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  • MDPI  (41,076)
  • Wiley-Blackwell  (10,011)
  • American Association for the Advancement of Science (AAAS)
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  • 2015-2019  (45,860)
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  • 2019  (45,860)
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  • 2015-2019  (45,860)
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  • 1
    Publication Date: 2019-12-03
    Description: Phytoplankton in the ocean are extremely diverse. The abundance of various intracellular pigments are often used to study phytoplankton physiology and ecology, and identify and quantify different phytoplankton groups. In this study, phytoplankton absorption spectra (aph(λ)) derived from underway flow-through AC-S measurements in the Fram Strait are combined with phytoplankton pigment measurements analyzed by high-performance liquid chromatography (HPLC) to evaluate the retrieval of various pigment concentrations at high spatial resolution. The performances of two approaches, Gaussian decomposition and the matrix inversion technique are investigated and compared. Our study is the first to apply the matrix inversion technique to underway spectrophotometry data. We find that Gaussian decomposition provides good estimates (median absolute percentage error, MPE 21–34%) of total chlorophyll-a (TChl-a), total chlorophyll-b (TChl-b), the combination of chlorophyll-c1 and -c2 (Chl-c1/2), photoprotective (PPC) and photosynthetic carotenoids (PSC). This method outperformed one of the matrix inversion algorithms, i.e., singular value decomposition combined with non-negative least squares (SVD-NNLS), in retrieving TChl-b, Chl-c1/2, PSC, and PPC. However, SVD-NNLS enables robust retrievals of specific carotenoids (MPE 37–65%), i.e., fucoxanthin, diadinoxanthin and 19′-hexanoyloxyfucoxanthin, which is currently not accomplished by Gaussian decomposition. More robust predictions are obtained using the Gaussian decomposition method when the observed aph(λ) is normalized by the package effect index at 675 nm. The latter is determined as a function of “packaged” aph(675) and TChl-a concentration, which shows potential for improving pigment retrieval accuracy by the combined use of aph(λ) and TChl-a concentration data. To generate robust estimation statistics for the matrix inversion technique, we combine leave-one-out cross-validation with data perturbations. We find that both approaches provide useful information on pigment distributions, and hence, phytoplankton community composition indicators, at a spatial resolution much finer than that can be achieved with discrete samples.
    Repository Name: EPIC Alfred Wegener Institut
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  • 2
    Publication Date: 2021-02-16
    Description: Arctic and subarctic regions are sensitive to climate change and, reversely, provide dramatic feedbacks to the global climate. With a focus on discovering paleoclimate and paleoceanographic evolution in the Arctic and Northwest Pacific Oceans during the last 20,000 years, we proposed this German–Sino cooperation program according to the announcement “Federal Ministry of Education and Research (BMBF) of the Federal Republic of Germany for a German–Sino cooperation program in the marine and polar research”. Our proposed program integrates the advantages of the Arctic and Subarctic marine sediment studies in AWI (Alfred Wegener Institute) and FIO (First Institute of Oceanography). For the first time, the collection of sediment cores can cover all climatological key regions in the Arctic and Northwest Pacific Oceans. Furthermore, the climate modeling work at AWI enables a “Data-Model Syntheses”, which are crucial for exploring the underlying mechanisms of observed changes in proxy records.
    Repository Name: EPIC Alfred Wegener Institut
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  • 3
    Publication Date: 2019-05-28
    Description: An intercomparison of radiance and irradiance ocean color radiometers (the second laboratory comparison exercise—LCE-2) was organized within the frame of the European Space Agency funded project Fiducial Reference Measurements for Satellite Ocean Color (FRM4SOC) May 8–13, 2017 at Tartu Observatory, Estonia. LCE-2 consisted of three sub-tasks: (1) SI-traceable radiometric calibration of all the participating radiance and irradiance radiometers at the Tartu Observatory just before the comparisons; (2) indoor, laboratory intercomparison using stable radiance and irradiance sources in a controlled environment; (3) outdoor, field intercomparison of natural radiation sources over a natural water surface. The aim of the experiment was to provide a link in the chain of traceability from field measurements of water reflectance to the uniform SI-traceable calibration, and after calibration to verify whether di�erent instruments measuring the same object provide results consistent within the expected uncertainty limits. This paper describes the third phase of LCE-2: The results of the field experiment. The calibration of radiometers and laboratory comparison experiment are presented in a related paper of the same journal issue. Compared to the laboratory comparison, the field intercomparison has demonstrated substantially larger variability between freshly calibrated sensors, because the targets and environmental conditions during radiometric calibration were di�erent, both spectrally and spatially. Major di�erences were found for radiance sensors measuring a sunlit water target at viewing zenith angle of 139� because of the di�erent fields of view. Major di�erences were found for irradiance sensors because of imperfect cosine response of di�users. Variability between individual radiometers did depend significantly also on the type of the sensor and on the specific measurement target. Uniform SI traceable radiometric calibration ensuring fairly good consistency for indoor, laboratory measurements is insu�cient for outdoor, field measurements, mainly due to the di�erent angular variability of illumination. More stringent specifications and individual testing of radiometers for all relevant systematic e�ects (temperature, nonlinearity, spectral stray light, etc.) are needed to reduce biases between instruments and better quantify measurement uncertainties.
    Repository Name: EPIC Alfred Wegener Institut
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  • 4
    Publication Date: 2019-05-28
    Description: An intercomparison of radiance and irradiance ocean color radiometers (The Second Laboratory Comparison Exercise—LCE-2) was organized within the frame of the European Space Agency funded project Fiducial Reference Measurements for Satellite Ocean Color (FRM4SOC) May 8–13, 2017 at Tartu Observatory, Estonia. LCE-2 consisted of three sub-tasks: 1) SI-traceable radiometric calibration of all the participating radiance and irradiance radiometers at the Tartu Observatory just before the comparisons; 2) Indoor intercomparison using stable radiance and irradiance sources in controlled environment; and 3) Outdoor intercomparison of natural radiation sources over terrestrial water surface. The aim of the experiment was to provide one link in the chain of traceability from field measurements of water reflectance to the uniform SI-traceable calibration, and after calibration to verify whether di�erent instruments measuring the same object provide results consistent within the expected uncertainty limits. This paper describes the activities and results of the first two phases of LCE-2: the SI-traceable radiometric calibration and indoor intercomparison, the results of outdoor experiment are presented in a related paper of the same journal issue. The indoor experiment of the LCE-2 has proven that uniform calibration just before the use of radiometers is highly e�ective. Distinct radiometers from di�erent manufacturers operated by di�erent scientists can yield quite close radiance and irradiance results (standard deviation s 〈 1%) under defined conditions. This holds when measuring stable lamp-based targets under stationary laboratory conditions with all the radiometers uniformly calibrated against the same standards just prior to the experiment. In addition, some unification of measurement and data processing must be settled. Uncertaint of radiance and irradiance measurement under these conditions largely consists of the sensor’s calibration uncertainty and of the spread of results obtained by individual sensors measuring the same object.
    Repository Name: EPIC Alfred Wegener Institut
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  • 5
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    MDPI
    In:  EPIC3Remote Sensing, MDPI, 11(9), pp. 1-18, ISSN: 2072-4292
    Publication Date: 2019-05-20
    Description: Real-time quality-controlled surface current data derived from X-Band marine radar (MR) measurements were evaluated to estimate their operational reliability. The presented data were acquired by the standard commercial o�-the-shelf MR-based sigma s6 WaMoS® II (WaMoS® II) deployed onboard the German Research vessel Polarstern. The measurement reliability is specified by an IQ value obtained by the WaMoS® II real-time quality control (rtQC). Data which pass the rtQC without objection are assumed to be reliable. For these data sets accuracy and correlation with corresponding vessel-mounted acoustic Doppler current profiler (ADCP) measurements are determined. To reduce potential misinterpretation due to short-term oceanic variability/turbulences, the evaluation of the WaMoS® II accuracy was carried out based on sliding means over 20 min of the reliable data only. The associated standard deviation �WaMoS = 0.02 m/s of the meanWaMoS® II measurements reflect a high precision of the measurement and the successful rtQC during di�erent wave, current and weather conditions. The direct comparison of 7272 WaMoS® II/ADCP northward and eastward velocity data pairs yield a correlation of r � 0.94, with jbiasDj � 0.06 m/s and �S = 0.05 m/s. This confirms that the MR-based surface current measurements are accurate and reliable.
    Repository Name: EPIC Alfred Wegener Institut
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  • 6
    Publication Date: 2019-09-01
    Description: Coring sediments in subglacial aquatic environments offers unique opportunities for research on paleo-environments and paleo-climates because it can provide data from periods even earlier than ice cores, as well as the overlying ice histories, interactions between ice and the water system, life forms in extreme habitats, sedimentology, and stratigraphy. However, retrieving sediment cores from a subglacial environment faces more difficulties than sediment coring in oceans and lakes, resulting in low yields from the most current subglacial sediment coring methods. The coring tools should pass through a hot water-drilled access borehole, then the water column, to reach the sediment layers. The access boreholes are size-limited by the hot water drilling tools and techniques. These holes are drilled through ice up to 3000–4000 m thick, with diameters ranging from 10–60 cm, and with a refreezing closure rate of up to 6 mm/h after being drilled. Several purpose-built streamline corers have been developed to pass through access boreholes and collect the sediment core. The main coring objectives are as follows: (i) To obtain undisturbed water–sediment cores, either singly or as multi-cores and (ii) to obtain long cores with minimal stratigraphic deformation. Subglacial sediment coring methods use similar tools to those used in lake and ocean coring. These methods include the following: Gravity coring, push coring, piston coring, hammer or percussion coring, vibrocoring, and composite methods. Several core length records have been attained by different coring methods, including a 290 cm percussion core from the sub-ice-shelf seafloor, a 400 cm piston core from the sub-ice-stream, and a 170 cm gravity core from a subglacial lake. There are also several undisturbed water–sediment cores that have been obtained by gravity corers or hammer corers. Most current coring tools are deployed by winch and cable facilities on the ice surface. There are three main limitations for obtaining long sediment cores which determines coring tool development, as follows: Hot-water borehole radial size restriction, the sedimentary structure, and the coring techniques. In this paper, we provide a general view on current developments in coring tools, including the working principles, corer characteristics, operational methods, coring site locations, field conditions, coring results, and possible technical improvements. Future prospects in corer design and development are also discussed.
    Repository Name: EPIC Alfred Wegener Institut
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  • 7
    Publication Date: 2019-10-21
    Description: Air temperatures in the Arctic have increased substantially over the last decades, which has extensively altered the properties of the land surface. Capturing the state and dynamics of Land Surface Temperatures (LSTs) at high spatial detail is of high interest as LST is dependent on a variety of surficial properties and characterizes the land–atmosphere exchange of energy. Accordingly, this study analyses the influence of different physical surface properties on the long-term mean of the summer LST in the Arctic Mackenzie Delta Region (MDR) using Landsat 30 m-resolution imagery between 1985 and 2018 by taking advantage of the cloud computing capabilities of the Google Earth Engine. Multispectral indices, including the Normalized Difference Vegetation Index (NDVI), Normalized Difference Water Index (NDWI) and Tasseled Cap greenness (TCG), brightness (TCB), and wetness (TCW) as well as topographic features derived from the TanDEM-X digital elevation model are used in correlation and multiple linear regression analyses to reveal their influence on the LST. Furthermore, surface alteration trends of the LST, NDVI, and NDWI are revealed using the Theil-Sen (T-S) regression method. The results indicate that the mean summer LST appears to be mostly influenced by the topographic exposition as well as the prevalent moisture regime where higher evapotranspiration rates increase the latent heat flux and cause a cooling of the surface, as the variance is best explained by the TCW and northness of the terrain. However, fairly diverse model outcomes for different regions of the MDR (R2 from 0.31 to 0.74 and RMSE from 0.51 °C to 1.73 °C) highlight the heterogeneity of the landscape in terms of influential factors and suggests accounting for a broad spectrum of different factors when modeling mean LSTs. The T-S analysis revealed large-scale wetting and greening trends with a mean decadal increase of the NDVI/NDWI of approximately +0.03 between 1985 and 2018, which was mostly accompanied by a cooling of the land surface given the inverse relationship between mean LSTs and vegetation and moisture conditions. Disturbance through wildfires intensifies the surface alterations locally and lead to significantly cooler LSTs in the long-term compared to the undisturbed surroundings.
    Repository Name: EPIC Alfred Wegener Institut
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  • 8
    Publication Date: 2021-07-23
    Description: In this work, laboratory tests with live bivalves as well as the conceptual design of additively manufactured surrogate models are presented. The overall task of this work is to develop a surrogate best fitting to the live mussels tested in accordance to the identified surface descriptor, i.e., the Abbott–Firestone Curve, and to the hydrodynamic behaviour by means of drag and inertia coefficients. To date, very few investigations have focused on loads from currents as well as waves. Therefore, tests with a towing carriage were carried out in a wave flume. A custom-made rack using mounting clamps was built to facilitate carriage-run tests with minimal delays. Blue mussels (Mytilus edulis) extracted from a site in Germany, which were kept in aerated seawater to ensure their survival for the test duration, were used. A set of preliminary results showed drag and inertia coefficients CD and CM ranging from 1.16–3.03 and 0.25 to 1.25. To derive geometrical models of the mussel dropper lines, 3-D point clouds were prepared by means of 3-D laser scanning to obtain a realistic surface model. Centered on the 3-D point cloud, a suitable descriptor for the mass distribution over the surface was identified and three 3-D printed surrogates of the blue mussel were developed for further testing. These were evaluated regarding their fit to the original 3-D point cloud of the live blue mussels via the chosen surface descriptor.
    Repository Name: EPIC Alfred Wegener Institut
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  • 9
    Publication Date: 2019-06-17
    Description: Automatic detection of icebergs in satellite images is regarded a useful tool to provide information necessary for safety in Arctic shipping or operations over large ocean areas in near-real time. In this work, we investigated the feasibility of automatic iceberg detection in Sentinel-1 Extra Wide Swath (EWS) SAR images which follow the preferred image mode in operational ice charting. As test region, we selected the Barents Sea where the size of many icebergs is on the order of the spatial resolution of the EWS-mode. We tested a new approach for a detection scheme. It is based on a combination of a filter for enhancing the contrast between icebergs and background, subsequent blob detection, and final application of a Constant False Alarm Rate (CFAR) algorithm. The filter relies mainly on the HV-polarized intensity which often reveals a larger difference between icebergs and sea ice or open water. The blob detector identifies locations of potential icebergs and thus shortens computation time. The final detection is performed on the identified blobs using the CFAR algorithm. About 2000 icebergs captured in fast ice were visually identified in Sentinel-2 Multi Spectral Imager (MSI) data and exploited for an assessment of the detection scheme performance using confusion matrices. For our performance tests, we used four Sentinel-1 EWS images. For judging the effect of spatial resolution, we carried out an additional test with one Sentinel-1 Interferometric Wide Swath (IWS) mode image. Our results show that only 8–22 percent of the icebergs could be detected in the EWS images, and over 90 percent of all detections were false alarms. In IWS mode, the number of correctly identified icebergs increased to 38 percent. However, we obtained a larger number of false alarms in the IWS image than in the corresponding EWS image. We identified two problems for iceberg detection: 1) with the given frequency–polarization combination, not all icebergs are strong scatterers at HV-polarization, and (2) icebergs and deformation structures present on fast ice can often not be distinguished since both may reveal equally strong responses at HV-polarization.
