5d) by means of EEDQ yields 6d. Reaction of (Ac4Gal)3-TRIS-Gly-SUCC-O-TDO (3g) with 25-hydroxycholesterol leads in a linear sequence to the oxysterol derivative 6f. Selective cleavage of the acetyl groups from galactose units yields the known compound 6b and the new derivatives 6e and 6g.
The complement fragments C3a and C5a were purified from zymosan-activated human serum by column chromatographic procedures after the bulk of the proteins had been removed by acidic polyethylene glycol precipitation. In the isolated in situ perfused rat liver C3a increased glucose and lactate output and reduced flow. Its effects were enhanced in the presence of the carboxypeptidase inhibitor DL-mercaptomethyl-3-guanidinoethylthio-propanoic acid (MERGETPA) and abolished by preincubation of the anaphylatoxin with carboxypeptidase B or with Fab fragments of an anti-C3a monoclonal antibody. The C3a effects were partially inhibited by the thromboxane antagonist BM13505. C5a had no effect. It is concluded that locally but not systemically produced C3a may play an important role in the regulation of local metabolism and hemodynamics during inflammatory processes in the liver.
In the isolated rat liver perfused in situ stimulation of the nerve bundles around the portal vein and the hepatic artery caused an increase of urate formation that was inhibited by the α1-blocker prazosine and the xanthine oxidase inhibitor allopurinol. Moreover, nerve stimulation increased glucose and lactate output and decreased perfusion flow. Infusion of noradrenaline had similar effects. Compared to nerve stimulation infusion of glucagon led to a less pronounced increase of urate formation and a twice as large increase in glucose output but a decrease in lactate release without affecting the flow rate. Insulin had no effect on any of the parameters studied.
Increase in prostanoid formation in rat liver macrophages (Kupffer cells) by human anaphylatoxin C3a
(1993)
Human anaphylatoxin C3a increases glycogenolysis in perfused rat liver. This action is inhibited by prostanoid synthesis inhibitors and prostanoid antagonists. Because prostanoids but not anaphylatoxin C3a can increase glycogenolysis in hepatocytes, it has been proposed that prostanoid formation in nonparenchymal cells represents an important step in the C3a-dependent increase in hepatic glycogenolysis. This study shows that (a) human anaphylatoxin C3a (0.1 to 10 mug/ml) dose-dependently increased prostaglandin D2, thromboxane B, and prostaglandin F2alpha formation in rat liver macrophages (Kupffer cells); (b) the C3a-mediated increase in prostanoid formation was maximal after 2 min and showed tachyphylaxis; and (c) the C3a-elicited prostanoid formation could be inhibited specifically by preincubation of C3a with carboxypeptidase B to remove the essential C-terminal arginine or by preincubation of C3a with Fab fragments of a neutralizing monoclonal antibody. These data support the hypothesis that the C3a-dependent activation of hepatic glycogenolysis is mediated by way of a C3a-induced prostanoid production in Kupffer cells.
"Considerons une particule mobile se mouvant aleatoirement sur la droite (ou sur un segment de droite). Supposons qu'il existe une probabilite F(x,y;s,t) bien definie pour que la particule se trouvant a l'instant s dans la position x se trouve a l'instant t (> s) a gauche de y, probabilite independante du mouvement anterieur de la particule...." Mit diesen Worten beginnt eines der berühmtesten mathematischen Manuskripte des letzten Jahrhunderts. Es stammt vom Soldaten Wolfgang Döblin, Sohn des deutschen Schriftstellers Alfred Döblin, und trägt den Titel "Sur l'equation de Kolmogoroff". Seine Veröffentlichung verbindet sich mit einer unglaublichen Geschichte. Wolfgang Döblin, stationiert mit seiner Einheit in den Ardennen im Winter 1939/1940, arbeitete an diesem Manuskript. Er entschloss sich, es als versiegeltes Manuskript an die Academie des Sciences in Paris zu schicken. Aber er kehrte nie aus diesem Krieg zurück. Sein Manuskript blieb 60 Jahre unter Verschluss im Archiv, und wurde erst im Jahre 2000 geöffnet. Wie weit Döblin damit seiner Zeit voraus war, wurde erkannt, nachdem es von Bernard Bru und Marc Yor ausgewertet worden war. Im ersten Satz umschreibt W. Döblin gleichzeitig das Programm des Manuskripts: "Wir betrachten ein bewegliches Teilchen, das sich zufällig auf der Geraden (oder einem Teil davon) bewegt." Er widmet sich damit der Aufgabe, die Fundamente eines Gebiets zu legen, das wir heute als stochastische Analysis bezeichnen.
