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  • Wiley-Blackwell  (31,922)
  • American Geophysical Union  (8,213)
  • American Association for the Advancement of Science (AAAS)
  • 2020-2024  (281)
  • 1970-1974  (39,871)
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  • 1
    Publication Date: 2024-04-07
    Description: PI3K biology; lymphoma; cancer
    Keywords: PI3K biology; lymphoma; cancer ; thema EDItEUR::P Mathematics and Science::PS Biology, life sciences
    Language: English
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  • 2
    Publication Date: 2024-04-03
    Description: oncogenic drivers; signaling; pathways; hematologic malignancies; cancer
    Keywords: oncogenic drivers; signaling; pathways; hematologic malignancies; cancer ; thema EDItEUR::M Medicine and Nursing
    Language: English
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  • 3
    Publication Date: 2023-01-07
    Description: Author Posting. © American Geophysical Union, 2022. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 49(13), (2022): e2022GL098554, https://doi.org/10.1029/2022GL098554.
    Description: Summertime heavy rainfall and its resultant floods are among the most harmful natural hazards in the US Midwest, one of the world's primary crop production areas. However, seasonal forecasts of heavy rain, currently based on preseason sea surface temperature anomalies (SSTAs), remain unsatisfactory. Here, we present evidence that sea surface salinity anomalies (SSSAs) over the tropical western Pacific and subtropical North Atlantic are skillful predictors of summer time heavy rainfall one season ahead. A one standard deviation change in tropical western Pacific SSSA is associated with a 1.8 mm day−1 increase in local precipitation, which excites a teleconnection pattern to extratropical North Pacific. Via extratropical air-sea interaction and long memory of midlatitude SSTA, a wave train favorable for US Midwest heavy rain is induced. Combined with soil moisture feedbacks bridging the springtime North Atlantic salinity, the SSSA-based statistical prediction model improves Midwest heavy rainfall forecasts by 92%, complementing existing SSTA-based frameworks.
    Description: This study is supported by the NSF PREEVENTS program under ICER-1663138 (LL) and ICER-1663704 (RWS and CCU).
    Description: 2023-01-07
    Keywords: Sea surface salinity ; Midwest precipitation ; Heavy rainfall ; Long-lead prediction
    Repository Name: Woods Hole Open Access Server
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  • 4
    Publication Date: 2023-01-14
    Description: Author Posting. © American Geophysical Union, 2022. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Oceans 127(7), (2022): e2021JC018276, https://doi.org/10.1029/2021JC018276.
    Description: Coastal communities across the United States (U.S.) are experiencing an increase in the frequency of high-tide flooding (HTF). This increase is mainly due to sea-level rise (SLR), but other factors such as intra- to inter-annual mean sea level variability, tidal anomalies, and non-tidal residuals also contribute to HTF events. Here we introduce a novel decomposition approach to develop and then analyze a new database of different sea-level components. Those components represent processes that act on various timescales to contribute to HTF along the U.S. coastline. We find that the relative importance of components to HTF events strongly varies in space and time. Tidal anomalies contribute the most along the west and northeast coasts, where HTF events mostly occur in winter. Non-tidal residuals are most important along the Gulf of Mexico and mid-Atlantic coasts, where HTF events mostly occur in fall. We also quantify the minimum number of components that were required to cause HTF events in the past and how this number changed over time. The results highlight that at present, due to SLR, fewer components are needed to combine to push water levels above HTF thresholds, but tidal anomalies alone are still not sufficient to reach HTF thresholds in most locations. Finally, we explore how co-variability between different components leads to compounding effects. In some places, positive correlation between sea-level components leads to significantly more HTF events than would be expected if sea-level components were uncorrelated, whereas in other places negative correlation leads to fewer HTF events.
    Description: his work was supported by NASA's Sea Level Change Team award number 80NSSC20K1241. S.L. also acknowledges support by the China Scholarship Council (no. 201904910413) and the Ministry of Science and Technology of the People's Republic of China (grant no. 2011YQ120045).
    Description: 2023-01-14
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  • 5
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    American Association for the Advancement of Science (AAAS)
    In:  EPIC3Science Advances, American Association for the Advancement of Science (AAAS), 9(50), ISSN: 2375-2548
    Publication Date: 2023-12-18
    Description: Antarctic krill, crucial to the Southern Ocean ecosystem and a vital fisheries resource, is endangered by climate change. Identifying drivers of krill biomass is therefore essential for determining catch limits and designating protection zones. We present a modeling approach to pinpointing effects of sea surface temperature, ice cover, chlorophyll levels, climate indices, and intraspecific competition. Our study reveals that larval recruitment is driven by both competition among age classes and chlorophyll levels. In addition, while milder ice and temperature in spring and summer favor reproduction and early larval survival, both larvae and juveniles strongly benefit from heavier ice and colder temperatures in winter. We conclude that omitting top-down control of resources by krill is only acceptable for retrospective or single-year prognostic models that use field chlorophyll data but that incorporating intraspecific competition is essential for longer-term forecasts. Our findings can guide future krill modeling strategies, reinforcing the sustainability of this keystone species.
    Repository Name: EPIC Alfred Wegener Institut
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  • 6
    Publication Date: 2023-02-25
    Description: Author Posting. © American Geophysical Union, 2022. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Solid Earth 127(8), (2022): e2021JB023814, https://doi.org/10.1029/2021jb023814.
    Description: Early arrival traveltime tomography and full waveform inversion were conducted on downward continued streamer seismic data at Dante's Domes oceanic core complex (OCC), providing unprecedented details of shallow P wave velocity structure. Together with reverse time migration images, seafloor morphology, in situ geological samples, magnetic and gravity data, the seismic constraints are used to infer the lithological distribution along the seismic profiles. Based on the striking similarity in velocity structure beneath the corrugated domes with other OCCs and drilling results from Atlantis Massif, we confidently reconfirmed the Southern Dome as dominantly gabbroic rocks, and the Northern Dome as serpentinized peridotites. A series of isolated gabbroic bodies embedded in the diabase and basaltic layers is observed in the breakaway zone, suggesting that the initiation of Dante's Domes OCC occurred over a long period during which there were several failed attempts to form a long-lived detachment fault. This early development of the OCC probably occurred under a regime of alternating magma starvation and magma replenishment. The predominantly gabbroic section, beneath the Southern Dome and extending to termination, indicates the OCC has been created with relatively high magma flux. We also imaged distinct shallow subseafloor reflections which are also termed as D reflectors underneath the corrugated domes. The location of the D reflectors is similar to those in the Atlantis Massif, with depths well correlated with the top of exhumed gabbroic bodies and the discontinuities in the D reflectors between gabbroic bodies. Our findings contribute to the understanding of processes controlling the OCCs initiation and evolution at slow spreading ridges.
