976 resultados para Surface-active


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Soybean lipoxygenase-1 is a model for lipoxygenase activity. While the mechanism of oxygenation is understood, the substrate binding mechanism has not yet been elucidated. Two putative binding mechanisms are the ¿head-first¿ and ¿tail-first¿ models, in which the carboxy-terminus or the methyl terminus of the fatty acid substrate is inserted into the active site while the remainder of the molecule protrudes from the surface, respectively. Previous work has demonstrated that derivatization of fatty acid substrates with D-tryptophan increases active site affinity. It has also been shown that while polyunsaturated fatty acids are the natural substrates of lipoxygenases, monounsaturated fatty acids can be oxygenated at a much slower rate. Starting with a monounsaturated fatty acid, oleic acid, as a platform, the molecule N-oleoyl-D-tryptophan (ODT) was synthesized with the anticipation of it being a potent competitive substrate-analogue inhibitor that could be used to discern the substrate binding mechanism. Inhibition kinetics demonstrated that this molecule functions as a partially competitive inhibitor, through an unknown mechanism. The implication behind partially competitive inhibition is that substrate and inhibitor molecules can bind simultaneously to the enzyme, which alludes to the presence of an allosteric binding domain. To investigate the possibility of an inhibitor binding site on the non-catalytic subunit, limited proteolysis was used to cleave the subunits apart which should have eliminated inhibition. Interestingly, it was observed that at high substrate concentrations the inhibitor was completely ineffective, but at low substrate concentrations the inhibitor maintained its standard efficacy. A satisfactory explanation for these results has not yet been determined.

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BACKGROUND: Peri-implantitis is associated with the presence of submarginal plaque, soft-tissue inflammation and advanced breakdown of the supporting bone. The progression of peri-implantitis following varying periods of continuing plaque accumulation has been studied in animal models. OBJECTIVE: The aim of the current experiment was to study the progression of peri-implantitis around implants with different surface roughness. MATERIAL AND METHODS: In five beagle dogs, three implants with either a sandblasted acid-etched surface (SLA) or a polished surface (P) were installed bilaterally in the edentulous premolar regions. After 3 months on a plaque control regimen, experimental peri-implantitis was induced by ligature placement and plaque accumulation was allowed to progress until about 40% of the height of the supporting bone had been lost. After this 4-month period, ligatures were removed and plaque accumulation was continued for an additional 5 months. Radiographs of all implant sites were obtained before and after 'active' experimental peri-implantitis as well as at the end of the experiment. Biopsies were harvested and the tissue samples were prepared for light microscopy. The sections were used for histometric and morphometric examinations. RESULTS: The radiographic examinations indicated that similar amounts of bone loss occurred at SLA and P sites during the active breakdown period, while the progression of bone loss was larger at SLA than at polished sites following ligature removal. The histological examination revealed that both bone loss and the size of the inflammatory lesion in the connective tissue were larger in SLA than in polished implant sites. The area of plaque was also larger at implants with an SLA surface than at implants with a polished surface. CONCLUSION: It is suggested that the progression of peri-implantitis, if left untreated, is more pronounced at implants with a moderately rough surface than at implants with a polished surface.

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Colloidal Nano-apatite Particles with Active Luminescent and Magentic Properties for Biotechnology Applications. The synthesis of functional nano-materials is a burgeoning field that has produced remarkable and consistent breakthroughs over the last two decades. Individual particles have become smaller and shown potential for well defined functionality. However, there are still unresolved problems, a primary one being the loss of functionality and novelty due to uncontrolled aggregation driven by surface energy considerations. As such the first design criteria to harness the true potential of nanoparticles is to prevent unwanted agglomeration by: (1) improving, and, if possible, (2) controlling aggregation behavior. This requires specific knowledge of the chemistry of the immediate locale of the intended application; especially for biologically relevant applications. The latter criterion is also application driven but should be considered, generally, to diversify the range of functional properties that can be achieved. We have now reason to believe that such a novel system with multifunctional capabilities can be synthesized rather conveniently and have far reaching impact in biotechnology and other applications in the near future. We are presently experimenting with the syntheses of spheroidal, metal-doped, colloidal apatite nano-particles (~10 nm) for several potential biomedical applications.