    Repository Name: EPIC Alfred Wegener Institut
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  • 10
    Publication Date: 2019-04-23
    Description: Thermokarst lakes in the Arctic and Subarctic release carbon from thawing permafrost in the form of methane and carbon dioxide with important implications for regional and global carbon cycles. Lake ice impedes the release of gas during the winter. For instance, bubbles released from lake sediments become trapped in downward growing lake ice, resulting in vertically-oriented bubble columns in the ice that are visible on the lake surface. We here describe a classification technique using an object-based image analysis (OBIA) framework to successfully map ebullition bubbles in airborne imagery of early winter ice on an interior Alaska thermokarst lake. Ebullition bubbles appear as white patches in high-resolution optical remote sensing images of snow-free lake ice acquired in early winter and, thus, can be mapped across whole lake areas. We used high-resolution (9–11 cm) aerial images acquired two and four days following freeze-up in the years 2011 and 2012, respectively. The design of multiresolution segmentation and region-specific classification rulesets allowed the identification of bubble features and separation from other confounding factors such as snow, submerged and floating vegetation, shadows, and open water. The OBIA technique had an accuracy of 〉95% for mapping ebullition bubble patches in early winter lake ice. Overall, we mapped 1195 and 1860 ebullition bubble patches in the 2011 and 2012 images, respectively. The percent surface area of lake ice covered with ebullition bubble patches for 2011 was 2.14% and for 2012 was 2.67%, representing a conservative whole lake estimate of bubble patches compared to ground surveys usually conducted on thicker ice 10 or more days after freeze-up. Our findings suggest that the information derived from high-resolution optical images of lake ice can supplement spatially limited field sampling methods to better estimate methane flux from individual lakes. The method can also be used to improve estimates of methane ebullition from numerous lakes within larger regions.
    Repository Name: EPIC Alfred Wegener Institut
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  • 11
    Publication Date: 2022-05-25
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Sathyendranath, S., Brewin, R. J. W., Brockmann, C., Brotas, V., Calton, B., Chuprin, A., Cipollini, P., Couto, A. B., Dingle, J., Doerffer, R., Donlon, C., Dowell, M., Farman, A., Grant, M., Groom, S., Horseman, A., Jackson, T., Krasemann, H., Lavender, S., Martinez-Vicente, V., Mazeran, C., Melin, F., Moore, T. S., Muller, D., Regner, P., Roy, S., Steele, C. J., Steinmetz, F., Swinton, J., Taberner, M., Thompson, A., Valente, A., Zuhlke, M., Brando, V. E., Feng, H., Feldman, G., Franz, B. A., Frouin, R., Gould, R. W., Hooker, S. B., Kahru, M., Kratzer, S., Mitchell, B. G., Muller-Karger, F. E., Sosik, H. M., Voss, K. J., Werdell, J., & Platt, T. An ocean-colour time series for use in climate studies: The experience of the ocean-colour climate change initiative (OC-CCI). Sensors, 19(19), (2019): 4285, doi: 10.3390/s19194285.
    Description: Ocean colour is recognised as an Essential Climate Variable (ECV) by the Global Climate Observing System (GCOS); and spectrally-resolved water-leaving radiances (or remote-sensing reflectances) in the visible domain, and chlorophyll-a concentration are identified as required ECV products. Time series of the products at the global scale and at high spatial resolution, derived from ocean-colour data, are key to studying the dynamics of phytoplankton at seasonal and inter-annual scales; their role in marine biogeochemistry; the global carbon cycle; the modulation of how phytoplankton distribute solar-induced heat in the upper layers of the ocean; and the response of the marine ecosystem to climate variability and change. However, generating a long time series of these products from ocean-colour data is not a trivial task: algorithms that are best suited for climate studies have to be selected from a number that are available for atmospheric correction of the satellite signal and for retrieval of chlorophyll-a concentration; since satellites have a finite life span, data from multiple sensors have to be merged to create a single time series, and any uncorrected inter-sensor biases could introduce artefacts in the series, e.g., different sensors monitor radiances at different wavebands such that producing a consistent time series of reflectances is not straightforward. Another requirement is that the products have to be validated against in situ observations. Furthermore, the uncertainties in the products have to be quantified, ideally on a pixel-by-pixel basis, to facilitate applications and interpretations that are consistent with the quality of the data. This paper outlines an approach that was adopted for generating an ocean-colour time series for climate studies, using data from the MERIS (MEdium spectral Resolution Imaging Spectrometer) sensor of the European Space Agency; the SeaWiFS (Sea-viewing Wide-Field-of-view Sensor) and MODIS-Aqua (Moderate-resolution Imaging Spectroradiometer-Aqua) sensors from the National Aeronautics and Space Administration (USA); and VIIRS (Visible and Infrared Imaging Radiometer Suite) from the National Oceanic and Atmospheric Administration (USA). The time series now covers the period from late 1997 to end of 2018. To ensure that the products meet, as well as possible, the requirements of the user community, marine-ecosystem modellers, and remote-sensing scientists were consulted at the outset on their immediate and longer-term requirements as well as on their expectations of ocean-colour data for use in climate research. Taking the user requirements into account, a series of objective criteria were established, against which available algorithms for processing ocean-colour data were evaluated and ranked. The algorithms that performed best with respect to the climate user requirements were selected to process data from the satellite sensors. Remote-sensing reflectance data from MODIS-Aqua, MERIS, and VIIRS were band-shifted to match the wavebands of SeaWiFS. Overlapping data were used to correct for mean biases between sensors at every pixel. The remote-sensing reflectance data derived from the sensors were merged, and the selected in-water algorithm was applied to the merged data to generate maps of chlorophyll concentration, inherent optical properties at SeaWiFS wavelengths, and the diffuse attenuation coefficient at 490 nm. The merged products were validated against in situ observations. The uncertainties established on the basis of comparisons with in situ data were combined with an optical classification of the remote-sensing reflectance data using a fuzzy-logic approach, and were used to generate uncertainties (root mean square difference and bias) for each product at each pixel.
    Description: This work was funded by the Ocean Colour Climate Change initiative of the European Space Agency (Grant Number 4000101437/10/I-LG). We acknowledge additional funding support by NERC through the National Centre for Earth Observation (Grant Number PR140015). Additional funding from a Simons Foundation Grant (549947, SS) is also gratefully acknowledged. V.B. also acknowledges funding from the European Union’s Horizon 2020 Research and Innovation Programme grant agreement N_ 810139: Project Portugal Twinning for Innovation and Excellence in Marine Science and Earth Observation – PORTWIMS.
    Keywords: ocean colour ; water-leaving radiance ; remote-sensing reflectance ; phytoplankton ; chlorophyll-a ; inherent optical properties ; Climate Change Initiative ; optical water classes ; Essential Climate Variable ; uncertainty characterisation
    Repository Name: Woods Hole Open Access Server
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  • 12
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    MDPI
    In:  EPIC3Atmosphere, MDPI, 10(12), ISSN: 2073-4433
    Publication Date: 2020-04-14
    Description: The heat imbalance is the fundamental driver for the atmospheric circulation. Therefore, it is crucially important to understand how it responds to global warming. In this study, the role of the ocean in reshaping the atmospheric meridional heat imbalance is explored based on observations and climate simulations. We found that ocean tends to strengthen the meridional heat imbalance over the mid-latitudes. This is primarily because of the uneven ocean heat uptake between the subtropical and subpolar oceans. Under global warming, the subtropical ocean absorbs relatively less heat as the water there is well stratified. In contrast, the subpolar ocean is the primary region where the ocean heat uptake takes place, because the subpolar ocean is dominated by upwelling, strong mixing, and overturning circulation. We propose that the enhanced meridional heat imbalance may potentially contribute to strengthening the water cycle, westerlies, jet stream, and mid-latitude storms.
    Repository Name: EPIC Alfred Wegener Institut
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  • 13
    Publication Date: 2022-10-26
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Pun, I., Chan, J. C. L., Lin, I., Chan, K. T. E., Price, J. F., Ko, D. S., Lien, C., Wu, Y., & Huang, H. Rapid intensification of Typhoon Hato (2017) over shallow water. Sustainability, 11(13), (2019): 3709, doi:10.3390/su11133709.
    Description: On 23 August, 2017, Typhoon Hato rapidly intensified by 10 kt within 3 h just prior to landfall in the city of Macau along the South China coast. Hato’s surface winds in excess of 50 m s−1 devastated the city, causing unprecedented damage and social impact. This study reveals that anomalously warm ocean conditions in the nearshore shallow water (depth 〈 30 m) likely played a key role in Hato’s fast intensification. In particular, cooling of the sea surface temperature (SST) generated by Hato at the critical landfall point was estimated to be only 0.1–0.5 °C. The results from both a simple ocean mixing scheme and full dynamical ocean model indicate that SST cooling was minimized in the shallow coastal waters due to a lack of cool water at depth. Given the nearly invariant SST in the coastal waters, we estimate a large amount of heat flux, i.e., 1.9k W m−2, during the landfall period. Experiments indicate that in the absence of shallow bathymetry, and thus, if nominal cool water had been available for vertical mixing, the SST cooling would have been enhanced from 0.1 °C to 1.4 °C, and sea to air heat flux reduced by about a quarter. Numerical simulations with an atmospheric model suggest that the intensity of Hato was very sensitive to air-sea heat flux in the coastal region, indicating the critical importance of coastal ocean hydrography.
    Description: The work of I.-F.P. is supported by Taiwan’s Ministry of Science and Technology Grant MOST 107-2111-M-008-001-MY3. The work of J.C.L.C. is supported by the Research Grants Council of Hong Kong Grant E-CityU101/16. The work of I.-I.L. is supported by Taiwan’s Ministry of Science and Technology (MOST 106-2111-M-002-011-MY3, MOST 108-2111-M-002-014-MY2). The work of K.T.F.C. is jointly supported by the National Natural Science Foundation of China (41775097), and the National Natural Science Foundation of China and Macau Science and Technology Development Joint Fund (NSFC-FDCT), China and Macau (41861164027).
    Keywords: Typhoon ; SST cooling ; Shallow water ; Vertical mixing ; Rapid intensification
    Repository Name: Woods Hole Open Access Server
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  • 14
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    American Geophysical Union (AGU)
    In:  EPIC3Journal of Geophysical Research: Oceans, American Geophysical Union (AGU), 124(8), pp. 5503-5528, ISSN: 2169-9275
    Publication Date: 2022-11-02
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , NonPeerReviewed
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  • 15
    Publication Date: 2022-10-26
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Gurumurthy, P., Orton, P. M., Talke, S. A., Georgas, N., & Booth, J. F. Mechanics and historical evolution of sea level blowouts in New York harbor. Journal of Marine Science and Engineering, 7(5), (2019): 160, doi:10.3390/jmse7050160.
    Description: Wind-induced sea level blowouts, measured as negative storm surge or extreme low water (ELW), produce public safety hazards and impose economic costs (e.g., to shipping). In this paper, we use a regional hydrodynamic numerical model to test the effect of historical environmental change and the time scale, direction, and magnitude of wind forcing on negative and positive surge events in the New York Harbor (NYH). Environmental sensitivity experiments show that dredging of shipping channels is an important factor affecting blowouts while changing ice cover and removal of other roughness elements are unimportant in NYH. Continuously measured water level records since 1860 show a trend towards smaller negative surge magnitudes (measured minus predicted water level) but do not show a significant change to ELW magnitudes after removing the sea-level trend. Model results suggest that the smaller negative surges occur in the deeper, dredged modern system due to a reduced tide-surge interaction, primarily through a reduced phase shift in the predicted tide. The sensitivity of surge to wind direction changes spatially with remote wind effects dominating local wind effects near NYH. Convergent coastlines that amplify positive surges also amplify negative surges, a process we term inverse coastal funneling.
    Description: This research was funded by the US Army Corps of Engineers (agreement no. W9127N-14-2-0015; S. Talke, PI), the NSF (Career Award 1455350; PI Talke), NASA’s Research Opportunities in Space and Earth Science ROSES-2012 (grant NNX14AD48G; Kushnir, PI), and a Provost’s Doctoral Fellowship, Stevens Institute of Technology.
    Keywords: Estuary ; Negative surge ; Blowout ; Storm surge ; Funneling ; Tide-surge interaction ; Wind set-down ; New York Harbor ; Dredging
    Repository Name: Woods Hole Open Access Server
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  • 16
    Publication Date: 2022-10-26
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Al Senafi, F., Anis, A., & Menezes, V. Surface heat fluxes over the northern Arabian Gulf and the northern Red Sea: Evaluation of ECMWF-ERA5 and NASA-MERRA2 reanalyses. Atmosphere, 10(9), (2019): 504, doi:10.3390/atmos10090504.
    Description: The air–sea heat fluxes in marginal seas and under extreme weather conditions constitute an essential source for energy transport and mixing dynamics. To reproduce these effects in numerical models, we need a better understanding of these fluxes. In response to this demand, we undertook a study to examine the surface heat fluxes in the Arabian Gulf (2013 to 2014) and Red Sea (2008 to 2010)—the two salty Indian Ocean marginal seas. We use high-quality buoy observations from offshore meteorological stations and data from two reanalysis products, the Modern-Era Retrospective analysis for Research and Applications version 2 (MERRA2) from the National Aeronautics and Space Administration (NASA) and ERA5, the fifth generation of the European Centre for Medium-Range Weather Forecasts (ECMWF) atmospheric reanalyses of global climate. Comparison of the reanalyses with the in situ-derived fluxes shows that both products underestimate the net heat fluxes in the Gulf and the Red Sea, with biases up to −45 W/m 2 in MERRA2. The reanalyses reproduce relatively well the seasonal variability in the two regions and the effects of wind events on air–sea fluxes. The results suggest that when forcing numerical models, ERA5 might provide a preferable dataset of surface heat fluxes for the Arabian Gulf while for the Red Sea the MERRA2 seems preferable.