    Description: This research was supported by the National Natural Science Foundation of China (91858207), Key Special Project for Introduced Talents Team of Southern Marine Science and Engineering Guangdong Laboratory (GML2019ZD0205), and Guangdong Basic and Applied Basic Research Foundation (2021B1515020023). M. X. acknowledges support from Special Foundation for National Science and Technology Basic Research Program of China (2018FY100505), Guangdong NSF research team project (2017A030312002), K. C. Wong Education Foundation (GJTD-2018-13), and the Chinese Academy of Sciences (Y4SL021001, QYZDY-SSWDQC005, 133244KYSB20180029, 131551KYSB20200021, and ISEE2021PY03). J. P. C. acknowledges support from the Independent Research and Development Program at WHOI.
    Repository Name: Woods Hole Open Access Server
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  • 7
    Publication Date: 2023-02-25
    Description: Author Posting. © American Geophysical Union, 2022. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Oceans 127(8),(2022): e2022JC018737, https://doi.org/10.1029/2022jc018737.
    Description: Gulf Stream Warm Core Rings (WCRs) have important influences on the New England Shelf and marine ecosystems. A 10-year (2011–2020) WCR dataset that tracks weekly WCR locations and surface areas is used here to identify the rings' path and characterize their movement between 55 and 75°W. The WCR dataset reveals a very narrow band between 66 and 71°W along which rings travel almost due west along ∼39°N across isobaths – the “Ring Corridor.” Then, west of the corridor, the mean path turns southwestward, paralleling the shelfbreak. The average ring translation speed along the mean path is 5.9 cm s−1. Long-lived rings (lifespan 〉150 days) tend to occupy the region west of the New England Seamount Chain (NESC) whereas short-lived rings (lifespan 〈150 days) tend to be more broadly distributed. WCR vertical structures, analyzed using available Argo float profiles indicate that rings that are formed to the west of the NESC have shallower thermoclines than those formed to the east. This tendency may be due to different WCR formation processes that are observed to occur along different sections of the Gulf Stream. WCRs formed to the east of the NESC tend to form from a pinch-off mechanism incorporating cores of Sargasso Sea water and a perimeter of Gulf Stream water. WCRs that form to the west of the NESC, form from a process called an aneurysm. WCRs formed through aneurysms comprise water mostly from the northern half of the Gulf Stream and are smaller than the classic pinch-off rings.
    Description: AS and AG are grateful for financial support from NOAA (NA11NOS0120038), NSF (OCE-1851242 and OCE-2123283), SMAST, and UMass Dartmouth. GG was supported by NSF under grant OCE-1657853. MA was supported by NSF under grant OCE-2122726 and by ONR under grant N00014-22-1-2112.
    Keywords: Gulf Stream ; Warm core rings ; Trajectories ; Eddies ; Aneurysm ; Ring formation
    Repository Name: Woods Hole Open Access Server
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  • 8
    Publication Date: 2023-02-25
    Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biasi, J., Asimow, P., Horton, F., & Boyes, X. Eruption rates, tempo, and stratigraphy of Paleocene flood basalts on Baffin Island, Canada. Geochemistry, Geophysics, Geosystems, 23(9), (2022): e2021GC010172, https://doi.org/10.1029/2021gc010172.
    Description: High-temperature melting in mantle plumes produces voluminous eruptions that are often temporally coincident with mass extinctions. Paleocene Baffin Island lavas—products of early Iceland mantle plume activity—are exceptionally well characterized geochemically but have poorly constrained stratigraphy, geochronology, and eruptive tempos. To provide better geologic context, we measured seven stratigraphic sections of the volcanic deposits and collected paleomagnetic data from 38 sites in the lavas and underlying Cretaceous sediments (Quqaluit Fm.). The average paleomagnetic pole from this study does not overlap with the expected pole for a stable North American locality at 60 Ma, yet the data have sufficient dispersion to average out secular variation. After ruling out other possibilities, we find that the picrites were probably erupted during a polarity transition, over less than 5 kyr. If so, the average eruption interval was ∼67 years per flow for the thickest sequence of exposed lavas. We also calculate that the flood basalts had a minimum total volume of ∼176 km3 (excluding submerged lavas in Baffin Bay). This implies a minimum eruption rate of ∼0.035 km3 yr−1, which is similar to rates found in West Greenland lavas but less than rates found in larger flood basalts. Despite this, the Baffin and West Greenland lavas temporally correlate with the “End C27n event” (a period of ∼2°C global warming) and may be its underlying cause.
    Description: his work was supported by the National Science Foundation (award #1911699 to F. Horton and award #2052963 to J. Biasi), Woods Hole Oceanographic Institution (WHOI) Andrew W. Mellon Foundation Endowed Fund for Innovative Research, a National Geographic Society grant (#CP4-144R-18), and internal funding from the Caltech Geological and Planetary Sciences Division.
    Keywords: Baffin island ; North Atlantic ; Flood basalt ; Paleomagnetism ; Volcanology ; Secular variation
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  • 9
    Publication Date: 2023-02-21
    Description: Author Posting. © American Geophysical Union, 2022. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 49(15), (2022): e2022GL099185, https://doi.org/10.1029/2022gl099185.
    Description: Several large strike slip faults in central and northern California accommodate plate motions through aseismic creep. Although there is no consensus regarding the underlying cause of aseismic creep, aqueous fluids and mechanically weak, velocity-strengthening minerals appear to play a central role. This study integrates field observations and thermodynamic modeling to examine possible relationships between the occurrence of serpentinite, silica-carbonate rock, and CO2-rich aqueous fluids in creeping faults of California. Our models predict that carbonation of serpentinite leads to the formation of talc and magnesite, followed by silica-carbonate rock. While abundant exposures of silica-carbonate rock indicate complete carbonation, serpentinite-hosted CO2-rich spring fluids are strongly supersaturated with talc at elevated temperatures. Hence, carbonation of serpentinite is likely ongoing in parts of the San Andres Fault system and operates in conjunction with other modes of talc formation that may further enhance the potential for aseismic creep, thereby limiting the potential for large earthquakes.
    Description: This work was supported by National Science Foundation (NSF) grants NSF-EAR-1220280 to F. K. and J. L., NSF-EAR-1219908 to D. G., and NSF-OCE-2001728 to J. L.
    Keywords: Mineral carbonation ; Serpentinite ; Talc ; CO2 ; Aseismic creep ; San Andreas Fault
    Repository Name: Woods Hole Open Access Server
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  • 10
    Publication Date: 2023-02-21
    Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Marsay, C. M., Landing, W. M., Umstead, D., Till, C. P., Freiberger, R., Fitzsimmons, J. N., Lanning, N. T., Shiller, A. M., Hatta, M., Chmiel, R., Saito, M., & Buck, C. S. Does sea spray aerosol contribute significantly to aerosol trace element loading? a case study from the US GEOTRACES Pacific Meridional Transect (GP15). Global Biogeochemical Cycles, 36(8), (2022): e2022GB007416. https://doi.org/10.1029/2022GB007416.