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Volcán Pacaya is one of three currently active volcanoes in Guatemala. Volcanic activity originates from the local tectonic subduction of the Cocos plate beneath the Caribbean plate along the Pacific Guatemalan coast. Pacaya is characterized by generally strombolian type activity with occasional larger vulcanian type eruptions approximately every ten years. One particularly large eruption occurred on May 27, 2010. Using GPS data collected for approximately 8 years before this eruption and data from an additional three years of collection afterwards, surface movement covering the period of the eruption can be measured and used as a tool to help understand activity at the volcano. Initial positions were obtained from raw data using the Automatic Precise Positioning Service provided by the NASA Jet Propulsion Laboratory. Forward modeling of observed 3-D displacements for three time periods (before, covering and after the May 2010 eruption) revealed that a plausible source for deformation is related to a vertical dike or planar surface trending NNW-SSE through the cone. For three distinct time periods the best fitting models describe deformation of the volcano: 0.45 right lateral movement and 0.55 m tensile opening along the dike mentioned above from October 2001 through January 2009 (pre-eruption); 0.55 m left lateral slip along the dike mentioned above for the period from January 2009 and January 2011 (covering the eruption); -0.025 m dip slip along the dike for the period from January 2011 through March 2013 (post-eruption). In all bestfit models the dike is oriented with a 75° westward dip. These data have respective RMS misfit values of 5.49 cm, 12.38 cm and 6.90 cm for each modeled period. During the time period that includes the eruption the volcano most likely experienced a combination of slip and inflation below the edifice which created a large scar at the surface down the northern flank of the volcano. All models that a dipping dike may be experiencing a combination of inflation and oblique slip below the edifice which augments the possibility of a westward collapse in the future.

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The Continental porphyry Cu‐Mo mine, located 2 km east of the famous Berkeley Pit lake of Butte, Montana, contains two small lakes that vary in size depending on mining activity. In contrast to the acidic Berkeley Pit lake, the Continental Pit waters have near-neutral pH and relatively low metal concentrations. The main reason is geological: whereas the Berkeley Pit mined highly‐altered granite rich in pyrite with no neutralizing potential, the Continental Pit is mining weakly‐altered granite with lower pyrite concentrations and up to 1‐2% hydrothermal calcite. The purpose of this study was to gather and interpret information that bears on the chemistry of surface water and groundwater in the active Continental Pit. Pre‐existing chemistry data from sampling of the Continental Pit were compiled from the Montana Bureau of Mines and Geology and Montana Department of Environmental Quality records. In addition, in March of 2013, new water samples were collected from the mine’s main dewatering well, the Sarsfield well, and a nearby acidic seep (Pavilion Seep) and analyzed for trace metals and several stable isotopes, including dD and d18O of water, d13C of dissolved inorganic carbon, and d34S of dissolved sulfate. In December 2013, several soil samples were collected from the shore of the frozen pit lake and surrounding area. The soil samples were analyzed using X‐ray diffraction to determine mineral content. Based on Visual Minteq modeling, water in the Continental Pit lake is near equilibrium with a number of carbonate, sulfate, and molybdate minerals, including calcite, dolomite, rhodochrosite (MnCO3), brochantite (CuSO4·3Cu(OH)2), malachite (Cu2CO3(OH)2), hydrozincite (Zn5(CO3)2(OH)6), gypsum, and powellite (CaMoO4). The fact that these minerals are close to equilibrium suggests that they are present on the weathered mine walls and/or in the sediment of the surface water ponds. X‐Ray Diffraction (XRD) analysis of the pond “beach” sample failed to show any discrete metal‐bearing phases. One of the soil samples collected higher in the mine, near an area of active weathering of chalcocite‐rich ore, contained over 50% chalcanthite (CuSO4·5H2O). This water‐soluble copper salt is easily dissolved in water, and is probably a major source of copper to the pond and underlying groundwater system. However, concentrations of copper in the latter are probably controlled by other, less‐soluble minerals, such as brochantite or malachite. Although the acidity of the Pavilion Seep is high (~ 11 meq/L), the flow is much less than the Sarsfield Well at the current time. Thus, the pH, major and minor element chemistry in the Continental Pit lakes are buffered by calcite and other carbonate minerals. For the Continental Pit waters to become acidic, the influx of acidic seepage (e.g., Pavilion Seep) would need to increase substantially over its present volume.