    Description: This study was funded by the Research Sector at Kuwait University (project #ZS03/16) and by NSF (grant #OCE-1435665) supporting V.M.
    Keywords: Arabian Gulf ; Red Sea ; Persian Gulf ; Merra 2 ; ERA 5 ; Heat fluxes
    Repository Name: Woods Hole Open Access Server
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  • 17
    Publication Date: 2022-07-04
    Description: The Arctic is directly impacted by climate change. The increase in air temperature drives the thawing of permafrost and an increase in coastal erosion and river discharge. This leads to a greater input of sediment and organic matter into coastal waters, which substantially impacts the ecosystems, the subsistence economy of the local population, and the climate because of the transformation of organic matter into greenhouse gases. Yet, the patterns of sediment dispersal in the nearshore zone are not well known, because ships do not often reach shallow waters and satellite remote sensing is traditionally focused on less dynamic environments. The goal of this study is to use the extensive Landsat archive to investigate sediment dispersal patterns specifically on an exemplary Arctic nearshore environment, where field measurements are often scarce. Multiple Landsat scenes were combined to calculate means of sediment dispersal and sea surface temperature under changing seasonal wind conditions in the nearshore zone of Herschel Island Qikiqtaruk in the western Canadian Arctic since 1982. We use observations in the Landsat red and thermal wavebands, as well as a recently published water turbidity algorithm to relate archive wind data to turbidity and sea surface temperature. We map the spatial patterns of turbidity and water temperature at high spatial resolution in order to resolve transport pathways of water and sediment at the water surface. Our results show that these pathways are clearly related to the prevailing wind conditions, being ESE and NW. During easterly wind conditions, both turbidity and water temperature are significantly higher in the nearshore area. The extent of the Mackenzie River plume and coastal erosion are the main explanatory variables for sediment dispersal and sea surface temperature distributions in the study area. During northwesterly wind conditions, the influence of the Mackenzie River plume is negligible. Our results highlight the potential of high spatial resolution Landsat imagery to detect small-scale hydrodynamic processes, but also show the need to specifically tune optical models for Arctic nearshore environments.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , NonPeerReviewed
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  • 18
    Publication Date: 2022-06-20
    Description: Time-variable gravity measurements from the Gravity Recovery and Climate Experiment (GRACE) and GRACE-Follow On (GRACE-FO) missions and satellite altimetry measurements from CryoSat-2 enable independent mass balance estimates of the Earth’s glaciers and ice sheets. Both approaches vary in terms of their retrieval principles and signal-to-noise characteristics. GRACE/GRACE-FO recovers the gravity disturbance caused by changes in the mass of the entire ice sheet with a spatial resolution of 300 to 400 km. In contrast, CryoSat-2measures travel times of a radar signal reflected close to the ice sheet surface, allowing changes of the surface topography to be determined with about 5 km spatial resolution. Here, we present a method to combine observations from the both sensors, taking into account the different signal and noise characteristics of each satellite observation that are dependent on the spatial wavelength. We include uncertainties introduced by the processing and corrections, such as the choice of the re-tracking algorithm and the snow/ice volume density model for CryoSat-2, or the filtering of correlated errors and the correction for glacial-isostatic adjustment (GIA) for GRACE. We apply our method to the Antarctic ice sheet and the time period 2011–2017, in which GRACE and CryoSat-2 were simultaneously operational, obtaining a total ice mass loss of 178 ± 23 Gt yr−1. We present a map of the rate of mass change with a spatial resolution of 40 km that is evaluable across all spatial scales, and more precise than estimates based on a single satellite mission.
    Repository Name: EPIC Alfred Wegener Institut
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  • 19
    Publication Date: 2022-05-06
    Description: This work focuses on the study of land subsidence processes by means of multi-temporal and multi-frequency InSAR techniques. Specifically, we retrieve the long-term evolution (2003–2018) of the creeping phenomenon producing ground fissuring in the Ciudad Guzmán (Jalisco state, Mexico) urban area. The city is located on the northern side of the Volcan de Colima area, one of the most active Mexican volcanoes. On September 21 2012, Ciudad Guzmán was struck by ground fissures of about 1.5 km of length, causing the deformation of the roads and the propagation of fissures in adjacent buildings. The field surveys showed that fissures follow the escarpments produced during the central Mexico September 19 1985 Mw 8.1 earthquake. We extended the SAR (Synthetic Aperture Radar) interferometric monitoring starting with the multi-temporal analysis of ENVISAT and COSMO-SkyMed datasets, allowing the monitoring of the observed subsidence phenomena a ecting the Mexican city. We processed a new stack of Sentinel-1 TOPSAR acquisition mode images along both descending and ascending paths and spanning the 2016–2018 temporal period. The resulting long-term trend observed by satellites, together with data from volcanic bulletin and in situ surveys, seems to suggest that the subsidence is due to the exploitation of the aquifers and that the spatial arrangement of ground deformation is controlled by the position of buried faults.
    Description: Published
    Description: id 2246
    Description: 2T. Deformazione crostale attiva
    Description: JCR Journal
    Keywords: subsidence ; multi-temporal analysis ; PS ; SBAS ; InSAR ; urban monitoring ; buried faults
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 20
    Publication Date: 2022-10-27
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Farris, A. S., Defne, Z., & Ganju, N. K. Identifying salt marsh shorelines from remotely sensed elevation data and imagery. Remote Sensing, 11(15), (2019): 1795, doi: 10.3390/rs11151795.
    Description: Salt marshes are valuable ecosystems that are vulnerable to lateral erosion, submergence, and internal disintegration due to sea level rise, storms, and sediment deficits. Because many salt marshes are losing area in response to these factors, it is important to monitor their lateral extent at high resolution over multiple timescales. In this study we describe two methods to calculate the location of the salt marsh shoreline. The marsh edge from elevation data (MEED) method uses remotely sensed elevation data to calculate an objective proxy for the shoreline of a salt marsh. This proxy is the abrupt change in elevation that usually characterizes the seaward edge of a salt marsh, designated the “marsh scarp.” It is detected as the maximum slope along a cross-shore transect between mean high water and mean tide level. The method was tested using lidar topobathymetric and photogrammetric elevation data from Massachusetts, USA. The other method to calculate the salt marsh shoreline is the marsh edge by image processing (MEIP) method which finds the unvegetated/vegetated line. This method applies image classification techniques to multispectral imagery and elevation datasets for edge detection. The method was tested using aerial imagery and coastal elevation data from the Plum Island Estuary in Massachusetts, USA. Both methods calculate a line that closely follows the edge of vegetation seen in imagery. The two methods were compared to each other using high resolution unmanned aircraft systems (UAS) data, and to a heads-up digitized shoreline. The root-mean-square deviation was 0.6 meters between the two methods, and less than 0.43 meters from the digitized shoreline. The MEIP method was also applied to a lower resolution dataset to investigate the effect of horizontal resolution on the results. Both methods provide an accurate, efficient, and objective way to track salt marsh shorelines with spatially intensive data over large spatial scales, which is necessary to evaluate geomorphic change and wetland vulnerability.
    Description: This project was supported by the U.S. Geological Survey (USGS) Coastal/Marine Natural Hazards and Resources Program as well as the Massachusetts O ce of Coastal Zone Management under interagency agreement 16ENMALQ006000.
    Keywords: Marsh edge ; Marsh shoreline ; Unmanned aircraft system ; UAS ; UAV ; Drone ; Lidar ; Salt marsh ; Coastal wetlands ; Plum Island
    Repository Name: Woods Hole Open Access Server
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  • 21
    Publication Date: 2022-10-27
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Costello, J. H., Colin, S. P., Gemmell, B. J., & Dabiri, J. O. Hydrodynamics of vortex generation during bell contraction by the hydromedusa Eutonina indicans (Romanes, 1876). Biomimetics, 4(3), (2019): 44, doi:10.3390/biomimetics4030044.
    Description: Swimming bell kinematics and hydrodynamic wake structures were documented during multiple pulsation cycles of a Eutonina indicans (Romanes, 1876) medusa swimming in a predominantly linear path. Bell contractions produced pairs of vortex rings with opposite rotational sense. Analyses of the momentum flux in these wake structures demonstrated that vortex dynamics related directly to variations in the medusa swimming speed. Furthermore, a bulk of the momentum flux in the wake was concentrated spatially at the interfaces between oppositely rotating vortices rings. Similar thrust-producing wake structures have been described in models of fish swimming, which posit vortex rings as vehicles for energy transport from locations of body bending to regions where interacting pairs of opposite-sign vortex rings accelerate the flow into linear propulsive jets. These findings support efforts toward soft robotic biomimetic propulsion
    Description: This research was supported by awards from the National Science Foundation (1536672, 1511721 to J.H.C.; 1536688, 1510929 to S.P.C., 1511996 to B.J.G. and 1511333 to J.O.D.).
    Keywords: Swimming ; Vortex rings ; Wakes
    Repository Name: Woods Hole Open Access Server
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  • 22
    Publication Date: 2022-10-27
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Estrada-Gomez, S., Caldas Cardoso, F., Johana Vargas-Munoz, L., Carlos Quintana-Castillo, J., Arenas Gomez, C. M., Steffany Pineda, S., & Maria Saldarriaga-Cordoba, M. Venomic, transcriptomic, and bioactivity analyses of Pamphobeteus verdolaga venom reveal complex disulfide-rich peptides that modulate calcium channels. Toxins, 11(9), (2019): 496, doi:10.3390/toxins11090496.
    Description: Pamphobeteus verdolaga is a recently described Theraphosidae spider from the Andean region of Colombia. Previous reports partially characterized its venom profile. In this study, we conducted a detailed analysis that includes reversed-phase high-performance liquid chromatography (rp-HPLC), calcium influx assays, tandem mass spectrometry analysis (tMS/MS), and venom-gland transcriptome. rp-HPLC fractions of P. verdolaga venom showed activity on CaV2.2, CaV3.2, and NaV1.7 ion channels. Active fractions contained several peptides with molecular masses ranging from 3399.4 to 3839.6 Da. The tMS/MS analysis of active fraction displaying the strongest activity to inhibit calcium channels showed sequence fragments similar to one of the translated transcripts detected in the venom-gland transcriptome. The putative peptide of this translated transcript corresponded to a toxin, here named ω-theraphositoxin-Pv3a, a potential ion channel modulator toxin that is, in addition, very similar to other theraphositoxins affecting calcium channels (i.e., ω-theraphotoxin-Asp1a). Additionally, using this holistic approach, we found that P. verdolaga venom is an important source of disulfide-rich proteins expressing at least eight superfamilies.
    Keywords: Theraphosidae ; Pamphobeteus ; Peptides ; Disulfide-rich peptide (DRP) ; Inhibitory cysteine knot (ICK) ; Venomics ; Transcriptome ; Ion channels
    Repository Name: Woods Hole Open Access Server
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  • 23
    Publication Date: 2022-10-27
    Description: © The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Boss, E., Sherwood, C. R., Hill, P., & Milligan, T. Advantages and limitations to the use of optical measurements to study sediment properties. Applied Sciences-Basel, 8(12), (2018):2692, doi:10.3390/app8122692.
    Description: Measurements of optical properties have been used for decades to study particle distributions in the ocean. They are useful for estimating suspended mass concentration as well as particle-related properties such as size, composition, packing (particle porosity or density), and settling velocity. Measurements of optical properties are, however, biased, as certain particles, because of their size, composition, shape, or packing, contribute to a specific property more than others. Here, we study this issue both theoretically and practically, and we examine different optical properties collected simultaneously in a bottom boundary layer to highlight the utility of such measurements. We show that the biases we are likely to encounter using different optical properties can aid our studies of suspended sediment. In particular, we investigate inferences of settling velocity from vertical profiles of optical measurements, finding that the effects of aggregation dynamics can seldom be ignored.
    Description: This work was supported by the Office of Naval Research and the United States Geological Survey Coastal and Marine Geology Program. The unique instrument platform and data acquisition system was designed and built by technical staff lead by Marinna Martini at the United States Geological Survey Woods Hole Coastal and Marine Science Center. This team was also responsible for deployment and recovery of the instrumentation. We thank the Woods Hole Oceanographic Institution (WHOI) MVCO staff for support during this experiment, and we thank the captains and crews of the R/V Connecticut and the R/V Tioga. Any use of trade, product, or firm names is for descriptive purposes only and does not imply endorsement by the United States Government. This paper has benefited significantly from insightful comments from D. Stramski, A. Aretxabaleta and two anonymous reviewers.
    Keywords: Particle dynamics ; Optical properties ; Suspended sediment
    Repository Name: Woods Hole Open Access Server
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  • 24
    Publication Date: 2022-10-27
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Signell, R. P., & Pothina, D. Analysis and visualization of coastal ocean model data in the cloud. Journal of Marine Science and Engineering, 7(4), (2019);110, doi:10.3390/jmse7040110.
    Description: The traditional flow of coastal ocean model data is from High-Performance Computing (HPC) centers to the local desktop, or to a file server where just the needed data can be extracted via services such as OPeNDAP. Analysis and visualization are then conducted using local hardware and software. This requires moving large amounts of data across the internet as well as acquiring and maintaining local hardware, software, and support personnel. Further, as data sets increase in size, the traditional workflow may not be scalable. Alternatively, recent advances make it possible to move data from HPC to the Cloud and perform interactive, scalable, data-proximate analysis and visualization, with simply a web browser user interface. We use the framework advanced by the NSF-funded Pangeo project, a free, open-source Python system which provides multi-user login via JupyterHub and parallel analysis via Dask, both running in Docker containers orchestrated by Kubernetes. Data are stored in the Zarr format, a Cloud-friendly n-dimensional array format that allows performant extraction of data by anyone without relying on data services like OPeNDAP. Interactive visual exploration of data on complex, large model grids is made possible by new tools in the Python PyViz ecosystem, which can render maps at screen resolution, dynamically updating on pan and zoom operations. Two examples are given: (1) Calculating the maximum water level at each grid cell from a 53-GB, 720-time-step, 9-million-node triangular mesh ADCIRC simulation of Hurricane Ike; (2) Creating a dashboard for visualizing data from a curvilinear orthogonal COAWST/ROMS forecast model.
    Description: This research benefited from National Science Foundation grant number 1740648, and EarthSim project was funded by ERDC projects PETTT BY17-094SP and PETTT BY16-091SP. This project also benefited from research credits granted by Amazon.
    Keywords: Ocean modeling ; Cloud computing ; Data analysis ; Geospatial data visualization
    Repository Name: Woods Hole Open Access Server
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  • 25
    Publication Date: 2022-10-27
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Goodwin, J. D., Munroe, D. M., Defne, Z., Ganju, N. K., & Vasslides, J. Estimating connectivity of hard clam (Mercenaria mercenaria) and eastern oyster (Crassostrea virginica) larvae in Barnegat Bay. Journal of Marine Science and Engineering, 7(6), (2019): 167, doi:10.3390/jmse7060167.