    Description: Atmospheric deposition represents a major input for micronutrient trace elements (TEs) to the surface ocean and is often quantified indirectly through measurements of aerosol TE concentrations. Sea spray aerosol (SSA) dominates aerosol mass concentration over much of the global ocean, but few studies have assessed its contribution to aerosol TE loading, which could result in overestimates of “new” TE inputs. Low-mineral aerosol concentrations measured during the U.S. GEOTRACES Pacific Meridional Transect (GP15; 152°W, 56°N to 20°S), along with concurrent towfish sampling of surface seawater, provided an opportunity to investigate this aspect of TE biogeochemical cycling. Central Pacific Ocean surface seawater Al, V, Mn, Fe, Co, Ni, Cu, Zn, and Pb concentrations were combined with aerosol Na data to calculate a “recycled” SSA contribution to aerosol TE loading. Only vanadium was calculated to have a SSA contribution averaging 〉1% along the transect (mean of 1.5%). We derive scaling factors from previous studies on TE enrichments in the sea surface microlayer and in freshly produced SSA to assess the broader potential for SSA contributions to aerosol TE loading. Maximum applied scaling factors suggest that SSA could contribute significantly to the aerosol loading of some elements (notably V, Cu, and Pb), while for others (e.g., Fe and Al), SSA contributions largely remained 〈1%. Our study highlights that a lack of focused measurements of TEs in SSA limits our ability to quantify this component of marine aerosol loading and the associated potential for overestimating new TE inputs from atmospheric deposition.
    Description: This research was supported by the National Science Foundation (NSF) grants OCE-1756103 to C. S. Buck, OCE-1756104 to W. M. Landing, OCE-1737024 to A.M. Shiller, OCE-1736906 to M. Hatta, OCE-1736875 to C. P. Till, OCE-1737167 to J. N. Fitzsimmons, and OCE-1736599 to M. Saito. In addition, N. T. Lanning was supported by the NSF Graduate Research Fellowship Program award 1746932.
    Keywords: Aerosols ; Trace elements ; GEOTRACES ; Sea spray aerosol ; Pacific Ocean
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  • 11
    Publication Date: 2023-02-21
    Description: Author Posting. © American Geophysical Union, 2022. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Solid Earth 127(8), (2022): e2022JB024497, https://doi.org/10.1029/2022JB024497.
    Description: During plastic deformation, strain weakening can be achieved, in part, via strain energy reduction associated with intragranular boundary development and grain boundary formation. Grain boundaries (in 2D) are segments between triple junctions, that connect to encircle grains; every boundary segment in the encircling loop has a high (〉10°) misorientation angle. Intragranular boundaries terminate within grains or dissect grains, usually containing boundary segments with a low (〈10°) misorientation angle. We analyze electron backscatter diffraction (EBSD) data from ice deformed at −30°C (Th≈ 0.9). Misorientation and weighted Burgers vector (WBV) statistics are calculated along planar intragranular boundaries. Misorientation angles change markedly along each intragranular boundary, linking low- (〈10°) and high-angle (10–38°) segments that exhibit distinct misorientation axes and WBV directions. We suggest that these boundaries might be produced by the growth and intersection of individual intragranular boundary segments comprising dislocations with distinct slip systems. There is a fundamental difference between misorientation axis distributions of intragranular boundaries (misorientation axes mostly confined to ice basal plane) and grain boundaries (no preferred misorientation axis). These observations suggest during progressive subgrain rotation, intragranular boundaries remain crystallographically controlled up to large misorientation angles (〉〉10°). In contrast, the apparent lack of crystallographic control for grain boundaries suggests misorientation axes become randomized, likely due to the activation of additional mechanisms (such as grain boundary sliding) after grain boundary formation, linking boundary segments to encircle a grain. Our findings on ice intragranular boundary development and grain boundary formation may apply more broadly to other rock-forming minerals (e.g., olivine, quartz).
    Description: This work was supported by a NASA fund (Grant No. NNX15AM69G) to David L. Goldsby and two Marsden Funds of the Royal Society of New Zealand (Grant Nos. UOO1116, UOO052) to David J. Prior. Sheng Fan was supported by the University of Otago doctoral scholarship, the Antarctica New Zealand doctoral scholarship, a research grant from New Zealand Ministry of Business, Innovation and Employment through the Antarctic Science Platform (ANTA1801) (Grant No. ASP-023-03), and a New Zealand Antarctic Research Institute (NZARI) Early Career Researcher Seed Grant (Grant No. NZARI 2020-1-5). Open access publishing facilitated by University of Otago, as part of the Wiley – University of Otago agreement via the Council of Australian University Librarians.
    Keywords: High temperature deformation ; Misorientation ; Weighted Burgers vector ; Intragranular boundary ; Grain boundary ; Boundary geometry
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  • 12
    Publication Date: 2023-08-08
    Description: 〈jats:p〉Arctic Ocean gateway fluxes play a crucial role in linking the Arctic with the global ocean and affecting climate and marine ecosystems. We reviewed past studies on Arctic–Subarctic ocean linkages and examined their changes and driving mechanisms. Our review highlights that radical changes occurred in the inflows and outflows of the Arctic Ocean during the 2010s. Specifically, the Pacific inflow temperature in the Bering Strait and Atlantic inflow temperature in the Fram Strait hit record highs, while the Pacific inflow salinity in the Bering Strait and Arctic outflow salinity in the Davis and Fram straits hit record lows. Both the ocean heat convergence from lower latitudes to the Arctic and the hydrological cycle connecting the Arctic with Subarctic seas were stronger in 2000–2020 than in 1980–2000. CMIP6 models project a continuing increase in poleward ocean heat convergence in the 21st century, mainly due to warming of inflow waters. They also predict an increase in freshwater input to the Arctic Ocean, with the largest increase in freshwater export expected to occur in the Fram Strait due to both increased ocean volume export and decreased salinity. Fram Strait sea ice volume export hit a record low in the 2010s and is projected to continue to decrease along with Arctic sea ice decline. We quantitatively attribute the variability of the volume, heat, and freshwater transports in the Arctic gateways to forcing within and outside the Arctic based on dedicated numerical simulations and emphasize the importance of both origins in driving the variability.〈/jats:p〉
    Repository Name: EPIC Alfred Wegener Institut
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  • 13
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    American Association for the Advancement of Science (AAAS)
    In:  EPIC3Science, American Association for the Advancement of Science (AAAS), 378(6617), pp. 230-230, ISSN: 0036-8075
    Publication Date: 2023-05-10
    Description: 〈jats:p〉 Next week, the Convention on the Conservation of Antarctic Marine Living Resources (CCAMLR) convenes in Hobart, Tasmania, to examine the state of marine life in the Southern Ocean. As part of the Antarctic Treaty System, this convention entered into force in 1982, and its focus on the region’s environmental integrity has never been more important, given the increasing effects of climate change and commercial fishing. An important focus over the past 40 years has been Antarctic krill, 〈jats:italic〉Euphausia superba〈/jats:italic〉 (hereafter krill), a keystone species that helps to hold this marine ecosystem together. Climate and fishing stresses should prompt the CCAMLR to address whether management of krill fishing is at a level that protects the Southern Ocean from losing its overall balance of marine life and the oceanic processes that regulate global climate. 〈/jats:p〉
    Repository Name: EPIC Alfred Wegener Institut
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  • 14
    Publication Date: 2023-02-07
    Description: We present measurements of soil CO2 effluxes combined with soil (222Rn) and (220Rn) from two high-degassing areas on the lower flanks of Mt. Etna volcano (ZE-SV on the E flank and PAT on the SW flank). Measurements were conducted periodically from June 2006 to January 2009 in the ZE-SV area and January 2007 to January 2009 in the PAT area. The results showed significant variations in discharge activity and style. Log values of (220Rn)/(222Rn) and CO2 efflux generally follow a negative correlation, herein parameterized as the Soil Gas Disequilibrium Index (SGDI). Deviations of the SGDI from this negative correlation provide insight into variance of localized and shallow system conditions, namely rock fracturing, residual magma degassing, and near surface interactions between magmatic gases and groundwater. Statistical analysis highlighted signal anomalies, both negative and positive, that were modeled according to the physical properties and the modes of transport for each of the SGDI gas components. The revealed anomalies show correspondence with episodes of magma ascent and eruption, thereby demonstrating the potential of using the SGDI as another instrument for forecasting volcanic activity. An important strength of the SGDI, compared to other magma gas proxies like CO2 or SO2, is that the very short and very different half-lives of 222Rn (t1/2 = 3.85 days) and 220Rn (t1/2 = 55 seconds) provide unique information on the timescales of soil gas transport. Coupling the SGDI with other pre-eruptive proxies enhances the volcanological community’s response capabilities, which is critical for effective hazard mitigation.