The effect of moderate rates of nitrogen deposition on ground floor vegetation is poorly predicted by uncontrolled surveys or fertilization experiments using high rates of nitrogen (N) addition. We compared the temporal trends of ground floor vegetation in permanent plots with moderate (7–13 kg ha−1 year−1) and lower bulk N deposition (4–6 kg ha−1 year−1) in southern Sweden during 1982–1998. We examined whether trends differed between growth forms (vascular plants and bryophytes) and vegetation types (three types of coniferous forest, deciduous forest, and bog). Trends of site-standardized cover and richness varied among growth forms, vegetation types, and deposition regions. Cover in spruce forests decreased at the same rate with both moderate and low deposition. In pine forests cover decreased faster with moderate deposition and in bogs cover decreased faster with low deposition. Cover of bryophytes in spruce forests increased at the same rate with both moderate and low deposition. In pine forests cover decreased faster with moderate deposition and in bogs and deciduous forests there was a strong non-linear increase with moderate deposition. The trend of number of vascular plants was constant with moderate and decreased with low deposition. We found no trend in the number of bryophyte species. We propose that the decrease of cover and number with low deposition was related to normal ecosystem development (increased shading), suggesting that N deposition maintained or increased the competitiveness of some species in the moderate-deposition region. Deposition had no consistent negative effect on vegetation suggesting that it is less important than normal successional processes.
Recent research has shown that the early lexical representations children establish in their second year of life already seem to be phonologically detailed enough to allow differentiation from very similar forms. In contrast to these findings children with specific language impairment show problems in discriminating phonologically similar word forms up to school age. In our study we investigated the question whether there would be differences in the processing of phonological details in normally developing and in children with low language performance in the second year of life. This was done by a retrospective study in which in the processing of phonological details was tested by a preferential looking experiment when the children were 19 months old. At the age of 30 months children were tested with a standardized German test of language comprehension and production (SETK2). The preferential looking data at 19 months revealed an opposite reaction pattern for the two groups: while the children scoring normally in the SETK2 increase their fixations of a pictured object only when it was named with the correct word, children with later low language performance did so only when presented with a phonologically slightly deviant mispronunciation. We suggest that this pattern does not point to a specific deficit in processing phonological information in these children but might be related to an instability of early phonological representations, and/or a generalized problem of information processing as compared to typically developing children.
Recent work has shown that English-learning 18-month-olds can detect the relationship between discontinuous morphemes such as is and -ing in Grandma is always running (Gomez, 2002; Santelmann & Jusczyk, 1998) but only at a maximum of 3 intervening syllables. In this article we examine the tracking of discontinuous dependencies in children acquiring German. Due to freer word order, German allows for greater distances between dependent elements and a greater syntactic variety of the intervening elements than English does. The aim of this study was to investigate whether factors other than distance may influence the child’s capacity to recognize discontinuous elements. Our findings provide evidence that children’s recognition capacities are affected not only by distance but also by their ability to linguistically analyze the material intervening between the dependent elements. We speculate that this result supports the existence of processing mechanisms that reduce a discontinuous relation to a local one based on subcategorization relations.
How do children determine the syntactic category of novel words? In this article we present the results of 2 experiments that investigated whether German children between 12 and 16 months of age can use distributional knowledge that determiners precede nouns and subject pronouns precede verbs to syntactically categorize adjacent novel words. Evidence from the head-turn preference paradigm shows that, although 12- to 13-month-olds cannot do this, 14- to 16-month-olds are able to use a determiner to categorize a following novel word as a noun. In contrast, no categorization effect was found for a novel word following a subject pronoun. To understand this difference we analyzed adult child-directed speech. This analysis showed that there are in fact stronger co-occurrence relations between determiners and nouns than between subject pronouns and verbs. Thus, in German determiners may be more reliable cues to the syntactic category of an adjacent novel word than are subject pronouns. We propose that the capacity to syntactically categorize novel words, demonstrated here for the first time in children this young, mediates between the recognition of the specific morphosyntactic frame in which a novel word appears and the word-to-world mapping that is needed to build up a semantic representation for the novel word.
Many methods have been proposed for the simulation of constrained mechanical systems. The most obvious of these have mild instabilities and drift problems. Consequently, stabilization techniques have been proposed A popular stabilization method is Baumgarte's technique, but the choice of parameters to make it robust has been unclear in practice. Some of the simulation methods that have been proposed and used in computations are reviewed here, from a stability point of view. This involves concepts of differential-algebraic equation (DAE) and ordinary differential equation (ODE) invariants. An explanation of the difficulties that may be encountered using Baumgarte's method is given, and a discussion of why a further quest for better parameter values for this method will always remain frustrating is presented. It is then shown how Baumgarte's method can be improved. An efficient stabilization technique is proposed, which may employ explicit ODE solvers in case of nonstiff or highly oscillatory problems and which relates to coordinate projection methods. Examples of a two-link planar robotic arm and a squeezing mechanism illustrate the effectiveness of this new stabilization method.
A Hamiltonian system in potential form (formula in the original abstract) subject to smooth constraints on q can be viewed as a Hamiltonian system on a manifold, but numerical computations must be performed in Rn. In this paper methods which reduce "Hamiltonian differential algebraic equations" to ODEs in Euclidean space are examined. The authors study the construction of canonical parameterizations or local charts as well as methods based on the construction of ODE systems in the space in which the constraint manifold is embedded which preserve the constraint manifold as an invariant manifold. In each case, a Hamiltonian system of ordinary differential equations is produced. The stability of the constraint invariants and the behavior of the original Hamiltonian along solutions are investigated both numerically and analytically.