    Description: Many marine organisms have a well-known adult sessile stage. Unfortunately, our lack of knowledge regarding their larval transient stage hinders our understanding of their basic ecology and connectivity. Larvae can have swimming behavior that influences their transport within the marine environment. Understanding the larval stage provides insight into population connectivity that can help strategically identify areas for restoration. Current techniques for understanding the larval stage include modeling that combines particle attributes (e.g., larval behavior) with physical processes of water movement to contribute to our understanding of connectivity trends. This study builds on those methods by using a previously developed retention clock matrix (RCM) to illustrate time dependent connectivity of two species of shellfish between areas and over a range of larval durations. The RCM was previously used on physical parameters but we expand the concept by applying it to biology. A new metric, difference RCM (DRCM), is introduced to quantify changes in connectivity under different scenarios. Broad spatial trends were similar for all behavior types with a general south to north progression of particles. The DRCMs illustrate differences between neutral particles and those with behavior in northern regions where stratification was higher, indicating that larval behavior influenced transport. Based on these findings, particle behavior led to small differences (north to south movement) in transport patterns in areas with higher salinity gradients (the northern part of the system) compared to neutral particles. Overall, the dominant direction for particle movement was from south to north, which at times was enhanced by winds from the south. Clam and oyster restoration in the southern portion of Barnegat Bay could serve as a larval supply for populations in the north. These model results show that coupled hydrodynamic and particle tracking models have implications for fisheries management and restoration activities.
    Description: This work is supported by the Barnegat Bay Partnership EPA grants CE98212311, CE98212312. We extend our deep thanks to anonymous reviewers and Lisa Lucas who provided thoughtful input that improved the manuscript. We thank Matthew Kozak and Ian Mitchell for technical advice and Elizabeth North for LTRANS guidance. Joe Caracapa and Jennifer Gius provided help running remote simulations. COAST model source code is available at https://code.usgs.gov/coawstmodel/COAWST [50]. The hydrodynamic model outoput is available at: http://geoport.whoi.edu/thredds/catalog/clay/usgs/users/zdefne/GRL/catalog.html [21] and particle tracking model outputs are available from the corresponding author upon request.
    Keywords: Bivalve connectivity ; Larval transport ; Modeling ; Retention clock ; RCM ; ROMS ; LTRANS ; Barnegat Bay ; Hard clam ; Eastern oyster
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  • 26
    Publication Date: 2022-10-26
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Le Roux, V., & Liang, Y. Ophiolitic pyroxenites record boninite percolation in subduction zone mantle. Minerals, 9(9), (2019): 565, doi: 10.3390/min9090565.
    Description: The peridotite section of supra-subduction zone ophiolites is often crosscut by pyroxenite veins, reflecting the variety of melts that percolate through the mantle wedge, react, and eventually crystallize in the shallow lithospheric mantle. Understanding the nature of parental melts and the timing of formation of these pyroxenites provides unique constraints on melt infiltration processes that may occur in active subduction zones. This study deciphers the processes of orthopyroxenite and clinopyroxenite formation in the Josephine ophiolite (USA), using new trace and major element analyses of pyroxenite minerals, closure temperatures, elemental profiles, diffusion modeling, and equilibrium melt calculations. We show that multiple melt percolation events are required to explain the variable chemistry of peridotite-hosted pyroxenite veins, consistent with previous observations in the xenolith record. We argue that the Josephine ophiolite evolved in conditions intermediate between back-arc and sub-arc. Clinopyroxenites formed at an early stage of ophiolite formation from percolation of high-Ca boninites. Several million years later, and shortly before exhumation, orthopyroxenites formed through remelting of the Josephine harzburgites through percolation of ultra-depleted low-Ca boninites. Thus, we support the hypothesis that multiple types of boninites can be created at different stages of arc formation and that ophiolitic pyroxenites uniquely record the timing of boninite percolation in subduction zone mantle.
    Description: This study was supported by National Science Foundation grants EAR-1220440 to V.L.R. and EAR-1624516 to Y.L. We thank the reviewers for their helpful suggestions, as well as Taylor Hough, Gretchen Swarr, Alberto Saal, Soumen Mallick, and Nilanjan Chatterjee for help with LA-ICP-MS and EPMA analyses, and Mark Kurz for help with sample collection.
    Keywords: Ophiolite ; Boninite ; Pyroxenite ; Josephine peridotite ; REE temperatures ; Diffusion ; Melt percolation ; Subduction zones
    Repository Name: Woods Hole Open Access Server
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  • 27
    Publication Date: 2022-08-12
    Description: The Arctic-Boreal regions experience strong changes of air temperature and precipitation regimes, which affect the thermal state of the permafrost. This results in widespread permafrost-thaw disturbances, some unfolding slowly and over long periods, others occurring rapidly and abruptly. Despite optical remote sensing offering a variety of techniques to assess and monitor landscape changes, a persistent cloud cover decreases the amount of usable images considerably. However, combining data from multiple platforms promises to increase the number of images drastically. We therefore assess the comparability of Landsat-8 and Sentinel-2 imagery and the possibility to use both Landsat and Sentinel-2 images together in time series analyses, achieving a temporally-dense data coverage in Arctic-Boreal regions. We determined overlapping same-day acquisitions of Landsat-8 and Sentinel-2 images for three representative study sites in Eastern Siberia. We then compared the Landsat-8 and Sentinel-2 pixel-pairs, downscaled to 60 m, of corresponding bands and derived the ordinary least squares regression for every band combination. The acquired coefficients were used for spectral bandpass adjustment between the two sensors. The spectral band comparisons showed an overall good fit between Landsat-8 and Sentinel-2 images already. The ordinary least squares regression analyses underline the generally good spectral fit with intercept values between 0.0031 and 0.056 and slope values between 0.531 and 0.877. A spectral comparison after spectral bandpass adjustment of Sentinel-2 values to Landsat-8 shows a nearly perfect alignment between the same-day images. The spectral band adjustment succeeds in adjusting Sentinel-2 spectral values to Landsat-8 very well in Eastern Siberian Arctic-Boreal landscapes. After spectral adjustment, Landsat and Sentinel-2 data can be used to create temporally-dense time series and be applied to assess permafrost landscape changes in Eastern Siberia. Remaining differences between the sensors can be attributed to several factors including heterogeneous terrain, poor cloud and cloud shadow masking, and mixed pixels.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Article , NonPeerReviewed , info:eu-repo/semantics/article
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  • 28
    Publication Date: 2022-05-06
    Description: In situ and remote-sensing measurements have been used to characterize the run-up phase and the phenomena that occurred during the August–November 2014 flank eruption at Stromboli. Data comprise videos recorded by the visible and infrared camera network, ground displacement recorded by the permanent-sited Ku-band, Ground-Based Interferometric Synthetic Aperture Radar (GBInSAR) device, seismic signals (band 0.02–10 Hz), and high-resolution Digital Elevation Models (DEMs) reconstructed based on Light Detection and Ranging (LiDAR) data and tri-stereo PLEIADES-1 imagery. This work highlights the importance of considering data from in situ sensors and remote-sensing platforms in monitoring active volcanoes. Comparison of data from live-cams, tremor amplitude, localization of Very-Long-Period (VLP) source and amplitude of explosion quakes, and ground displacements recorded by GBInSAR in the crater terrace provide information about the eruptive activity, nowcasting the shift in eruptive style of explosive to effusive. At the same time, the landslide activity during the run-up and onset phases could be forecasted and tracked using the integration of data from the GBInSAR and the seismic landslide index. Finally, the use of airborne and space-borne DEMs permitted the detection of topographic changes induced by the eruptive activity, allowing for the estimation of a total volume of 3.07 ± 0.37 × 106 m3 of the 2014 lava flow field emplaced on the steep Sciara del Fuoco slope.
    Description: This work has been financially supported by the “Presidenza del Consiglio dei Ministri – Dipartimento della Protezione Civile” (Presidency of the Council of Ministers – Department of Civil Protection) within the framework of the InGrID2015-2016 and SAR.NET2017 projects (Scientific Responsibility: NC); this publication, however, does not reflect the position and the official policies of the Department. FDiT has been supported by a post-doc fellowship founded by the “Università degli Studi di Firenze – Ente Cassa di Risparmio di Firenze” (D.R. n. 127804 (1206) 2015; “Volcano Sentinel” project). This work has been financially supported by "Volcano Sentinel—extension” project (Call: “Settore ricerca scientifica e innovazione tecnologica”; founded by: Ente Cassa di Risparmio di Firenze. Scientific Responsibility: FeDiT).
    Description: Published
    Description: id 2035
    Description: 5V. Processi eruttivi e post-eruttivi
    Description: JCR Journal
    Keywords: landslides ; effusive activity ; Ground-Based InSAR ; infrared live cam ; seismic monitoring ; PLEIADES ; Digital Elevation Models ; optical sensors ; Stromboli volcano ; The 2014 effusive eruption ; Remote-sensing measurements
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 29
    Publication Date: 2022-06-08
    Description: We collected and analysed 58 samples of groundwater from wells in the Barcellona-Milazzo Plain, one of the most important coastal aquifers of Sicily (Italy), to determine major, minor, and trace element concentrations. In this area, geogenic and anthropogenic sources of heavy metals and other pollutants co-act, making the individuation of the main pollution sources difficult. Our work was aimed at the application of geostatistical criteria for discriminating between these pollution sources. We used probability plots for separating anomalous values from background concentrations, which were plotted on maps and related to possible sources of pollutants. Our results indicate that hydrothermal fluid circulation and the water–rock interaction of country rocks that host mineralized ore deposits generate a significant flux of heavy metals to groundwater, as well as anthropogenic sources like intense agriculture and industrial activities. In particular, NO3, F, and Ni exceed the Maximum Admitted Concentrations (MACs) established by the WHO and Italian legislation for drinking-water. The spatial distributions of geogenic and anthropogenic sources were so deeply interlocked that their separation was not easy, also employing geostatistical tools. This complex scenario makes the implementation of human health risk mitigation actions difficult, since the flow of pollutants is in many cases controlled by simple water–rock interaction processes.
    Description: Published
    Description: id 285
    Description: 6A. Geochimica per l'ambiente
    Description: JCR Journal
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 30
    Publication Date: 2022-05-26
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Sutherland, K. R., Gemmell, B. J., Colin, S. P., & Costello, J. H. Maneuvering performance in the colonial siphonophore, Nanomia bijuga. Biomimetics, 4(3), (2019): 62, doi:10.3390/biomimetics4030062.
    Description: The colonial cnidarian, Nanomia bijuga, is highly proficient at moving in three-dimensional space through forward swimming, reverse swimming and turning. We used high speed videography, particle tracking, and particle image velocimetry (PIV) with frame rates up to 6400 s−1 to study the kinematics and fluid mechanics of N. bijuga during turning and reversing. N. bijuga achieved turns with high maneuverability (mean length–specific turning radius, R/L = 0.15 ± 0.10) and agility (mean angular velocity, ω = 104 ± 41 deg. s−1). The maximum angular velocity of N. bijuga, 215 deg. s−1, exceeded that of many vertebrates with more complex body forms and neurocircuitry. Through the combination of rapid nectophore contraction and velum modulation, N. bijuga generated high speed, narrow jets (maximum = 1063 ± 176 mm s−1; 295 nectophore lengths s−1) and thrust vectoring, which enabled high speed reverse swimming (maximum = 134 ± 28 mm s−1; 37 nectophore lengths s−1) that matched previously reported forward swimming speeds. A 1:1 ratio of forward to reverse swimming speed has not been recorded in other swimming organisms. Taken together, the colonial architecture, simple neurocircuitry, and tightly controlled pulsed jets by N. bijuga allow for a diverse repertoire of movements. Considering the further advantages of scalability and redundancy in colonies, N. bijuga is a model system for informing underwater propulsion and navigation of complex environments.
    Description: This research was funded by the National Science Foundation (NSF) 1829932 and 173764 to K.R.S., NSF 1830015, 1536672, 1511721 to J.H.C., 1455440, 1536688, 1829913 to S.P.C., NSF 1511996 to B.J.G.
    Keywords: turn ; reverse ; agility ; maneuverability ; propulsion ; Nanomia bijuga
    Repository Name: Woods Hole Open Access Server
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  • 31
    Publication Date: 2022-05-26
    Description: © The Author(s), 2019. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Foglini, F., Grande, V., Marchese, F., Bracchi, V. A., Prampolini, M., Angeletti, L., Castellan, G., Chimienti, G., Hansen, I. M., Gudmundsen, M., Meroni, A. N., Vertino, A., Badalamenti, F., Corselli, C., Erdal, I., Martorelli, E., Savini, A., & Taviani, M. (2019). Application of hyperspectral imaging to underwater habitat mapping, Southern Adriatic Sea. Sensors, 19(10), (2019): 2261, doi:10.3390/s19102261.
    Description: Hyperspectral imagers enable the collection of high-resolution spectral images exploitable for the supervised classification of habitats and objects of interest (OOI). Although this is a well-established technology for the study of subaerial environments, Ecotone AS has developed an underwater hyperspectral imager (UHI) system to explore the properties of the seafloor. The aim of the project is to evaluate the potential of this instrument for mapping and monitoring benthic habitats in shallow and deep-water environments. For the first time, we tested this system at two sites in the Southern Adriatic Sea (Mediterranean Sea): the cold-water coral (CWC) habitat in the Bari Canyon and the Coralligenous habitat off Brindisi. We created a spectral library for each site, considering the different substrates and the main OOI reaching, where possible, the lower taxonomic rank. We applied the spectral angle mapper (SAM) supervised classification to map the areal extent of the Coralligenous and to recognize the major CWC habitat-formers. Despite some technical problems, the first results demonstrate the suitability of the UHI camera for habitat mapping and seabed monitoring, through the achievement of quantifiable and repeatable classifications.
    Description: Flagship Project RITMARE (La Ricerca Italiana per il Mare) and EVER-EST projects (ID: 674907).