    Description: Published
    Description: 167-202
    Description: 4V. Processi pre-eruttivi
    Keywords: Soil gases ; radon ; carbon dioxide ; volcano monitoring ; 04.08. Volcanology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 15
    Publication Date: 2023-02-16
    Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Fabbrizzi, A., Parnell‐Turner, R., Gregg, P., Fornari, D., Perfit, M., Wanless, V., & Anderson, M. Relative timing of off‐axis volcanism from sediment thickness estimates on the 8°20’N seamount chain, East Pacific Rise. Geochemistry, Geophysics, Geosystems, 23(9), (2022): e2022GC010335, https://doi.org/10.1029/2022gc010335.
    Description: Volcanic seamount chains on the flanks of mid-ocean ridges record variability in magmatic processes associated with mantle melting over several millions of years. However, the relative timing of magmatism on individual seamounts along a chain can be difficult to estimate without in situ sampling and is further hampered by Ar40/Ar39 dating limitations. The 8°20’N seamount chain extends ∼170 km west from the fast-spreading East Pacific Rise (EPR), north of and parallel to the western Siqueiros fracture zone. Here, we use multibeam bathymetric data to investigate relationships between abyssal hill formation and seamount volcanism, transform fault slip, and tectonic rotation. Near-bottom compressed high-intensity radiated pulse, bathymetric, and sidescan sonar data collected with the autonomous underwater vehicle Sentry are used to test the hypothesis that seamount volcanism is age-progressive along the seamount chain. Although sediment on seamount flanks is likely to be reworked by gravitational mass-wasting and current activity, bathymetric relief and Sentry vehicle heading analysis suggest that sedimentary accumulations on seamount summits are likely to be relatively pristine. Sediment thickness on the seamounts' summits does not increase linearly with nominal crustal age, as would be predicted if seamounts were constructed proximal to the EPR axis and then aged as the lithosphere cooled and subsided away from the ridge. The thickest sediments are found at the center of the chain, implying the most ancient volcanism there, rather than on seamounts furthest from the EPR. The nonlinear sediment thickness along the 8°20’N seamounts suggests that volcanism can persist off-axis for several million years.
    Description: This work was supported by National Science Foundation awards OCE-1356610, OCE-1356822, OCE-1357150, OCE-1754419, OCE-1834797, OCE-2001314, and OCE-2001331.
    Keywords: Off-axis seamounts ; East Pacific Rise ; Sediment thickness ; Seafloor morphology ; Autonomous underwater vehicle ; Eruption history
    Repository Name: Woods Hole Open Access Server
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  • 16
    Publication Date: 2023-02-17
    Description: Author Posting. © American Geophysical Union, 2021. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 35(3), (2021): e2020GB006764, https://doi.org/10.1029/2020GB006764
    Description: Export of Particulate Organic Carbon (POC) is mainly driven by gravitational sinking. Thus, traditionally, it is thought that larger, faster-sinking particles make up most of the POC export flux. However, this need not be the case for particles whose sinking speeds are comparable to the vertical velocities of a dynamic flow field that can influence the descent rate of particles. Particles with different settling speeds are released in two process-oriented model simulations of an upper ocean eddying flow in the Northeast Pacific to evaluate the impact of (1) ocean dynamics on the respective contribution of the different sinking-velocity classes to POC export, and (2) the particle number size-spectrum slope. The analysis reveals that the leading export mechanism changes from gravitationally driven to advectively driven as submesoscale dynamics become more active in the region. The vertical velocity associated with submesoscale dynamics enhances the contribution of slower-sinking particles to POC export flux by a factor ranging from 3 to 10, especially where the relative abundance of small particles is large (i.e., steep particle size-spectrum slope). Remineralization generally decreases the total amount of biomass exported, but its impact is weaker in dynamical regimes where submesoscale dynamics are present and export is advectively driven. In an advectively driven export regime, remineralization processes counter-intuitively enhance the role of slower-sinking particles to the point where these slower-sinking velocity classes dominate the export, therefore challenging the traditional paradigm for POC export. This study demonstrates that slow-sinking particles can be a significant contribution, and at times, even dominate the export flux.
    Description: The work was funded by NASA grant NNX16AR48 G, to complement the EXport Processes in the global Ocean from RemoTe Sensing (EXPORTS) program.
    Description: 2021-08-17
    Keywords: Export ; Flux ; Particulate organic carbon ; Sinking rates ; Submeso-scales ; Vertical velocities
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  • 17
    Publication Date: 2023-02-17
    Description: Author Posting. © American Geophysical Union, 2021. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geophysical Research Letters 48(19), (2021): e2021GL095088, https://doi.org/10.1029/2021GL095088.