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Epithelial cell polarization involves several kinase signaling cascades that eventually divide the surface membrane into an apical and a basolateral part. One kinase, which is activated during the polarization process, is phosphoinositide 3-kinase (PI3K). In MDCK cells, the basolateral potassium channel Kv7.1 requires PI3K activity for surface-expression during the polarization process. Here, we demonstrate that Kv7.1 surface expression requires tonic PI3K activity as PI3K inhibition triggers endocytosis of these channels in polarized MDCK. Pharmacological inhibition of SGK1 gave similar results as PI3K inhibition, whereas overexpression of constitutively active SGK1 overruled it, suggesting that SGK1 is the primary downstream target of PI3K in this process. Furthermore, knockdown of the ubiquitin ligase Nedd4-2 overruled PI3K inhibition, whereas a Nedd4-2 interaction-deficient Kv7.1 mutant was resistant to both PI3K and SGK1 inhibition. Altogether, these data suggest that a PI3K-SGK1 pathway stabilizes Kv7.1 surface expression by inhibiting Nedd4-2-dependent endocytosis and thereby demonstrates that Nedd4-2 is a key regulator of Kv7.1 localization and turnover in epithelial cells.

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The Lyme disease agent Borrelia burgdorferi can persistently infect humans and other animals despite host active immune responses. This is facilitated, in part, by the vls locus, a complex system consisting of the vlsE expression site and an adjacent set of 11 to 15 silent vls cassettes. Segments of nonexpressed cassettes recombine with the vlsE region during infection of mammalian hosts, resulting in combinatorial antigenic variation of the VlsE outer surface protein. We now demonstrate that synthesis of VlsE is regulated during the natural mammal-tick infectious cycle, being activated in mammals but repressed during tick colonization. Examination of cultured B. burgdorferi cells indicated that the spirochete controls vlsE transcription levels in response to environmental cues. Analysis of PvlsE::gfp fusions in B. burgdorferi indicated that VlsE production is controlled at the level of transcriptional initiation, and regions of 5' DNA involved in the regulation were identified. Electrophoretic mobility shift assays detected qualitative and quantitative changes in patterns of protein-DNA complexes formed between the vlsE promoter and cytoplasmic proteins, suggesting the involvement of DNA-binding proteins in the regulation of vlsE, with at least one protein acting as a transcriptional activator.

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Cytochromes P450 are a superfamily of heme-thiolate proteins that function in a concert with another protein, cytochrome P450 reductase, as terminal oxidases of an enzymatic system catalyzing the metabolism of a variety of foreign compounds and endogenous substrates. In order to better understand P450s catalytic mechanism and substrate specificity, information about the structure of the active site is necessary. Given the lack of a crystal structure of mammalian P450, other methods have been used to elucidate the substrate recognition and binding site structure in the active center. In this project I utilized the photoaffinity labeling technique and site-directed mutagenesis approach to gain further structural insight into the active site of mammalian cytochrome P4501AI and examine the role of surface residues in the interaction of P4501A1 with the reductase. ^ Four crosslinked peptides were identified by photoaffinity labeling using diazido benzphetamine as a substrate analog. Alignment of the primary structure of cytochrome P4501A1 with that of bacterial cytochrome P450102 (the crystal structure of which is known) revealed that two of the isolated crosslinked peptides can be placed in the vicinity of heme (in the L helix region and β10-β11 sheet region of cytochrome P450102) and could be involved in substrate binding. The other two peptides were located on the surface of the protein with the label bound specifically to Lys residues that were proposed to be involved in reductase-P450 interaction. ^ Alternatively, it has been shown that some of the organic hydroperoxides can support P450 catalyzed reactions in the absence of NADPH, O2 and reductase. By means of photoaffinity labeling the cumene hydroperoxide binding region was identified. Using azidocumene as the photoaffinity label, the tripeptide T501-L502-K503 was shown to be the site where azidocumene covalently binds to P4501A1. The sequence alignment of cytochrome P4501A1 with cytochrome P450102 predicts that this region might correspond to β-sheet structure localized on the distal side of the heme ring near the I helix and the oxygen binding pocket. The role of Thr501 in the cumene hydroperoxide binding was confirmed by mutations of this residue and kinetic analysis of the effects of the mutations. ^ In addition, the role of two lysine residues, Lys271 and Lys279, in the interaction with reductase was examined by means of site-directed mutagenesis. The lysine residues were substituted with isoleucine and enzymatic activity of the wild type and the mutants were compared in reductase- and cumene hydroperoxide-supported systems. The lysine 279 residue has been shown to play a critical role in the P4501A1-reductase interaction. ^