    Keywords: hyperspectral camera ; spectral library ; habitat mapping ; coralligenous ; cold-water coral ; Adriatic Sea
    Repository Name: Woods Hole Open Access Server
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  • 32
    Publication Date: 2023-03-31
    Description: Coeval changes in atmospheric CO2 and 14C contents during the last deglaciation are often attributed to ocean circulation changes that released carbon stored in the deep ocean during the Last Glacial Maximum (LGM). Work is being done to generate records that allow for the identification of the exact mechanisms leading to the accumulation and release of carbon from the oceanic reservoir, but these mechanisms are still the subject of debate. Here we present foraminifera 14C data from five cores in a transect across the Chilean continental margin between ~540 and ~3,100 m depth spanning the last 20,000 years. Our data reveal that during the LGM, waters at ~2,000 m were 50% to 80% more depleted in Δ14C than waters at ~1,500 m when compared to modern values, consistent with the hypothesis of a glacial deep ocean carbon reservoir that was isolated from the atmosphere. During the deglaciation, our intermediate water records reveal homogenization in the Δ14C values between ~800 and ~1,500 m from ~16.5–14.5 ka cal BP to ~14–12 ka cal BP, which we interpret as deeper penetration of Antarctic Intermediate Water. While many questions still remain, this process could aid the ventilation of the deep ocean at the beginning of the deglaciation, contributing to the observed ~40 ppm rise in atmospheric pCO2.
    Repository Name: EPIC Alfred Wegener Institut
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  • 33
    Publication Date: 2023-06-21
    Description: Histone methylation patterns are important epigenetic regulators of mammalian development, notably through stem cell identity maintenance by chromatin remodeling and transcriptional control of pluripotency genes. But, the implications of histone marks are poorly understood in distant groups outside vertebrates and ecdysozoan models. However, the development of the Pacific oyster Crassostrea gigas is under the strong epigenetic influence of DNA methylation, and Jumonji histone-demethylase orthologues are highly expressed during C. gigas early life. This suggests a physiological relevance of histone methylation regulation in oyster development, raising the question of functional conservation of this epigenetic pathway in lophotrochozoan. Quantification of histone methylation using fluorescent ELISAs during oyster early life indicated significant variations in monomethyl histone H3 lysine 4 (H3K4me), an overall decrease in H3K9 mono- and tri-methylations, and in H3K36 methylations, respectively, whereas no significant modification could be detected in H3K27 methylation. Early in vivo treatment with the JmjC-specific inhibitor Methylstat induced hypermethylation of all the examined histone H3 lysines and developmental alterations as revealed by scanning electronic microscopy. Using microarrays, we identified 376 genes that were differentially expressed under methylstat treatment, which expression patterns could discriminate between samples as indicated by principal component analysis. Furthermore, Gene Ontology revealed that these genes were related to processes potentially important for embryonic stages such as binding, cell differentiation and development. These results suggest an important physiological significance of histone methylation in the oyster embryonic and larval life, providing, to our knowledge, the first insights into epigenetic regulation by histone methylation in lophotrochozoan development.
    Repository Name: EPIC Alfred Wegener Institut
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  • 34
    Publication Date: 2023-06-21
    Description: The sea-ice climatology and sea-ice trends and variability are evaluated in simulations with the new version of the coupled Arctic atmosphere-ocean-sea ice model HIRHAM–NAOSIM 2.0. This version utilizes upgraded model components for the coupled subsystems, which include physical and numerical improvements and higher horizontal and vertical resolution, and a revised coupling procedure with the aid of the coupling software YAC (Yet Another Coupler). The model performance is evaluated against observationally based data sets and compared with the previous version. Ensemble simulations for the period 1979–2016 reveal that Arctic sea ice is thicker in all seasons and closer to observations than in the previous version. Wintertime biases in sea-ice extent, upper ocean temperatures, and near-surface air temperatures are reduced, while summertime biases are of similar magnitude as in the previous version. Problematic issues of the current model configuration and potential corrective measures and further developments are discussed.
    Repository Name: EPIC Alfred Wegener Institut
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  • 35
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    Biopolymers 25 (1986), S. 1-4 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 36
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    Biopolymers 25 (1986), S. 17-30 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mononucleotide conformations are important in understanding the structural aspects of nucleic acids and polynucleotides. In order to study the influence of stacking interactions between adjacent bases in a polynucleotide on the preferred conformations of mononucleotides, conformational energy calculations have been carried out on dinucleoside monophosphate fragments. Four base sequences - d(ApT), d(TpA), d(CpG), and d(GpC) -  have been analyzed in the framework of helical structures. Flexibility of the furanose ring has been incorporated in the investigations. Energetically favored conformers of the four compounds correspond to a variety of left- and right-handed uniform helical structures, similar to those of the commonly observed polymorphous forms. Implications of these investigations on the further understanding of double-helical polynucleotide conformations are briefly discussed.
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  • 37
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have measured vibrational CD spectra in the 3600-1250 cm-1 region of two monodisperse, protected octapeptides, which form right-handed 310-helices in CDC13 solution. The spectra are similar in sign pattern to those obtained for right-handed α-helices in solution but are smaller in magnitude and, additionally, provide evidence of some line-shape differences. The delineation of this type of ordered conformation was accomplished by means of 1H-nmr. Such a solution structure is consistent with the x-ray crystal structure of one of these molecules.
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  • 38
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    Biopolymers 25 (1986), S. 135-152 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of a series of biologically active gastrin fragments with calcium ions has been investigated by CD in trifluoroethanol. It was found that the gastrin octapeptide pGlu10,Nle15-HG[10-17] binds one calcium ion per molecule. The hypothesis is made that the binding involves the C-terminal, biologically important tetrapeptide. When the chain is elongated to the gastrin nonamer pGlu9,Nle15-HG[9-17], a second binding site is available, which is most likely situated at the N-terminal part of the molecule. Further elongation of the peptide chain up to the dodecapeptide pGlu6,Nle15-HG[6-17] does not provide any additional binding site. Saturation of the two sites in the shorter peptides produces different changes in the chiroptical properties in the near- and far-uv. As the chain is elongated, this difference tends to disappear. This result is consistent with an increased conformational order of the longer peptides. In the shorter fragments, the strength of this second binding is appreciably lower than that of the first, while in the longer peptides, the strength of the two bindings is comparable. On the assumption that the variation of the CD properties is proportional to the extent of binding, the constant for the binding of the second ion was determined to be of the order of 5 × 105 L/mol for the nonapeptide.
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  • 39
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    Biopolymers 25 (1986) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 40
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 41
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 42
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    Biopolymers 25 (1986), S. 249-266 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We present molecular mechanical calculations on the complexes of netropsin with dA6·dT6, d(TATATA)2, d(CGCGCG)2, and d(CGCGAATTCGCG)2. The complexes were model built using computer graphics and then completely energy refined. Our calculations are consistent with the observed AT preference for netropsin and suggest that mixed sugar pucker geometries should be more stable than uniform in netropsin complexes with poly[d(A-T)]·poly[d(A-T)] and poly(dA)·poly(dt). The netropsin·d(TATATA) and netropsin·dA6·dT6 complexes are significantly different in structure, leading to a possible reason why the observed thermodynamics of netropsin-association with poly[d(A-T)]·poly[d(A-T)] and with poly(dA)·poly(dT) are so different. We also model built and energy refined a structure of netropsin-d(CGCGAATTCGCG)2 using as a guide the nmr data of Patel [(1982) Proc. Natl. Acad. Sci. USA, 79, 6424-6428] and found a three-dimensional structure qualitatively consistent with the NOE enhancements observed by him. After our calculations were completed, we learned of an x-ray structure of a netropsin:d(CGCGAATTCGCG)2 complex, and we compared the structure found in our calculation with the x-ray structure.
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  • 43
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We utilize the dynamic quenching of the triplet state of methylene blue by molecular oxygen to observe changes in the rate at which oxygen can penetrate the helix as a function of base-pair composition. The results indicate that the interior of the oligonucleotide dA-dT is more accessible than dG-dC to small molecules such as dioxygen.
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  • 44
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    Biopolymers 25 (1986) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 45
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    Biopolymers 25 (1986), S. 375-392 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of spermine with nucleic acids is simulated theoretically using refined semi-empirical energy formulae and an advanced minimization procedure. Various nucleic acids are considered: model homopolymeric DNA's, a dodecamer (CGCGAATTCGCG) of type B-DNA, as well as a transfer RNA, tRNAPhe. The dominant role of electrostatic potential in determining the preferential binding sites of spermine is demonstrated in each of these cases and the role of counterions, nucleic acid structure, and base-pair sequence is analyzed.
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  • 46
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    Biopolymers 25 (1986), S. 241-247 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Permittivity ε′ and dielectric loss ε″ of aqueous Na-DNA gels have been measured at 10 GHz in the temperature interval -15 to + 45°C. The experimental results are analyzed in terms of a three-component equation (Na-DNA, interfacial water, bulk water) and yield a value of 35 water molecules/nucleotide interacting with DNA. According to theoretical and experimental data the presence of strongly bonded and weakly bonded water is considered. The modified water exhibits a mean dielectric relaxation time two-or threefold greater than that of bulk water.
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  • 47
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    Biopolymers 25 (1986), S. 291-306 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of solvent viscosity (ηs) and temperature (T) on the shape of the concentration dependence of the principal and total recoils in creep-recovery viscoelastometry experiments has been studied for T4 DNA solutions. The range of DNA concentration (c) was 2 - 40 μg/ml; glycerol, 70-80% v/v, sucrose, 60% v/v; NaCl, 5 mM - 1M; and T, 275 - 323 K. A linear proportionality between recoil and c was obtained at high ηs/T. At low ηs/T, the c-dependence was nonlinear, approaching saturation at higher c. At low c, the slope of both curves was the same. Transition between “linear” and “nonlinear” values occurred over a narrow range of ηs/T (a width of 1-5 K if ηs/T was changed by varying T). (ηs/T)tr, the midpoint of the transition, was independent of solvent properties other than viscosity. Also, (ηs/T)tr increased with c. For a given c, ηs/T values above this transitional value yield linear behavior; below this, nonlinear behavior. The ratio of linear to nonlinear recoil values is a linear function of c with Kc, the slope of this dependence, independent of ηs and T. A kinetic model for the observed nonlinearity of recoil with c is presented. It explains the independence of Kc on ηs and T. An attempt has been made to explain the linear-nonlinear transitions by comparison of τ1 and TR, the lifetime of the contact points of the polymer network in the de Gennes theory. The nonlinear values are consistent with a pseudogel that exists when τ1 〈 TR. At τ1 〉 TR, the DNA behavior is similar to that in dilute solutions (linear values). Thus, the condition for transition is τ1 = TR. However, some unsolved problems remain.
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  • 48
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    Biopolymers 25 (1986), S. 337-350 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: If protein single crystals larger than those suitable for x-ray analysis are obtained, various spectroscopic, thermal, mechanical, and electrical measurements become possible. To understand the factors governing the crystal size, tetragonal lysozyme crystals were grown in batches at 15°C from solutions of different protein and salt concentrations between pH 4-7. The number and size of the crystals, and the protein concentration remaining in the supernatant, varied markedly with the initial salt amount, pH, and cation species, but large crystals always grew when the initial protein concentration (P) was in a narrow range of 2.5-3 times the crystal solubility (S). It was also shown (1) that the period before the first crystals appeared (D) varied as D ∝ (P/S)-n, where n ≃ 5, and (2) that many previous experiments used more supersaturated solutions than the optimal ones thus determined. The reason why large crystals grow only from moderately supersaturated solutions is discussed. The crystal size of the orthorhombic form grown at 40°C was less sensitive to pH and P than the tetragonal form. An effort to measure D and the solubility at 40°C revealed many differences between the two crystal forms, which we ascribe to different interactions to promote crystallization.
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  • 49
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    Biopolymers 25 (1986), S. 393-405 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pinellin is a plant protein extracted from the rhizome of the Chinese herb Pinellia. It has the ability to abort early pregnancy in mice as well as in rabbits. Studies on the conformational changes of pinellin have been carried out in our laboratory using intrinsic fluorescence and CD. Experimental results show that some tryptophanyl side chains are buried more deeply than others, which results in the heterogeneity of tryptophanyl emission. CD data indicated a high content of β-pleated sheet and β-turn for the backbone conformation. The results of fluorescence and CD measurements both demonstrated the presence of intermediates along the path of denaturation. The following was proposed as the unfolding mechanism of pinellin in 6M guanidine hydrochloride: native state → first intermediate → second intermediate → fully unfolded state.
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  • 50
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    Biopolymers 25 (1986), S. 469-487 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fourier transform ir (FTIR) spectra of 21 globular proteins have been obtained at 2 cm-1 resolution from 1600 to 1700 cm-1 in deuterium oxide solution. Fourier self-deconvolution was applied to all spectra, revealing that the amide I band of each protein except casein consists of six to nine components. The components are observed at 11 well-defined frequencies, although all proteins do not exhibit components at every characteristic frequency. The root mean square (RMS) deviation of 124 individual values from the 11 average characteristic frequencies is 1.9 cm-1. The observed components are assigned to helical segments, extended beta-segments, unordered segments, and turns. Segments with similar structures do not necessarily exhibit band components with identical frequencies. For instance, the lower frequency beta-structure band can vary within a range of approximately 15 cm-1. The relative areas of the individual components of the deconvolved spectra were determined by a Gauss-Newton, iterative curve-fitting procedure that assumed Gaussian band envelopes for the deconvolved components. The measured areas were used to estimate the percentage of helix and beta-structure for each of 21 globular proteins. The results are in good general agreement with values derived from x-ray data by Levitt and Greer. The RMS deviation between 22 values (alpha- and beta-content of 11 beta-rich proteins measured by both techniques) is 2.5 percentage points; the maximum absolute deviation is 4 percentage points.
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  • 51
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A time-resolved fluorescence study of ethidium bromide (EB) in the presence of poly(dG-dC) and of poly(dG-dC) modified by chlorodiethylenetriamine platinum(II) chloride is presented under solvent conditions in which these polymers adopt the Z-conformation (high ionic strength). It is shown that these polynucleotides can intercalate a very small quantity of EB. The binding parameters have been determined. The fluorescence lifetime of EB is slightly higher when bound to the Z-conformation (≃25 ns) than when bound to the B-conformation (≃23.7 ns). The nature of the salt has been checked. In the presence of 2.5M NaClO4, no transition from the Z-conformation to another conformation is observed when EB is added. On the contrary, in the presence of 4.25M NaCl, EB induces a cooperative transition from the Z-conformation to a conformation characterized by a much higher affinity for EB intercalation. In the case of poly(dG-dC) this last conformation is identical to the one observed at low ionic strength (B-conformation), but in the case of the platinated polymer this conformation is slightly different, as judged by the smaller value of the fluorescence lifetime of the intercalated EB.