    Description: The physical circulation of the Southern Ocean sets the surface concentration and thus air-sea exchange of CO2. However, we have a limited understanding of the three-dimensional circulation that brings deep carbon-rich waters to the surface. Here, we introduce and analyze a novel high-resolution ocean model simulation with active biogeochemistry and online Lagrangian particle tracking. We focus our attention on a subset of particles with high dissolved inorganic carbon (DIC) that originate below 1,000 m and eventually upwell into the near-surface layer (upper 200 m). We find that 71% of the DIC-enriched water upwelling across 1,000 m is concentrated near topographic features, which occupy just 33% of the Antarctic Circumpolar Current. Once particles upwell to the near-surface layer, they exhibit relatively uniform pCO2 levels and DIC decorrelation timescales, regardless of their origin. Our results show that Southern Ocean bathymetry plays a key role in delivering carbon-rich waters to the surface.
    Description: Riley X. Brady was supported by the Department of Energy's Computational Science Graduate Fellowship (DE-FG02-97ER25308), and particularly benefited from the fellowship's summer practicum at Los Alamos National Lab. Nicole S. Lovenduski and Riley X. Brady were further supported by the U.S. Department of Energy Biological and Environmental Research program (DE-SC0022243) and by the National Science Foundation (NSF-PLR 1543457; NSF-OCE 1924636; NSF-OCE 1752724; NSF-OCE 1558225). Mathew E. Maltrud and Phillip J. Wolfram were supported as part of the Energy Exascale Earth System Model (E3SM) project, funded by the U.S. Department of Energy, Office of Science, Office of Biological and Environmental Research. This research used resources provided by the Los Alamos National Laboratory Institutional Computing Program, which is supported by the U.S. Department of Energy National Nuclear Security Administration under Contract No. 89233218CNA000001.
    Keywords: Southern Ocean ; Carbon cycle ; Upwelling ; Lagrangian modeling ; Ocean biogeochemistry ; Climate modeling
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  • 18
    Publication Date: 2023-01-20
    Description: Author Posting. © American Geophysical Union, 2022. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Biogeosciences 127(8), (2022): e2022JG006810, https://doi.org/10.1029/2022jg006810.
    Description: Submarine groundwater discharge (SGD) has been widely recognized as an important source of dissolved nutrients in coastal waters and affects nutrient biogeochemistry. In contrast, little information is available on SGD impacts on coastal carbon budgets. Here, we assessed the SGD and associated carbon (dissolved inorganic carbon [DIC] and total alkalinity [TA]) fluxes in Liaodong Bay (the largest bay of the Bohai Sea, China) and discussed their border implications for coastal DIC budget and buffering capacity. Based on 223Ra and 228Ra mass balance models, the SGD flux was estimated to be (0.92–1.43) × 109 m3 d−1. SGD was the largest contributor of DIC, accounting for 55%–77% of the total DIC sources. The low ratio (〈1) of SGD-derived TA to DIC fluxes and negative correlation between radium isotopes and pH in seawater implied that SGD would potentially reduce seawater pH in Liaodong Bay. Combining the groundwater carbon data in Liaodong Bay with literature data, we found that the SGD-derived DIC flux off China was 4–9 times greater than those from rivers. By analyzing the TA/DIC ratios in groundwater along the Chinese coast and related carbon fluxes, SGD was thought to partially reduce the CO2 buffer capacity in receiving seawater. These results obtained at the bay scale and national scale suggest that SGD is a significant component of carbon budget and may play a critical role in modulating coastal buffering capacity and atmospheric CO2 sequestration.
    Description: his research was supported by National Natural Science Foundation of China (Grant Nos. 42130703, 42007170) and the Science, Technology and Innovation Commission of Shenzhen (Grant No. 20200925174525002.
    Description: 2023-01-20
    Keywords: Submarine groundwater discharge ; Radium isotopes ; Dissolved inorganic carbon ; Total alkalinity ; Carbon budgets ; Buffering capacity
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  • 19
    Publication Date: 2023-02-28
    Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Seltzer, A. M., & Tyne, R. L. Retrieving a “Weather Balloon” from the last Ice Age. AGU Advances, 3(4), (2022): e2022AV000747, https://doi.org/10.1029/2022AV000747.
    Description: “How cold was the last ice age?” is a question that paleoclimate scientists have been trying to answer for decades. Constraining the magnitude of climate change since the Last Glacial Maximum (∼20,000 years ago) can help improve our understanding of Earth's climate sensitivity and, therefore enhance our ability to predict future change (Tierney et al., 2020). Of course, there is no single answer to this question: there is spatial structure to LGM temperature change that is linked to fundamental climate system properties and processes. Consequently, paleoclimate scientists have focused on variations of this question, like “What was the latitudinal gradient of LGM temperature change?” (Chiang et al., 2003), “What was the land-sea contrast?” (Rind & Peteet, 1985) or “What was the change in ocean heat content?” (Bereiter et al., 2018). These questions inform large-scale atmospheric and oceanic circulation, the intensity of the water cycle, and planetary energy balance; the answers to these questions come from proxies like planktic and benthic foraminifera, speleothems, ice cores, pollen records, ancient groundwater, lake sediments, and glacial moraines, to name a few. In short, the paleoclimate community has developed a proxy “tool kit” equipped to map changes across the Earth's surface and into the ocean interior; but, until now, no “tool” existed for the upper atmosphere.
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  • 20
    Publication Date: 2023-02-28
    Description: Author Posting. © American Geophysical Union, 2022. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 36(8), (2022): e2022GB007320, https://doi.org/10.1029/2022GB007320.
    Description: Biogeochemical cycles in the Arctic Ocean are sensitive to the transport of materials from continental shelves into central basins by sea ice. However, it is difficult to assess the net effect of this supply mechanism due to the spatial heterogeneity of sea ice content. Manganese (Mn) is a micronutrient and tracer which integrates source fluctuations in space and time while retaining seasonal variability. The Arctic Ocean surface Mn maximum is attributed to freshwater, but studies struggle to distinguish sea ice and river contributions. Informed by observations from 2009 IPY and 2015 Canadian GEOTRACES cruises, we developed a three-dimensional dissolved Mn model within a 1/12° coupled ocean-ice model centered on the Canada Basin and the Canadian Arctic Archipelago (CAA). Simulations from 2002 to 2019 indicate that annually, 87%–93% of Mn contributed to the Canada Basin upper ocean is released by sea ice, while rivers, although locally significant, contribute only 2.2%–8.5%. Downstream, sea ice provides 34% of Mn transported from Parry Channel into Baffin Bay. While rivers are often considered the main source of Mn, our findings suggest that in the Canada Basin they are less important than sea ice. However, within the shelf-dominated CAA, both rivers and sediment resuspension are important. Climate-induced disruption of the transpolar drift may reduce the Canada Basin Mn maximum and supply downstream. Other micronutrients found in sediments, such as Fe, may be similarly affected. These results highlight the vulnerability of the biogeochemical supply mechanisms in the Arctic Ocean and the subpolar seas to climatic changes.