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The sensitivity of the gas flow field to changes in different initial conditions has been studied for the case of a highly simplified cometary nucleus model. The nucleus model simulated a homogeneously outgassing sphere with a more active ring around an axis of symmetry. The varied initial conditions were the number density of the homogeneous region, the surface temperature, and the composition of the flow (varying amounts of H2O and CO2) from the active ring. The sensitivity analysis was performed using the Polynomial Chaos Expansion (PCE) method. Direct Simulation Monte Carlo (DSMC) was used for the flow, thereby allowing strong deviations from local thermal equilibrium. The PCE approach can be used to produce a sensitivity analysis with only four runs per modified input parameter and allows one to study and quantify non-linear responses of measurable parameters to linear changes in the input over a wide range. Hence the PCE allows one to obtain a functional relationship between the flow field properties at every point in the inner coma and the input conditions. It is for example shown that the velocity and the temperature of the background gas are not simply linear functions of the initial number density at the source. As probably expected, the main influence on the resulting flow field parameter is the corresponding initial parameter (i.e. the initial number density determines the background number density, the temperature of the surface determines the flow field temperature, etc.). However, the velocity of the flow field is also influenced by the surface temperature while the number density is not sensitive to the surface temperature at all in our model set-up. Another example is the change in the composition of the flow over the active area. Such changes can be seen in the velocity but again not in the number density. Although this study uses only a simple test case, we suggest that the approach, when applied to a real case in 3D, should assist in identifying the sensitivity of gas parameters measured in situ by, for example, the Rosetta spacecraft to the surface boundary conditions and vice versa.

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Here we report the first study on the electrochemical energy storage application of a surface-immobilized ruthenium complex multilayer thin film with anion storage capability. We employed a novel dinuclear ruthenium complex with tetrapodal anchoring groups to build well-ordered redox-active multilayer coatings on an indium tin oxide (ITO) surface using a layer-by-layer self-assembly process. Cyclic voltammetry (CV), UV-Visible (UV-Vis) and Raman spectroscopy showed a linear increase of peak current, absorbance and Raman intensities, respectively with the number of layers. These results indicate the formation of well-ordered multilayers of the ruthenium complex on ITO, which is further supported by the X-ray photoelectron spectroscopy analysis. The thickness of the layers can be controlled with nanometer precision. In particular, the thickest layer studied (65 molecular layers and approx. 120 nm thick) demonstrated fast electrochemical oxidation/reduction, indicating a very low attenuation of the charge transfer within the multilayer. In situ-UV-Vis and resonance Raman spectroscopy results demonstrated the reversible electrochromic/redox behavior of the ruthenium complex multilayered films on ITO with respect to the electrode potential, which is an ideal prerequisite for e.g. smart electrochemical energy storage applications. Galvanostatic charge–discharge experiments demonstrated a pseudocapacitor behavior of the multilayer film with a good specific capacitance of 92.2 F g−1 at a current density of 10 μA cm−2 and an excellent cycling stability. As demonstrated in our prototypical experiments, the fine control of physicochemical properties at nanometer scale, relatively good stability of layers under ambient conditions makes the multilayer coatings of this type an excellent material for e.g. electrochemical energy storage, as interlayers in inverted bulk heterojunction solar cell applications and as functional components in molecular electronics applications.

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Pits have been observed on many cometary nuclei mapped by spacecraft(1-4). It has been argued that cometary pits are a signature of endogenic activity, rather than impact craters such as those on planetary and asteroid surfaces. Impact experiments(5,6) andmodels(7,8) cannot reproduce the shapes of most of the observed cometary pits, and the predicted collision rates imply that few of the pits are related to impacts(8,9). Alternative mechanisms like explosive activity(10) have been suggested, but the driving process remains unknown. Here we report that pits on comet 67P/Churyumov-Gerasimenko are active, and probably created by a sinkhole process, possibly accompanied by outbursts. We argue that after formation, pits expand slowly in diameter, owing to sublimation-driven retreat of the walls. Therefore, pits characterize how eroded the surface is: a fresh cometary surface will have a ragged structure with many pits, while an evolved surface will look smoother. The size and spatial distribution of pits imply that large heterogeneities exist in the physical, structural or compositional properties of the first few hundred metres below the current nucleus surface.