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  • 52
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    Biopolymers 25 (1986), S. 539-554 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Intensities of polarized fluorescence from ethidium bound to phage λ DNA undergoing agarose gel electrophoresis were measured. The intensities were strongly field dependent at voltage gradients of 8 V/cm, consistent with a partial orientation of DNA helices in the direction of electrophoresis about 500 times larger than seen in the same field in solution. Such an orientation was predicted by a reptation model of gel electrophoresis advanced by Lumpkin et al. [(1985) Biopolymers, 24, 1573-1593]. The present results can be fit successfully to this theory with a single adjustable parameter, the gel-DNA contact distance. Also, λ DNA electrophoretic mobilities in the same concentration gel were determined using the same buffer system. Both orientation and mobility measurements can be fit to the reptation theory within a factor of two using the same values of two parameters, the gel-DNA contact distance and the ratio of DNA charge to frictional coefficient.
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  • 53
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    Biopolymers 25 (1986), S. 527-537 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The association of heparin with thrombin was investigated by fluorometric titration. A maximum of 25% of the fluorescence of fluorescein-labeled heparin (FTC-heparin) was quenched at thrombin saturation in the absence of NaCl. FTC-heparin (H) associated tightly with thrombin (T) and the association constant of the ternary complex, H2T, formed in the absence of NaCl, was calculated to be 1.7 × 108M-1. However, the association was strongly influenced by the NaCl concentration, and the association constant of the equimolar complex, HT, formed in 0.15M NaCl was found to be 1 × 106M-1. The first-order rate constant, kapp, for inactivation of thrombin by antithrombin III (AT III) and low-affinity heparin (LA-heparin) was comparable with that of high-affinity heparin (HA-heparin) in the absence of NaCl, but decreased with an increase in the concentration of NaCl. The decreased enhancement of the thrombin-AT III reaction by LA-heparin at high NaCl concentration appeared to result from a decreased association of thrombin with LA-heparin, thus reducing the formation of the ternary complex, thrombin-LA-heparin-AT III.
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  • 54
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    Biopolymers 25 (1986), S. 607-625 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electron-diffraction pattern of an oriented film of poly(α-aminoisobutyric acid) in the 310-helical conformation has been analyzed. The conformation was obtained by a linked-atom least-squares refinement of average values from crystal structures. Specimens treated with dichloracetic acid, to improve their crystallinity, conform to space group R3c with a = 21.8 Å, c = 5.95 Å. The structure contains channels that can accommodate molecules of dichloracetic acid. One molecule of acid per six residues fills the channels, and the R-factor then is 34% using 23 reflections. Ir evidence is presented to show that the acid may hydrogen bond to the peptide groups. Some reflections occasionally observed on the diffraction photographs are attributed to a 15/4 α-helix. The significance of the results is considered in relation to Aib-containing peptides.
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  • 55
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    Biopolymers 25 (1986), S. 639-654 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Four different types of ir experiments, involving changes in pH, changes in pressure, and the use of nonaqueous solvents, and with either albumin molecules dissolved in saline or adsorbed albumin films, support the hypothesis that the bandwidth of the amide I vibration of albumin is directly related to the amount of bound water in this protein. From the amide I band narrowing and the amide I shift to higher frequencies, it is proposed that a more ordered helix structure results as the amount of bound water is decreased.
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  • 56
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have recorded one-dimensional exchangeable proton and two-dimensional nonexchangeable proton nmr spectra on the complex of netropsin with the self-complementary d(G-G-T-A-T-A-C-C) duplex in aqueous solution between 25° and 35°C. The antibiotic amide, pyrrole, and methylene protons, and the nucleic acid base and sugar H1′, H2′, H2″, and H3′ protons, have been assigned from an analysis of the two-dimensional nuclear Overhauser effect (NOESY) spectra of the complex. We observe intermolecular NOEs between the antibiotic concave face amide, pyrrole, and CH2 resonances, and the adenosine H2 and sugar H1′ protons of base-pairs T3·A6 and A4·T5 in the central TATA core of the d(G1-G2-T3-A4-T5-A6-C7-C8) duplex. We present a molecular model outlining these seven antibiotic-DNA contacts for the complex in solution. The observed line-broadening of several base and sugar protons at the TATA minor groove netropsin binding site in the complex at 35°C are interpreted in terms of intermediate exchange between two orientations of bound netropsin on the duplex.
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  • 57
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The amino acid sequence of the collagen α1(I) chain (calf) is analyzed. Deviations of random tripeptide distribution leads to the definition of clusters. Inside these regions, collagen-typical tripeptides are located. Besides Gly-Pro-Hyp, Gly-Pro-Ala, and Gly-Ala-Hyp, the polar sequences Gly-Glu-Hyp, Gly-Ala-Arg, Gly-Glu-Arg, and Gly-Pro-Lys form typical sequences. The neighborhood of each tripeptide is analyzed and classified. The proximity to the collagen-typical tripeptides is registered. Cluster theory: Less-typical sequences also fold as members of the collagen triple helix and they are as reasonable as well as important for the collagen structure as the cluster tripeptides, but only the latter are important for the nucleation of the triple-helical folding.
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  • 58
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    Biopolymers 25 (1986), S. 1087-1093 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solvent accessible peptide bonds in proteins exhibit a 1-3° compression of the OCN bond angle and a corresponding expansion of the NCCa bond angle, relative to buried peptide bonds. These changes are consistent with an increase in hydrogen bonding to the carbonyl oxygen accompanying solvent exposure (J. D. Dunitz and F. K. Winkler, (1975) Acta Cryst. B31, 251-263). For amphiphilic structures such as α-helices, systematic differences in peptide-bond geometry between solvent-exposed and buried residues will generate significant curvature. A decrease of 4° in the OCN bond angle between hydrophilic and hydrophobic sides of an amphiphilic helix will lead to smooth bending, with a radius of curvature of about 70 Å. This curvature is in the range observed for α-helices in proteins. Helix curvature is estimated to have only a small effect on the magnitude and direction of the helical dipole moment.
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  • 59
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    Biopolymers 25 (1986), S. 1157-1175 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Small-angle neutron scattering (SANS) was used to examine concentrated bovine serum albumin solutions of up to 20% protein w/v. At higher protein concentrations, scattering data show distinct features that can be ascribed to strong intermolecular interactions. Differential scattering cross-sections are fitted to a theoretical model of interparticle potential consisting of a hard core plus an exponentially decaying “tail.” For moderate ionic strength (0.03M K Acetate, pH 5.9), the intermolecular interaction agrees with the double-layer repulsive part of the well-known DLVO (Derjaguin, Landau, Verwey, Overbeek) theory for interacting colloidal particles. We thus demonstrate that it is possible to determine size parameters and the surface charge of protein molecules in dense solutions. At high salt concentrations (≥0.2M NaCl) data can be fitted by the same potential model, although interpretation in terms of DLVO theory is not possible. Even in this case, however, “effective” molecular size and potential parameters can be determined.
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    Biopolymers 25 (1986), S. 1179-1184 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 61
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    Biopolymers 25 (1986), S. 1229-1247 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A computational method for attempting to predict protein complexes from the coordinates of the individual proteins has been developed. It is based on matching complementary patterns of knobs and holes. The computer algorithm correctly and uniquely predicts the association of the alpha and beta subunits to form the αβ dimer corresponding to the α1β1 interface in the hemoglobin tetramer. It fails to correctly dock trypsin inhibitor onto trypsin. Nevertheless, this lone success is still a significant advance over previous protein-docking algorithms. The method is also important because it introduces several ways to measure the shape of protein surface regions.
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  • 62
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    Biopolymers 25 (1986), S. 1209-1228 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We studied the interactions of the substitution-inert inversion-labile complexes Fe(bipy)32+ and Fe(phen)32+ [and the inversion-stable complex Ru(bipy)32+] with DNA. The association of these complexes to DNA is mainly electrostatic, and Fe(phen)32+ shows a more effective binding to DNA than the two bipyridyl complexes, possibly owing to a different binding mode. The interactions are enantioselective, leading to a Pfeiffer shift in the diastereomeric inversion equilibria and an excess of the Δ-enantiomer of Fe(phen)32+ and Fe(bipy)32+, which is directly monitorable through CD. The partition constants for the inversion equilibrium range from 1.3 to 2.0 for Fe(bipy)32+ and Fe(phen)32+, depending on ionic conditions. From flow LD information about the orientation of the complexes on DNA was obtained: it is consistent with a fit of the Δ-enantiomer in the major groove of the right-handed DNA helix. The mechanisms of interaction are discussed against equilibrium, spectroscopic, and kinetic data.
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  • 63
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    Biopolymers 25 (1986), S. 1283-1297 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The distribution of bound Mn2+ ions about poly(rI)·poly(rC) has been studied by measuring the effect of this paramagnetic metal ion on the relaxation behavior of poly(rI)·poly(rC) protons. By combining selective spin - lattice and spin - spin relaxation rates for various protons, some of the principle regions of ion association can be identified. The relaxation data on the CH6 proton are consistent with a 〈 10% occupancy of phosphate inner-sphere binding sites. The broadening of the imino proton resonance requires a substantial occupancy of sites located in the major groove, possibly near IN7. This would also be consistent with the observation that IH8 resonance is the proton most susceptible to relaxation by Mn2+. The relaxation data for the IH2 proton indicate a relatively low occupancy of minor-groove binding sites (e.g., IN3).
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  • 64
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The combination of ultrafiltration and difference spectroscopy allows the quantitative determination of spectra of thionine bound to heparin. The spectra of the bound dye do not depend on the degree of coverage; this and the shape of the Scatchard plot show that “all-or-none” binding is valid. A calculus of variations based on a modification of the Hill plot shows that aggregates of seven thionine cations are bound. Tetrasaccharides with an average charge of two carboxylate and five sulfate groups are suggested to be the binding sites. The binding constant given for one mole thionine is 4.4 · 105 M-1. The Gibbs enthalpy for binding of one mole of thionine is -31.7 kJ·M-1 at 20°C.
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  • 65
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The kinetics of ethidium's intercalative binding to DNA packaged in bacteriophage T7 and two T7 deletion mutants have been determined, using enhancement of fluorescence to quantitate binding. At a constant ethidium concentration, the results can be described as first-order binding with two different rate constants, k1* (= k1 + k-1) and k2* (= k2 + k-2). The larger rate constant (k1*) was at least four orders of magnitude smaller than the comparable first-order forward rate constant for binding to DNA released from its capsid. At 25°C values of k1* decreased as the amount of DNA packaged per internal volume increased. This latter observation indicates that the rate of ethidium's binding to packaged T7 DNA is limited by an event that occurs inside of the DNA-containing region of T7, not by the crossing of T7 capsid's outer shell. Arrhenius plots of kM1* are biphasic, indicating a transition for packaged DNA at a temperature of 20°C. The data indicate that k1* s are limited by either sieving of ethidium during its passage through the packaged DNA or subsequent hindered intercalation.
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  • 66
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    Biopolymers 25 (1986) 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 67
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    Biopolymers 25 (1986), S. 1399-1417 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The three-dimensional structure was determined by x-ray crystallography for d(T[p](CE)T), a uv photoproduct of the cyanoethyl (CE) derivative of d(TpT), having the cis-syn cyclobutane (CB) geometry and the S-configuration at the chiral phosphorus atom. The crystals of C23H30N5O12P · 2H2O belong to the orthorhombic space group P212121 (Z = 4), with cell dimensions a = 11.596 Å, b = 14.834 Å, and c = 15.946 Å, containing two water molecules per asymmetric unit. The CB ring is puckered with a dihedral angle of 151°. The two pyrimidine bases are rotated by -29° from the position of direct overlap of their corresponding atoms. This represents a major distortion of DNA, since in DNA adjacent thymines are rotated by +36°. The pyrimidine rings are puckered with Cremer-Pople parameters for T[p] and in parentheses [p]T: Q: 0.24 Å (0.31 Å); θ: 123° (120°); φ: 141° (86°). These represent half-chairs designated as 6H1 (T[p]) and 6H5 ([p]T). The CB and pyrimidine ring conformations are interrelated, and we postulate that they execute a coupled interconversion in solution. The T[p] segment has the syn glycosyl conformation, a 2T3 sugar pucker, and gauche- conformation at C4′-C5′; the [p]T segment is anti, 3T4, trans. The C5′-O5′ torsion of the [p]T unit is -124.5°, and the C3′-O3′ torsion of the T[p] unit is -152.9°. Bond angles and bond lengths involving the phosphorus atom are similar to those of other phosphotriesters. The P-O3′ and P-05′ torsion angles are -138.1° and 58.6°, respectively. Several intermolecular (but no intramolecular) hydrogen bonds are found in the crystal.
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    Biopolymers 25 (1986), S. 1505-1517 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Light-scattering techniques have been used to measure the z-average radius of gyration Rg z-average translational diffusion coefficient Dt and weight-average molecular weight Mw of porcine submaxillary mucin (PSM) in solution. PSM isolated at low shear in the presence of protease inhibitors has a Mw about twice as large as a sample prepared without these precautions. The former sample has a Mw of 17 × 106 in 0.1M NaCl, which decreases to 8 × 106 in 6M guanidine hydrochloride (GdnHCl) and then to 2 × 106 on addition of 0.1M mercaptoethanol to the 6M GdnHCl solution. The Rg or D-1t values obtained for PSM in this work superimpose with those of other authors for different mucin glycoproteins, leading to linear log-log relationships to the molecular weight of the protein core. Comparison of these results with those in the literature for denatured proteins suggest that mucins are linear random coils in which the protein core is stiffened by the presence of the oligosaccharide side chains. The length of the oligosaccharides and the nature of the solvent have little effect on the extension of the protein core. This suggests that the stiffness of the protein core is maintained by steric repulsion of the residues at the beginning of the oligosaccharide chains.
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    Biopolymers 25 (1986), S. 1493-1504 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformation of melittin, a surface-active polypeptide, in solution was studied by CD spectra between 190 and 240 nm. The molecule was essentially unordered (possibly with a trace of helix) in water without salt at neutral pH. Upon deprotonation of four of the six cationic groups at pH 12 the polypeptide became partially helical (about 35%). The addition of NaDodSO4 to an aqueous melittin solution first caused the solution to become turbid but it became clear again in excess surfactant solution. The conformational changes depended on the molar NaDodSO4/melittin ratio, R. With R from 2.34 to 23.4, the melittin solution was turbid and the polypeptide conformation was probably a mixture of α-helix and β-sheets. This was supported by the ir spectrum of the turbid solution, which indicated the presence of both conformations. With R = 46.8 or 468 (1 or 10 mM NaDodSO4) the polypeptide conformation was characteristic of an α-helix, about 70-80% of the molecule, regardless of whether the surfactant was above or below its critical micelle concentration. This compared well with the x-ray results of 92% helix in crystals. The lower helicity of melittin in NaDodSO4 solution might be attributed to the end effects that destabilize the first and last turn of an helix at its N- and C-terminus, respectively.