    Description: This work was funded by the Natural Sciences and Engineering Research Council of Canada (NSERC) Climate Change and Atmospheric Research Grant: GEOTRACES (RGPCC 433848-12) and VITALS (RGPCC 433898), an NSERC Discovery Grant (RGPIN-2016-03865) to SEA, and by the University of British Columbia through a four year fellowship to BR. Computing resources were provided by Compute Canada (RRG 2648 RAC 2019, RRG 2969 RAC 2020, and RRG 1541 RAC 2021).
    Keywords: GEOTRACES ; Arctic Ocean ; Trace elements ; Canadian Arctic Archipelago ; Ocean modeling ; Micronutrients
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  • 21
    Publication Date: 2023-02-28
    Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Shinevar, W., Jagoutz, O., & Behn, M. WISTFUL: whole‐rock interpretative seismic toolbox for ultramafic lithologies. Geochemistry, Geophysics, Geosystems, 23(8), (2022): e2022GC010329, https://doi.org/10.1029/2022gc010329.
    Description: To quantitatively convert upper mantle seismic wave speeds measured into temperature, density, composition, and corresponding and uncertainty, we introduce the Whole-rock Interpretative Seismic Toolbox For Ultramafic Lithologies (WISTFUL). WISTFUL is underpinned by a database of 4,485 ultramafic whole-rock compositions, their calculated mineral modes, elastic moduli, and seismic wave speeds over a range of pressure (P) and temperature (T) (P = 0.5–6 GPa, T = 200–1,600°C) using the Gibbs free energy minimization routine Perple_X. These data are interpreted with a toolbox of MATLAB® functions, scripts, and three general user interfaces: WISTFUL_relations, which plots relationships between calculated parameters and/or composition; WISTFUL_geotherms, which calculates seismic wave speeds along geotherms; and WISTFUL_inversion, which inverts seismic wave speeds for best-fit temperature, composition, and density. To evaluate our methodology and quantify the forward calculation error, we estimate two dominant sources of uncertainty: (a) the predicted mineral modes and compositions, and (b) the elastic properties and mixing equations. To constrain the first source of uncertainty, we compiled 122 well-studied ultramafic xenoliths with known whole-rock compositions, mineral modes, and estimated P-T conditions. We compared the observed mineral modes with modes predicted using five different thermodynamic solid solution models. The Holland et al. (2018, https://doi.org/10.1093/petrology/egy048) solution models best reproduce phase assemblages (∼12 vol. % phase root-mean-square error [RMSE]) and estimated wave speeds. To assess the second source of uncertainty, we compared wave speed measurements of 40 ultramafic rocks with calculated wave speeds, finding excellent agreement (Vp RMSE = 0.11 km/s). WISTFUL easily analyzes seismic datasets, integrates into modeling, and acts as an educational tool.
    Description: Funding for this study was provided by NSF Grants EAR-17-22935 (OJ) and EAR-18-44340 (MB).
    Keywords: Seismic velocity ; Seismic wave speed ; Thermodynamic modeling ; Density ; Composition ; Elastic moduli
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  • 22
    Publication Date: 2023-03-02
    Description: Author Posting. © American Geophysical Union, 2022. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 36(9), (2022): e2021GB007145, https://doi.org/10.1029/2021gb007145.
    Description: In this study, we compare mechanistic and empirical approaches to reconstruct the air-sea flux of biological oxygen (F[O2]bio-as) by parameterizing the physical oxygen saturation anomaly (ΔO2[phy]) in order to separate the biological contribution from total oxygen. The first approach matches ΔO2[phy] to the monthly climatology of the argon saturation anomaly from a global ocean circulation model's output. The second approach derives ΔO2[phy] from an iterative mass balance model forced by satellite-based physical drivers of ΔO2[phy] prior to the sampling day by assuming that air-sea interactions are the dominant factors driving the surface ΔO2[phy]. The final approach leverages the machine-learning technique of Genetic Programming (GP) to search for the functional relationship between ΔO2[phy] and biophysicochemical parameters. We compile simultaneous measurements of O2/Ar and O2 concentration from 14 cruises to train the GP algorithm and test the validity and applicability of our modeled ΔO2[phy] and F[O2]bio-as. Among the approaches, the GP approach, which incorporates ship-based measurements and historical records of physical parameters from the reanalysis products, provides the most robust predictions (R2 = 0.74 for ΔO2[phy] and 0.72 for F[O2]bio-as; RMSE = 1.4% for ΔO2[phy] and 7.1 mmol O2 m−2 d−1 for F[O2]bio-as). We use the empirical formulation derived from GP approach to reconstruct regional, inter-annual, and decadal variability of F[O2]bio-as based on historical oxygen records. Overall, our study represents a first attempt at deriving F[O2]bio-as from snapshot measurements of oxygen, thereby paving the way toward using historical O2 data and a rapidly growing number of O2 measurements on autonomous platforms for independent insight into the biological pump.
    Description: N. Cassar was supported by the “Laboratoire d'Excellence” LabexMER (ANR-10-LABX-19) and co-funded by a grant from the French government under the program “Investissements d'Avenir.” Y. Huang was supported by grants from the China NSF (Nos. 42130401 and 42141002). Y. Huang was also partly supported by Chinese State Scholarship Fund to study at Duke University as a joint PhD student (No. 201806310052). R. Eveleth was supported by the NSF GRFP under grant (No. 1106401). D. Nicholson was supported by the NSF OCE-1129973 and OCE-1923915.
    Keywords: Air-sea gas biological oxygen flux ; Physical oxygen saturation anomaly ; Total dissolved oxygen ; Mechanistic and empirical models
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  • 23
    Publication Date: 2023-03-08
    Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Sayani, H., Cobb, K., Monteleone, B., & Bridges, H. Accuracy and reproducibility of coral Sr/Ca SIMS timeseries in modern and fossil corals. Geochemistry, Geophysics, Geosystems, 23(9), (2022): e2021GC010068, https://doi.org/10.1029/2021gc010068.
    Description: Coral strontium-to-calcium ratios (Sr/Ca) provide quantitative estimates of past sea surface temperatures (SST) that allow for the reconstruction of changes in the mean state and climate variations, such as the El Nino-Southern Oscillation, through time. However, coral Sr/Ca ratios are highly susceptible to diagenesis, which can impart artifacts of 1–2°C that are typically on par with the tropical climate signals of interest. Microscale sampling via Secondary Ion Mass Spectrometry (SIMS) for the sampling of primary skeletal material in altered fossil corals, providing much-needed checks on fossil coral Sr/Ca-based paleotemperature estimates. In this study, we employ a set modern and fossil corals from Palmyra Atoll, in the central tropical Pacific, to quantify the accuracy and reproducibility of SIMS Sr/Ca analyses relative to bulk Sr/Ca analyses. In three overlapping modern coral samples, we reproduce bulk Sr/Ca estimates within ±0.3% (1σ). We demonstrate high fidelity between 3-month smoothed SIMS coral Sr/Ca timeseries and SST (R = −0.5 to −0.8; p 〈 0.5). For lightly-altered sections of a young fossil coral from the early-20th century, SIMS Sr/Ca timeseries reproduce bulk Sr/Ca timeseries, in line with our results from modern corals. Across a moderately-altered section of the same fossil coral, where diagenesis yields bulk Sr/Ca estimates that are 0.6 mmol too high (roughly equivalent to −6°C artifacts in SST), SIMS Sr/Ca timeseries track instrumental SST timeseries. We conclude that 3–4 SIMS analyses per month of coral growth can provide a much-needed quantitative check on the accuracy of fossil coral Sr/Ca-derived estimates of paleotemperature, even in moderately altered samples.