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During "Meteor" Cruise 6/1966 in the northwest Atlantic a systematic survey of the bottom topography of the southeast Greenland continental margin was undertaken. Eighty-seven profiles transverse to the shelf edge at distances of 3-4 nautical miles and two longitudinal profiles parallel to the coast were carried out with the ELAC Narrow Beam Echo-Sounder giving a reliable record of even steep slopes. On the basis of the echo soundings the topography and morphology of the continental shelf and slope are evaluated. A detailed bathymetric chart and a serial profile chart were designed as working material for the morphological research. These maps along with the original echograms are morphometrically evaluated. The analysis of the sea bottom features is the basis of a subsequent morphogenetical interpretation, verified and extended by means of interpretation of magnetic data and sediment analysis (grain size, roundness, lithology). The results of the research are expressed in a geomorphological map. The primary findings can be summarized as follows: 1) The southeast Greenland shelf by its bottom topography can be clearly designated as a glacially formed area. The glacial features of the shelf can be classified into two zones nearly parallel to the coast: glacial erosion forms on the inner shelf and glacial accumulation forms on the outer shelf. The inner shelf is characterized by the rugged and hummocky topography of ice scoured plains with clear west/east slope asymmetry. On the outer shelf three types of glacial accumulation forms can be recognized: ice margin deposits with clearly expressed terminal moraines, glacial till plains and glaciomarine outwash fans. Both zones of the shelf can be subdivided into two levels of relief. The ice scoured plains, with average depths of 240 meters (m), are dissected to a maximum depth of 1060 m (Gyldenloves Trough) by trough valleys, which are the prolongations of the Greenland fjords. The banks of the outer shelf, with an average depth of 180 m, surround glacial basins with a maximum depth of 670 meters. 2) The sediments of the continental shelf can be classified as glacial due to their grain size distribution and the degree of roundness of the gravel particles. The ice margin deposits on the outer shelf can be recognized by their high percentage of gravels. On the inner shelf a rock surface is suggested, intermittently covered by glacial deposits. In the shelf troughs fine-grained sediments occur mixed with gravels. 3) Topography and sediments show that the southeast Greenland shelf was covered by an ice sheet resting on the sea floor during the Pleistocene ice-age. The large end moraines along the shelf edge probably indicate the maximum extent of the Wurm shelf ice resting on the sea floor. The breakthroughs of the end moraines in front of the glacial basins suggest that the shelf ice has floated further seaward over the increasing depths. 4) Petrographically the shelf sediments consist of gneisses, granites and basalts. While gneisses and granites occire on the nearby coast, basalt is not known to exist here. Either this material has been drifted by icebergs from the basalt province to the north or exists on the southeast Greenland shelf itself. The last interpretation is supported bythe high portion of basalt contained in the sediment samples taken and the strong magnetic anomalies probably caused by basaltic intrusions. 5) A magnetic profile allows the recognition of two magnetically differing areas which approximately coincide with the glacial erosion and accumulation zones. The inner shelf shows a strong and variable magnetic field because the glacially eroded basement forms the sea floor. The outer shelf is characterized by a weak and homogenous magnetic field, as the magnetized basement lies at greater depthy, buried by a thick cover of glacial sediments. The strong magnetic anomalies of the inner shelf are probably caused by dike swarms, similar to those observed further to the north in the Kangerdlugssuaq Fjord region. This interpretation is supported by the high basalt content of the sediment samples and the rough topography of the ice scoured plains which correlates in general with the magnetic fluctuations. The dike structures of the basement have been differentially eroded by the shelf ice. 6) The continental slope, extending from the shelf break at 313 m to a depth of 1270 m with an average slope of 11°, is characterized by delta-shaped projections in front of the shelf basins, by marginal plateaus, ridges and hills, by canyons and slumping features. The projections could be identified as glaciomarine sediment fans. This conclusion is supported by the strong decrease of magnetic field intensity. The deep sea hills and ridges with their greater magnetic intensities have to be regarded as basement outcrops projecting through the glaciomarine sediment cover. The upper continental rise, sloping seaward at about 2°, is composed of wide sediment fans and slump material. A marginal depression on the continental rise running parallel to the shelf edge has been identified. In this depression bottom currents capable of erosion have been recorded. South of Cape Farvel the depression extends to the accumulation zone of the "Eirik" sedimentary ridge. 7) By means of a study of the recent marine processes, postglacial modification of the ice-formed relief can be postulated. The retention effect of the fjord troughs and the high velocity of the East Greenland stream prevents the glacial features from being buried by sediments. Bottom currents capable of active erosion have only been found in the marginal depression on the continental rise. In addition, at the time of the lowest glacio-eustatic sea level, the shelf bottom was not situated in the zone of wave erosion. Only on the continental slope and rise bottom currents, sediment slumps and turbidity currents have led to significant recent modifications. Considering these results, the geomorphological development of the southeast Greenland continental terrace can be suggested as follows: 1. initial formation of a "peneplain", 2. fluvial incision, 3. submergence, and finally 4. glacial modification.