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    Biopolymers 25 (1986), S. 1565-1577 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Short segments of polypeptide, from a protein for which the primary sequence but not the three-dimensional structure is known, are compared to a library of known structures. The basis of comparison is the probability with which residues in the unknown segment might substitute through evolution for residues in segments of known structure. In test cases, segments from known structures that are similar in sequence to those from a protein treated as unknown are often found to be similar in three-dimensional structure to one another and to the true structure of the “unknown” segment. This provides a basis for prediction of the local configuration (secondary structure) of polypeptides.
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    Biopolymers 25 (1986), S. 1603-1606 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Biopolymers 25 (1986), S. 1615-1621 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: X-ray diffraction studies have been carried out on a single crystal of the photosynthetic inhibitors N-(3,4-dichlorophenyl)-N′-dimethylurea (DCMU) and its newly synthesized spin-labeled analog N-(3,4-dichlorophenyl)-N′-(3,3,5,5-tetramethylpiperidine-4-oxyl)-urea (DTPU). The synthesis of DTPU as well as its crystallographic data are reported. The crystal system of both compounds is monoclinic with a space group P21/c. The cell constants of DCMU are a = 7.759(1), b = 14.737(3), c = 9.233(2) Å, β = 100.99(6)°; of DTPU they are a = 6.976(1), b = 11.998(2), c = 23.585(3) Å, β = 91.38(5)°. Comparison of conformational parameters of DCMU and DTPU reveal differences in the dihedral angle between the aromatic ring and the ureido plane. The measured volumes of DCMU and DTPU are 259.1 and 493.3 Å3, respectively. These figures suggest the size of the binding site of the inhibitors in the photosynthetic membrane.
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  • 73
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The conformational analysis of a protected homodipeptide of 1-aminocyclopentanecarboxylic acid (Acc5) has been carried out. 1H-nmr studies establish a β-turn conformation for Boc-Acc5-Acc5-NHMe in chloroform and dimethylsulfoxide solutions involving the methylamide NH in an intramolecular hydrogen bond. Supportive evidence for the formation of an intramolecular hydrogen bond is obtained from ir studies. X-ray diffraction studies reveal a type III β-turn conformation in the solid state stabilized by a 4 → 1 hydrogen bond between the Boc CO and methylamide NH groups. The φ,ψ values for both Acc5 residues are close to those expected for an ideal 310-helical conformation (φ≃ ± 60°, ψ∼ ±30°).
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    Biopolymers 25 (1986), S. 1685-1695 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decrease in mobility of viscous glycol-water solvents when associated with native DNA is quantified from a study of the loss of the exciting-wavelength dependence of the phosphorescence spectrum of free and bound proflavin with increasing temperature. The data are interpreted in terms of a distribution of rate constants with an Arrhenius temperature dependence. Over the temperature range of the experiments a relative decrease of ∼ 104 in the average rate constant is observed for reorientation of the solvent when associated with DNA. The basis for this large reduction is found to derive from a large decrease in the pre-exponential factors (i.e., activation entropy) associated with the reorientation rate constants. The changes in the distribution of rate constants and the activation parameters for solvent mobility induced by DNA do not resemble the changes observed for any one of a number of small ion or molecule perturbations. The results suggest the presence of disorganized, relatively immobile solvent in association with DNA.
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  • 75
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The three-dimensional Poisson-Boltzmann equation for the distribution of counterion charge density around double-helical DNA has been solved for solutions of .01M, .10M, and .20M monovalent salt. The polymers, poly[d(CpGp)] and poly[d(m5CpGp)], were studied in the B- and the Z-conformations. The effect of methylation on the relative stabilities of these conformers in solutions of different ionic strengths is known to favor the Z-form. Accumulation of charge density around the B- and the Z-conformers is compared in detail. The relative electrostatic stabilities of the B- and Z-conformers in .01M, .10M, and .20M solutions are compared and discussed in terms of the ion-DNA interactions and the self-energy of the structured ionic environment. The ion-DNA interaction energies, termed “phosphate screening,” monotonically decrease with ionic strength and are consistent with a B-to-Z conformation change induced in either polymer by increased electrolyte concentration. However, these calculated energies alone do not account for the fact that the ionic strength at the midpoint of the transition of the methylated polymer is substantially lower than that of its unmethylated analogues. The phosphate screening effect is counterbalanced by changes in the self-energy required for the creation of the structured counterion environment. This self-energy of the electrolyte environment monotonically increases with ionic strength. Methylation-induced shifts in the overall conformational equilibria depend on the relative changes of these competing effects. Increasing salt concentration is calcualted to favor the Z-conformer. The effect of methylation, lowering the ionic strength of the transition midpoint, is proposed to originate in minor structural changes in the Z-form of the polymer, making the groove more accessible to counterions in the G(3′ - 5′)C region. This allows a redistribution of counterion density and a lowering of the self-energy of the ionic environment, conferring added stability to the Z-conformation, as indicated by calculations of relative entropies. The experimentally observed temperature dependence of the B-to-Z transition, however, cannot be explained without assuming the release of bound water. Maps of the calculated three-dimensional structure at the counterion distribution near the surface of these molecules in both the B- and the Z-forms are also presented.
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  • 76
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Fourier transform ir vibrational circular dichroism (VCD) spectra in the amide I′ region of poly(L-lysine) in D2O solutions have confirmed the existence of three distinct conformational states and an unordered conformational state in this homopolypeptide. Characteristic VCD spectra are presented for the right-handed α-helix, the antiparallel β-sheet, an extended helix conformation previously referred to as the so-called “random coil,” and a completely unordered conformation characterized by the absence of any amide I′ VCD. VCD for the antiparallel β-sheet in solution and the unordered chain conformation are presented for the first time. Each of the four different VCD spectra is unique in appearance and lends weight to the view that VCD has the potential to become a sensitive new probe of the secondary structure of proteins in solution.
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  • 77
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The hinge-bending mode of hen egg white lysozyme is studied by a constrained minimization technique. Results with and without a bound inhibitor, tri-N-acetyl-glucosamine, are obtained. The frequency of the mode with the inhibitor is found to be 4.3 cm-1, in contrast to 3.0 cm-1 for the free enzyme. Also, the hinge-bending angle with the lowest energy is shifted 10° towards a more closed cleft in the bound species. The main contribution to these differences arise from interactions with the residues lining the cleft and those on the back side of it. Structural details that account for the energetics are presented. The method of calculation is somewhat different from a previous study [J. A. McCammon, B. R. Gelin, M. Karplus & P. G. Wolynes, (1976) Nature 262, 325-326] to reduce the likelihood of artifacts in the results.
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    Biopolymers 25 (1986), S. 1859-1864 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The overall dynamics of the Pf1 filamentous bacteriophage particle in solution are characterized by nmr experiments. The chemical-shift anisotropy powder-pattern lineshapes from both DNA and protein backbone sites of the virus are motionally averaged in the same way, indicating that the entire particle undergoes rapid (〈 104 Hz) reorientation about the long axis of the filament when the virus is in solution at high pH. In contrast, the virus particles in samples at low pH are immobile on this time scale.
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  • 79
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The structure and internal motions of the protein hen egg white lysozyme are studied by analysis of simulation and experimental data. A molecular dynamics simulation and an energy minimization of the protein in vacuum have been made and the results compared with high-resolution structures and temperature factors of hen egg white lysozyme in two different crystal forms and of the homologous protein human lysozyme. The structures obtained from molecular dynamics and energy minimization have root-mean-square deviations for backbone atoms of 2.3 Å and 1.1-1.3 Å, respectively, relative to the crystal structures; the different crystal structures have root-mean-square deviations of 0.73-0.81 Å for the backbone atoms. In comparing the backbone dihedral angles, the difference between the dynamics and the crystal structure on which it is based is the same as that between any two crystal structures. The internal fluctuations of atomic positions calculated from the molecular dynamics trajectory agree well with the temperature factors from the three structures. Simulation and crystal results both show that there are large motions for residues involved in exposed turns of the backbone chain, relatively smaller motions for residues involved in the middle of helices or β-sheet structures, and relatively small motions of residues near disulfide bridges. Also, both the simulation and crystal data show that side-chain atoms have larger fluctuations than main-chain atoms. Moreover, the regions that have large deviations among the x-ray crystal structures, which indicates flexibility, are found to have large fluctuations in the simulation.
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  • 80
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interaction of the carbocyanine dye Stains-all with the Ca2+-binding proteins calmodulin, troponin C, and parvalbumin has been monitored by means of absorption spectra and CD. In the absence of Ca2+, complexes with Stains-all of all three proteins exhibit at high dye: protein mole ratios an intense J absorption band at 600-650 nm, which is associated with a characteristic CD spectrum. In the cases of calmodulin and troponin C, the J-band is progressively lost as the dye: protein ratio decreases and is replaced by bands of the γ and β types at 450-550 nm, which likewise give rise to characteristic CD spectra. For parvalbumin, only the J-band is observed; its intensity is undiminished at the lowest dye: protein ratios examined. In the presence of excess Ca2+ the J-band is lost for all three proteins. For calmodulin and troponin C it is replaced by σ- and β-bands; in the case of parvalbumin the bound dye is released. A tentative model has been proposed to account for these observations.
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  • 81
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The average conformation of Met-enkephalin was determined by using an adaptive, importance-sampling Monte Carlo algorithm (SMAPPS - Statistical Mechanical Algorithm for Predicting Protein Structure). In the calculation, only the backbone dihedral angles (φ and ψ) were allowed to vary; i.e., all side-chain (χ) and peptide-bond (ω) dihedral angles were kept fixed at the values corresponding to a low-energy structure of the pentapeptide. The total conformational energy for each randomly generated structure of the polypeptide was obtained by summing over the interaction energies of all pairs of nonbonded atoms of the whole molecule. The interaction energies were computed by the program ECEPP/2 (Empirical Conformational Energy Program for Peptides). Solvent effects were not included in the computation. The calculation was repeated until a total of 10 independent average conformations were established. The regions of conformational space occupied by the average structures were compared with the regions of low conditional free energy obtained by SMAPPS in the first paper of this series. Such a comparison provides an analysis of the capacity of SMAPPS to adjust the Monte Carlo search to regions of highest probability. The results demonstrate that the ability of SMAPPS to focus the Monte Carlo search is excellent. Finally, the 10 independent average conformations and the mean of the 10 average structures were utilized as the initial conformations for a direct energy minimization of the pentapeptide. Of the 11 final energy-minimized structures, three of the conformations were found to be equivalent to the conformation of lowest energy determined previously. In addition, all but two of the remaining energy-minimized structures were found to correspond to one of the two other conformations of high probability obtained in the first paper of this series. These results indicate that a set of independent average conformations can provide a rational, unbiased choice for the initial conformation, to be used in a direct energy minimization of a polypeptide. The final energy-minimized structures consequently constitute a set of low-energy conformations, which include the global energy minimum.
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    Biopolymers 25 (1986), S. 1623-1633 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The interpretation of ΔGDH2O (the free energy change for the reaction, globular conformation ⇋ randomly coiled conformation, in the absence of denaturant), in terms of the free energies of transfer of various parts of the protein molecule from water to denaturant solution, is unsatisfactory because the latter are assumed to be identical to the transfer-free energies of similar groups attached to smaller model compounds. We have made empirical adjustments to transfer-free energy theory that make possible linear extrapolation of the free energy of denaturation of a protein from transition region to zero denaturant concentration. The modified theory, used to analyze the denaturation of proteins by guanidine hydrochloride and urea, allowed us to calculate reasonable values for Δα, the average change in accessibility to solvent of the component groups of protein.
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  • 83
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    Biopolymers 25 (1986), S. 1659-1672 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The multidimensional statistical technique of discriminant analysis is used to allocate amino acid sequences to one of four secondary structural classes: high α content, high β content, mixed α and β, low content of ordered structure. Discrimination is based on four attributes: estimates of percentages of α and β structures, and regular variations in the hydrophobic values of residues along the sequence, occurring with periods of 2 and 3.6 residues. The reliability of the method, estimated by classifying 138 sequences from the Brookhaven Protein Data Bank, is 80%, with no misallocations between α-rich and β-rich classes. The reliability can be increased to 84% by making no allocation for proteins classified with odds close to 1. Classification using previously developed secondary structural prediction methods is considerably less reliable, the best result being 64% obtained using predictions based on the Delphi method.
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  • 84
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    Biopolymers 25 (1986), S. 1717-1733 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The distributions of charged groups in 32 proteins of known three-dimensional structure have been analyzed to determine how regularly the groups are spread over the molecule's surfaces, and to identify and to study those proteins where charge asymmetry would seem important for their function. The distributions have been analyzed in terms of charge “polarity,” surface “charge density,” and electric dipole moments. More detailed studies of the distributions for individual proteins are made using map projections specifically developed for this purpose. In the light of the results obtained we discuss the role of charged groups in relation to protein function.
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  • 85
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    Biopolymers 25 (1986) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 86
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    Biopolymers 25 (1986), S. 1803-1812 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Changes in the 31P-nmr spectra of sonicated natural DNA fragments were investigated in ethanol solutions where the fragments underwent, as checked by CD, the B-to-A conformational transition. The study produced the following conclusions: (1) The high DNA concentrations used for the 31P-nmr measurements promote the transition compared to dilute solutions that are commonly used for CD measurements. (2) The B-to-A transition was reflected in a cooperative downfield shift of the DNA 31P-nmr resonance, consistent with unwinding of the double helix. (3) Prior to the transition, the changes in chemical shift of double-and single-stranded DNAs were almost identical. It thus appears that the effect of ethanol on the geometry and hydration of phosphodiester linkages does not depend heavily on DNA base-base interactions. (4) The A-form resonances were 30-40% narrower than the B-form resonances, which is attributed to marked sequence-dependent variations in the latter conformation and to their reduction in the former. (5) The B-form DNA aggregated in the concentrated 31P-nmr samples in the presence of ethanol, judged from a milky opalescence of the solution and a substantial broadening of its 31P-nmr resonance. The broadening abruptly disappeared as soon as DNA adopted the A-form so that DNA, in dependence on the secondary structure, showed different tendencies to condense in the presence of ethanol. The condensation increased cooperativity of the B-to-A interconversion.