    Description: We'd also like to thank Yolande Berta and Georgia Tech's Center for Nanostructure Characterization for providing access to their SEM facilities, and the Khaled bin Sultan Living Ocean Foundation and The Nature Conservancy for financial and logistical support for field excursions to Palmyra. Funding for this work was provided by the National Science Foundation (Award Numbers 1502832 and 2002458 to K.M.C) and the National Oceanic and Atmospheric Administration (Award Number: NA11OAR4310165 to K.M.C).
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  • 24
    Publication Date: 2023-03-08
    Description: Author Posting. © American Geophysical Union, 2020. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Oceans 125(5), (2020): e2019JC016007, doi:10.1029/2019JC016007.
    Description: Benthic inputs of nutrients help support primary production in the Chukchi Sea and produce nutrient‐rich water masses that ventilate the halocline of the western Arctic Ocean. However, the complex biological and redox cycling of nutrients and trace metals make it difficult to directly monitor their benthic fluxes. In this study, we use radium‐228, which is a soluble radionuclide produced in sediments, and a numerical model of an inert, generic sediment‐derived tracer to study variability in sediment inputs to the Chukchi Sea. The 228Ra observations and modeling results are in general agreement and provide evidence of strong benthic inputs to the southern Chukchi Sea during the winter, while the northern shelf receives higher concentrations of sediment‐sourced materials in the spring and summer due to continued sediment‐water exchange as the water mass traverses the shelf. The highest tracer concentrations are observed near the shelfbreak and southeast of Hanna Shoal, a region known for high biological productivity and enhanced benthic biomass.
    Description: This study presents data from multiple Arctic expeditions over the past two decades, and we are indebted to the captains, crews, and scientific parties that made this data collection possible. This work was funded by NSF awards OCE‐1458305 to M. Charette, OCE‐1458424 to W. Moore, OCE‐1434085 to D. Kadko, PLR‐1504333 to R. Pickart, and OPP‐1822334 to M. Spall. Funding was also provided by National Oceanic and Atmospheric Administration Grant NA14‐OAR4320158 to R. Pickart. L. Kipp was supported by an Ocean Frontier Institute Postdoctoral Fellowship. Radium data used in this manuscript are available in Table S1.
    Description: 2020-10-27
    Keywords: Chukchi Sea ; Benthic flux ; Radium‐228 ; GEOTRACES
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  • 25
    Publication Date: 2023-03-11
    Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Tarry, D., Ruiz, S., Johnston, T., Poulain, P., Özgökmen, T., Centurioni, L., Berta, M., Esposito, G., Farrar, J., Mahadevan, A., & Pascual, A. Drifter observations reveal intense vertical velocity in a surface ocean front. Geophysical Research Letters, 49(18), (2022): e2022GL098969, https://doi.org/10.1029/2022gl098969.
    Description: Measuring vertical motions represent a challenge as they are typically 3–4 orders of magnitude smaller than the horizontal velocities. Here, we show that surface vertical velocities are intensified at submesoscales and are dominated by high frequency variability. We use drifter observations to calculate divergence and vertical velocities in the upper 15 m of the water column at two different horizontal scales. The drifters, deployed at the edge of a mesoscale eddy in the Alboran Sea, show an area of strong convergence (urn:x-wiley:00948276:media:grl64766:grl64766-math-0001(f)) associated with vertical velocities of −100 m day−1. This study shows that a multilayered-drifter array can be an effective tool for estimating vertical velocity near the ocean surface.
    Description: This research was supported by the Office of Naval Research (ONR) Departmental Research Initiative CALYPSO under program officers Terri Paluszkiewicz and Scott Harper. The authors' ONR Grant No. are as follows: DT, SR, AM, and AP N000141613130, TMSJ N000146101612470, PP N000141812418, TO N000141812138, LRC N000141712517, and N00014191269, MB and GE N000141812782 and N000141812039, and JTF N000141812431.
    Keywords: Drifters ; Vertical velocity ; Submesoscale ; Kinematic properties ; Fronts ; Alboran Sea
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  • 26
    Publication Date: 2023-03-11
    Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Biasi, J., Tivey, M., & Fluegel, B. Volcano monitoring with magnetic measurements: a simulation of eruptions at axial seamount, Kilauea, Baroarbunga, and Mount Saint Helens. Geophysical Research Letters, 49(17), (2022): e2022GL100006, https://doi.org/10.1029/2022GL100006.
    Description: Monitoring of active volcanic systems is a challenging task due in part to the trade-offs between collection of high-quality data from multiple techniques and the high costs of acquiring such data. Here we show that magnetic data can be used to monitor volcanoes by producing similar data to gravimetric techniques at significantly lower cost. The premise of this technique is that magma and wall rock above the Curie temperature are magnetically “transparent,” but not stationary within the crust. Subsurface movements of magma can affect the crustal magnetic field measured at the surface. We construct highly simplified magnetic models of four volcanic systems: Mount Saint Helens (1980), Axial Seamount (2015–2020), Kīlauea (2018), and Bárðarbunga (2014). In all cases, observed or inferred changes to the magmatic system would have been detectable by modern magnetometers. Magnetic monitoring could become common practice at many volcanoes, particularly in developing nations with high volcanic risk.
    Description: This work was supported by the NSF Grant No 2052963 to J. Biasi and an internal Woods Hole Oceanographic Institution grant to M. Tivey.
    Keywords: Magnetism ; Volcanic hazards ; Hawaii ; Iceland ; Volcanology ; Monitoring
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  • 27
    Publication Date: 2023-03-11
    Description: © The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Bullock, E., Kipp, L., Moore, W., Brown, K., Mann, P., Vonk, J., Zimov, N., & Charette, M. Radium inputs into the Arctic Ocean from rivers a basin‐wide estimate. Journal of Geophysical Research: Oceans, 127(9), (2022): e2022JC018964, https://doi.org/10.1029/2022jc018964.