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yResults of 13 field investigations between 1966 and 1990 of the southwestern to eastern margin of Kötlujökull and its proglacial area are summarized with respect to sandar and their formation. Generally, the results are based on sedimentological examinations in the field and laboratory, on analyses of aerial photographs, and investigations of the glacier slope. The methods permitted a more detailed reconstruction of sandar evolution in the proglacial area of Kötlujökull since 1945, of tendencies in development and of single data going back until the last decades of the 19th century. Accordingly, there existed special periods of "flachsander"-formations with raised coarsegrained "sanderwurzels" resultant from the outbreak of subglacial meltwater tunneloutlets and other periods with "hochsander-"formations by supraglacial drainage. At present the belts of hochsanders in front of the glacier come up to more than 4 m in thickness and 1000 m in width, therefore containing perhaps more sediment direct in front of Kötlujökull than the old belts of flachsanderwurzels. In one case the explosion-like subglacial meltwater outburst combined with the genesis of a sanderwurzel could be observed for a time and is thoroughly discussed. The event is referred to the outburst of a sub- to inglacial meltwater body being under extreme hydrostatic press ures which is combined with the genesis of a new subglacial tunneloutlet as a new flachsander. Often these outbursts led to the destruction of a morainic belt more than 1000 m in width. Presumably the whole event was finished in not more than a few days. In addition to a characteristic pear-shaped form and water-moved stones up to diameters of 1 m the wurzels possess a single "main-channel" with rectangular cross-sections as far as 4 m deep and 50 m wide just as small flat channels resembling fish bones in connection with the main channel. Presumably, they have been active only in the last stage of wurzel formation. With regard to the subglacial tunnel gates long-living L-meltwater outlets are distinguished from short-living K-meltwater outlets. These are always combined with a raised coarse-grained sanderwurzel, but its meltwater discharge is generally decreasing and ceases after some years, whereas the discharge of L-meltwater outlets continues unchanged for long times (except seasonal differences). The material of flachsanders is preponderantly composed of mugearitic and andesitic cobble extending at least for some kilometres from the glacier margin, whereas the hochsanders correspond to medium to coarse sands without clay and without alternations into the direction of flow. The hochsander fans are covered with small braidet channels. Their sedimentary structures are determined by the short time changing of supraglacial meltwater discharge and the upper flow regime combined with the development of antidunes, which rule the channel-flows during the main activity periods in summer. Unlike the subglacial drainage the supraglacial drainage led to only weak effects of erosion on the glacier foreland. So the hochsanders refilled depressions of morainic areas or grew up on older flachsanderwurzels. Whereas all large flachsanders developed in front of approximate stationary glacier margins, the evolution of coherent belts of hochsanders were combined with progressive glacier fronts. On the other hand, there was obviously no evolution at all of large sandar in front of back-melting margins of Kötlujökull. Based on examinations of the glacier surface and on analyses of aerial photographs the different types of sandar are referred to different structures of the glacier snout. Finally chances of surviving of sandar in the proglacial area of Kötlujökull are shortly discussed just as the possibility of an application of the Islandic research results on Pleistocene sandar in northern Germany.