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  • 87
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monte Carlo computer simulations were performed to elucidate the dynamic aspects of the folding and unfolding transitions of island-model protein. Five different types of model proteins were designed, according to characteristics of backbone structure. The computer simulations clearly show that the unfolding and folding transitions are all-or-none processes between the N-and U-states. They are typical Poisson processes. From the Arrhenius plots of rate constants, the activation enthalpies of folding and unfolding were determined. In addition, the folding pathways were determined along the reaction coordinate. Formations of several local structures along a polypeptide chain are almost simultaneous, but the most probable time sequence of events exists at the moment of transition. That is the most probable folding pathway. The unfolding pathway was found to be just the reverse process of the most probable folding pathway. The relationship between the fluctuations in each equilibrium state and the transition process was considered. In contrast to the theory of absolute reaction rate, the transient states are widely distributed along the reaction coordinate. From analysis of the “transient process,” we tried to determine the critical states from which the transient process starts. As a result, we found that the unfolding transition occurs at the stage near the N-state. During the U-state, large joined blocks rarely appear, but they appear in the transient process towards the N-state. However, the “branch point” between the N- and U-states lies near the N-state, and joined blocks tend to unfold prior to passing over the branch point. We concluded that the stability of later folding intermediates is important for selection of the folding pathway, while preferential selection of an early folding intermediate is important in acceleration of the folding rate. The effects of intrachain cross-linking and peptide fragment binding on the rate constants were examined by using computer simulations of model proteins. In general, a small-sized loop formed by cross-linking accelerates the folding rate and a large-sized loop contributes much to the stabilization of the native conformation. We also found that peptide fragment binding contributes little to the acceleration of the folding rate of the residual protein.
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  • 88
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    Biopolymers 25 (1986), S. 1875-1893 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The heat denaturation of pepsinized bovine nonfibrillar and fibrillar collagen was studied by differential scanning calorimetry. For fibrillar preparations that had been rapidly precipitated with stirring at low ionic strength, then resuspended at physiological ionic strength, multiple denaturational transitions were observed. At heating rates of 10°C/min, melting endotherms occurred at about 44, 50, 53, and 57°C. Fibrillar collagen that was slowly gelled without stirring at physiological ionic strength exhibited a similar series of endotherms, but the lower melting transitions were less conspicuous. In contrast, nonfibrillar bovine collagen in acidic solution showed only a single denaturational transition at 40°C. Nonfibrillar solutions at pH 7, to which inhibitors of fibrillogenesis were added, showed a major endotherm as high as 46°C. These results suggest that reconstituted fibrillar collagen contains a heterogeneous fibril population, possibly including molecules in a nonfibrillar state. It was proposed that the multiple melting endotherms of such preparations were due to sequential melting of molecular and fibril classes, each with a distinct melting temperature. The fibrillar classes may represent three or more types of banded and nonbanded species that differ from each other in packing order, collagen concentration, and possibly also in fibril width and level of cross-linking.
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  • 89
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The proton nmr and CD spectra of gramicidin S (GS) cyclic-(Val1,1′-Orn2,2′-Leu3,3′-D-Phe4,4′-Pro5,5′)2 and of GS analogs - namely, [D-Ala4,4′]-GS, [Gly4,4′]-GS, and [L-Ala4,4′]-GS - were analyzed. The molecular conformation of [D-Ala4,4′]-GS is similar to that of GS, with the trans form about the D-Ala-Pro peptide bond. The molecular conformation of [Gly4,4′]-GS depends on the solvent composition of dimethylsulfoxide-d6/trifluoroethanol (DMSO)-d6/TFE and DMSO-d6/H2O as well as the solute concentration. In DMSO-d6 solution, [Gly4,4′]-GS forms the GS-type conformation of the monomer at lower concentration. At higher concentration, the GS-type conformer is converted to the other one that forms molecular aggregates. The cis form about the X-Pro peptide bonds is found for [Gly4,4′]-GS and [L-Ala4,4′]-GS in DMSO-d6 and for [L-Ala4,4′]-GS in TFE solution. The large temperature dependences of α-proton chemical shifts of [L-Ala4,4′]-GS in DMSO-d6 solution indicate that the conformer equilibrium changes with temperature. The GS-type conformation is not formed in [L-Ala4,4′]-GS. The two active peptide analogs, [D-Ala4,4′]-GS and [Gly4,4′]-GS, interact with the phospholipid membrane, taking the GS-type conformation. By contrast, an inactive analog, [L-Ala4,4′]-GS, does not interact with phospholipid membrane. The activities of GS analogs are found to correlate to the formation of the GS-type conformation upon binding with phospholipid membrane.
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  • 90
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    Biopolymers 25 (1986), S. 2359-2373 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The distinctive transverse banding pattern of fibrin fibers clearly indicates ordering of molecules in the longitudinal direction. In this study we examined the fibers of fibrin clots, as well as two types of fibrinogen polymers, by thin-section electron microscopy. The fibrinogen polymers have a transverse banding pattern identical to that of fibrin fibers - clearly indicating a regular longitudinal repeat - but they are larger in diameter, and show little or no branching. We therefore expected their overall ordering to be better than that of fibrin fibers. Several different fixation protocols were used. We readily observed the typical transverse banding seen previously by negative stain and metal replication techniques. However, only very rarely was any regular lateral lattice seen in any of the samples. X-ray diffraction was used to examine unfixed specimens of the two fibrinogen polymers and, once again, although a longitudinal repeat was evident, only rarely was evidence for lateral crystallinity seen. The electron-microscope and x-ray results showed that the needles and pellet fibers of fibrinogen have essentially the same internal architecture as thick fibrin fibers, and that all three types of polymer, although clearly transversely banded, have almost no crystallinity in their lateral protofibril packing.
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  • 91
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the formation of the complex between bovine β-trypsin and the porcine pancreatic secretory trypsin inhibitor (PSTI; Kazal-type inhibitor) was investigated following the spectral changes associated with the displacement of proflavine from the enzyme, upon inhibitor binding, between pH 3.5 and 8.0 (I = 0.1M) at 21 ± 0.5°C. With inhibitor in excess over the enzyme ([PSTI] ≥ 5 × [bovine β-trypsin]), the time course of the reaction corresponds to a pseudo-first-order process. Over the whole pH range explored, the concentration dependence of the rate is second order at low PSTI concentrations but tends to first order at high inhibitor concentrations. This behavior may be explained by a relatively fast pre-equilibrium followed by a limiting first-order process. Values of kinetic parameters for PSTI binding to bovine β-trypsin depend, between pH 3.5 and 8.0, on the acid-base equilibrium of a single ionizing group (probably His-57 of bovine β-trypsin) that undergoes an acidic pKa shift from 7.0 in the free bovine β-trypsin to 5.5 in the enzyme:PSTI complex. Kinetics of the bovine β-trypsin:PSTI adduct formation has been analyzed and compared with that of other (pro)enzyme:inhibitor reactions. Considering the known molecular structures of free serine (pro)enzymes, of Kazal- and Kunitz-type inhibitors, as well as of their complexes, the binding behavior of PSTI to bovine β-trypsin has been related to the inferred stereochemistry of the proteinase:inhibitor contact region.
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  • 92
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    Weinheim : Wiley-Blackwell
    Chemie in unserer Zeit 20 (1986), S. 1-10 
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 93
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    Biopolymers 25 (1986) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 94
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    Biopolymers 25 (1986), S. 317-335 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We report here a novel ir technique that we use to determine the apparent van't Hoff's energy for the distillation of water from protein amide and acid groups. The method is used to study the hydration properties of ten different proteins. The results show that water removal from the environment of ion-paired acid groups (those ≤ 4 Å from a basic group on the protein surface) requires less energy than water removal from the environment of nonpaired acid groups. These observations are supported by an analysis of the solvent distributions in protein crystal structures. A model is proposed for the interaction between water and protein acid groups, and this model is used to account for the distributions and properties of certain eye-lens proteins.
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  • 95
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A set of large positive extrinsic CD bands ([θ]333 = 2.6 X 104 deg-cm2/decimole phosphate) in the 〉 300 nm region as well as diminution of the intrinsic signals (θ275) have been observed in the CD spectra of various nucleic acids complexed with the achiral compound, N-poly{α-[N-(4-pyridylethylene-4-pyridyl-N′-)α′-p-xylyl]dibromide}-4-pyridylethylene-4-pyridinium bromide, (polymer X).1,2,5 The signal changes are attributed to the binding of polymer X chromophores isogeometrically to the DNA helix in an ordered chiral arrangement. Fractionation of polymer X gives 10 well-separated oligomers. The oligomers were characterized by nmr. Their interactions with DNA have been investigated with respect to r(r = ratio of equivalents of polymer X charge/g-atoms DNA phosphorus) and n (oligomer chain length). In all cases where n ≥ 1, [θ]333 increases linearly with increasing r between 0 and 0.32, and is accompanied by a corresponding decrease in [θ]275, which becomes negative as r approaches .32. Extrinsic band intensities reveal a dependence on n up to n = 5, above which increases in nonspecific binding result in a reduction in normalized band intensities. Polymer X shows a strong preference for B-form nucleic acids and induces maximum extrinsic CD signal intensities with A-T homopolymers. Alterations in helix hydration are believed to accompany complex formation. Inversions in [θ]275 of the octamer X-poly(dA-dT) complex have been attributed to the “alternating B” conformation of poly(dA-dT).3 Similar inversions are not observed in other nucleic acid-octamer X complexes. Visible and CD spectrometry data from competition studies in the presence of the antibiotics actinomycin D (AMD), daunomycin (DM), and distamycin A (DST) are consistent with “nonclassical” intercalation as the mode of binding, and these data place the potential binding site in or near the hydrophobic region of the minor groove. Reductions in [θ]333 with increasing urea further implicate the involvement of hydrophobic interactions in the formation of an asymmetric complex. Stabilization of the helix results in all cases as evidenced by alterations in Tm; corresponding changes, however, in cooperativity are not clearly discernable. Viscosity and light-scattering data indicate no changes in molecular weight due to aggregation, and as such are not consistent with a transition to the ψ-DNA upon complex formation.
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  • 96
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    Biopolymers 25 (1986), S. 519-523 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The vacuum CD spectra of poly(rG-dC)·poly(rG-dC) and poly(dG-m5dC)·poly(dG-m5dC) have been obtained for the low-salt Z-conformations of both polymers. The spectra are very similar to those for the high-salt Z-forms. This behavior is consistent with the suggestion that the low- and high-salt Z-forms are comprised of different proportions of ZI- and ZII-conformations.
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  • 97
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chain association of pectic molecules with different levels and patterns of esterification during calcium-induced gelation was studied by methods such as light scattering, viscometry, and determination of calcium activity coefficient and of calcium transport parameter. A gel point can be determined, assuming a power law including a critical ratio (equivalent concentration of calcium ions/pectin carboxylic groups) and quasi-critical exponents varying in the range 0.50-1.26. The values of these critical parameters were discussed as a function of polymer concentration, of level and pattern of esterification, and of the nature of the divalent counterion. The lower these values are, the better, apparently, the gel-forming ability of the pectins is.
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  • 98
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    Biopolymers 25 (1986), S. 555-570 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sequences 74-91 and 77-91 of E. coli thioredoxin, which according to x-ray structure contain an irregular β-turn, a hairpinlike structural element, have been synthesized and their conformational properties in solution have been investigated by means of CD spectroscopy. In addition, analogs of these sequences, containing the regular β-turn element Gly-Pro-(Gly)2, have also been prepared and investigated. These are BOC-Ile-Gly-Pro-(Gly)2-Val-OMe (III) and BOC-(Ile)3Gly-Pro-(Gly)2-(Val)5-OMe (IV) that on the basis of probability, should form hairpin structures stabilized by intramolecular interactions. While the natural sequences were shown to be unable to adopt structures characterized by an intrinsic conformational stability, the two analogs showed evidence of intramolecular folding in methanol and trifluoroethanol-water solution. In particular, the CD spectra are indicative of β-structure. The most interesting case was observed for compound IV, as the highest degree of conformational order was present in solutions containing a large proportion of water. In addition, the formation of this structure took place in a highly cooperative manner. The results are utilized to discuss whether and to what extent conformationally stable folding peptide units of small size can be formed in aqueous solution.
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  • 99
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational properties of 5-fluorouracil derivatives are compared to uracil derivatives. FUrd, 5′-FUMP, and poly(FU) are studied as a function of pH and temperature by 19F- and 1H-nmr spectroscopy, and the corresponding uracil derivatives by 1H-nmr spectroscopy. FUrd exhibits no significant conformational changes with solution pH (5-10). In contrast, at low pH (6-7) 5′-FUMP and 5′-UMP show similar conformational features, while at high pH (9) 5′-FUMP shows significant conformational alterations. Also, poly(U) and poly(FU) are conformationally similar at low pH, but increasing pH induces changes in poly(FU). These changes are observed in the backbone [γ(C4′-C5′)], furanose, and furanose-base conformations. The apparent pKa of N3-H ionization of the FUra base is determined by 1H- and 19F-nmr to range from 7.5 to 8.2 [FUrd 〈 5′-FUMP 〈 5′-FUDP 〈 poly(FU)]. These observations are interpreted as a result of electrostatic interactions generated between the ionized phosphate group and the negatively charged base moiety as the pH is raised. The interaction properties of poly(FU) with ApA are studied by 1H- and 19F-nmr spectroscopy, and these properties compared to those published for poly(U). Poly(FU) forms a complex with ApA inducing upfield 1H-shifts in both components, and downfield 19F- shifts in poly(FU). The base stoichiometry of the complex for poly(U)·ApA is 2U:1A at various U/A ratios. In contrast, the base stoichiometry of the poly(FU)·ApA complex appears to be dependent on the FU/A ratio. At high FU/A ratio, the complex is 2FU:1A, and as the FU/A ratio approaches unity the complex becomes 1FU:1A.
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  • 100
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The sequential polypeptides (L-Arg-X-Gly)n, where X represents amino acid residues Ala, Val, and Leu, were prepared as models of arginine-rich histones to be used in studying their structure and their interactions with DNA. The polymerization was carried out on the pentachlorophenyl active esters of the appropriate tripeptides, while the toluene-4-sulfonyl group was used for protecting the arginine guanido group. CD was employed to investigate the conformation of (L-Arg-X-Gly)n polymers in aqueous solutions, at different pH, as well as in trifluoroenthanol and hexafluoroisopropyl alcohol solutions. In aqueous solutions (at pH 7 and 12) the prepared sequential polymers behaved as a random coil. The CD spectra in various trifluoroethanol-water or hexafluoroisopropyl alcohol-water mixtures indicated that the degree of helical conformation of the studied polytripeptides increased in the order of Ala → Val → Leu. The opposite was true for the β-structure. Characteristics of β-turn are excluded from the poly(L-Arg-L-Leu-Gly), which assumed the most pronounced helical conformation. The poly(L-Arg-L-Val-Gly) exerts a significant preference to the β-turn structure compared to that of poly(L-Arg-L-Ala-Gly). Thus the probability for helical, β-structure or β-turn conformations of the polymers was analyzed in relation to the bulkiness and length, and to the special features of the X-residue side chain (β-branching). We concluded that the prepared sequential arginine-containing polypeptides are plausible models for histone fractions, f3 and f2α1.
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