    Description: Radium isotopes have been used to trace nutrient, carbon, and trace metal fluxes inputs from ocean margins. However, these approaches require a full accounting of radium sources to the coastal ocean including rivers. Here, we aim to quantify river radium inputs into the Arctic Ocean for the first time for 226Ra and to refine the estimates for 228Ra. Using new and existing data, we find that the estimated combined (dissolved plus desorbed) annual 226Ra and 228Ra fluxes to the Arctic Ocean are [7.0–9.4] × 1014 dpm y−1 and [15–18] × 1014 dpm y−1, respectively. Of these totals, 44% and 60% of the river 226Ra and 228Ra, respectively are from suspended sediment desorption, which were estimated from laboratory incubation experiments. Using Ra isotope data from 20 major rivers around the world, we derived global annual 226Ra and 228Ra fluxes of [7.4–17] × 1015 and [15–27] × 1015 dpm y−1, respectively. As climate change spurs rapid Arctic warming, hydrological cycles are intensifying and coastal ice cover and permafrost are diminishing. These river radium inputs to the Arctic Ocean will serve as a valuable baseline as we attempt to understand the changes that warming temperatures are having on fluxes of biogeochemically important elements to the Arctic coastal zone.
    Description: This study was a broad, collaborative effort that would not have been possible without contributions from numerous funding sources, including the National Science Foundation (NSF-0751525, NSF-1736277, NSF-1458305, NSF-1938873, NSF-2048067, NSF-2134865), the NERC-BMBF project CACOON [NE/R012806/1] (UKRI NERC) and BMBF-03F0806A, and an EU Starting Grant (THAWSOME-676982).
    Keywords: Radium isotopes ; Arctic Ocean ; River fluxes
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  • 28
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    American Association for the Advancement of Science (AAAS)
    In:  EPIC3Science Advances, American Association for the Advancement of Science (AAAS), 9(26), pp. eadf9696-eadf9696, ISSN: 2375-2548
    Publication Date: 2024-03-01
    Description: Dissolved iron (dFe) availability limits the uptake of atmospheric CO2 by the Southern Ocean (SO) biological pump. Hence, any change in bioavailable dFe in this region can directly influence climate. On the basis of Fe uptake experiments with Phaeocystis antarctica, we show that the range of dFe bioavailability in natural samples is wider (〈1 to ~200% compared to free inorganic Fe′) than previously thought, with higher bioavailability found near glacial sources. The degree of bioavailability varied regardless of in situ dFe concentration and depth, challenging the consensus that sole dFe concentrations can be used to predict Fe uptake in modeling studies. Further, our data suggest a disproportionately major role of biologically mediated ligands and encourage revisiting the role of humic substances in influencing marine Fe biogeochemical cycling in the SO. Last, we describe a linkage between in situ dFe bioavailability and isotopic signatures that, we anticipate, will stimulate future research.
    Repository Name: EPIC Alfred Wegener Institut
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  • 29
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    American Association for the Advancement of Science (AAAS)
    In:  EPIC3Ocean-Land-Atmosphere Research, American Association for the Advancement of Science (AAAS), 2, ISSN: 2771-0378
    Publication Date: 2024-02-13
    Description: 〈jats:p〉Rapidly shrinking Arctic sea ice has had substantial impacts on the Earth system. Therefore, reliably estimating the Arctic sea-ice thickness (SIT) using a combination of available observations and numerical modeling is urgently needed. Here, for the first time, we assimilate the latest CryoSat-2 summer SIT data into a coupled ice-ocean model. In particular, an incremental analysis update scheme is implemented to overcome the discontinuity resulting from the combined assimilation of biweekly SIT and daily sea-ice concentration (SIC) data. Along with improved estimates of sea-ice volume, our SIT estimates corrected the overestimation of SIT produced by the reanalysis that assimilates only SIC in summer in areas where the sea ice is roughest and experiences strong deformation, e.g., around the Fram Strait and Greenland. This study suggests that the newly developed CryoSat-2 SIT product, when assimilated properly using our approach, has great potential for Arctic sea-ice simulation and prediction.〈/jats:p〉
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  • 30
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    American Association for the Advancement of Science (AAAS)
    In:  EPIC3Science, American Association for the Advancement of Science (AAAS), 382(6677), pp. 1384-1389, ISSN: 0036-8075
    Publication Date: 2024-02-22
    Description: The marine-based West Antarctic Ice Sheet (WAIS) is considered vulnerable to irreversible collapse under future climate trajectories, and its tipping point may lie within the mitigated warming scenarios of 1.5° to 2°C of the United Nations Paris Agreement. Knowledge of ice loss during similarly warm past climates could resolve this uncertainty, including the Last Interglacial when global sea levels were 5 to 10 meters higher than today and global average temperatures were 0.5° to 1.5°C warmer than preindustrial levels. Using a panel of genome-wide, single-nucleotide polymorphisms of a circum-Antarctic octopus, we show persistent, historic signals of gene flow only possible with complete WAIS collapse. Our results provide the first empirical evidence that the tipping point of WAIS loss could be reached even under stringent climate mitigation scenarios.
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  • 31
    Publication Date: 2024-01-31
    Description: The response of permafrost to submergence can vary between ice-rich late Pleistocene deposits and the thermokarst basins that thawed out during the Holocene. We hypothesize that inundated Alases offshore thaw faster than submerged Yedoma. To test this hypothesis, we estimated depths to the top of ice-bearing permafrost offshore of the Bykovsky Peninsula in northeast Siberia using electrical resistivity surveys. The surveys traversed submerged lagoon deposits, drained and refrozen Alas deposits, and undisturbed Yedoma from the coastline to 373 m offshore. While the permafrost degradation rates of the submerged Yedoma were in the range of similar sites, the submerged Alas permafrost degradation rates were up to 170% faster. Given the abundance of thermokarst basins and lakes along parts of the Arctic coastline, its effect on subsea permafrost degradation must be similarly prevalent. Remote sensing analyses suggest that 54% of lagoons wider than 500 m originated in thermokarst basins.
    Repository Name: EPIC Alfred Wegener Institut
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  • 32
    Publication Date: 2024-01-31
    Description: Permafrost thaw leads to thermokarst lake formation and talik growth tens of meters deep, enabling microbial decomposition of formerly frozen organic matter (OM). We analyzed two 17-m-long thermokarst lake sediment cores taken in Central Yakutia, Russia. One core was from an Alas lake in a Holocene thermokarst basin that underwent multiple lake generations, and the second core from a young Yedoma upland lake (formed ca. 70 years ago) whose sediments have thawed for the first time since deposition. This comparison provides a glance into OM fate in thawing Yedoma deposits. We analyzed total organic carbon (TOC) and dissolved organic carbon (DOC) content, n-alkanes concentrations, and bacterial and archaeal membrane markers. Furthermore, we conducted one-year-long incubations (4 °C, dark) and measured anaerobic carbon dioxide (CO2) and methane (CH4) production. The sediments from both cores contained little TOC (0.7±0.4 wt%), but DOC values were relatively high, with highest values in the frozen Yedoma lake sediments (1620 mg L-1). Cumulative GHG production after one year was highest in the Yedoma lake sediments (226±212 μg CO2-C gdw-1, 28±36 μg CH4-C gdw-1) and 3 and 1.5 times lower in the Alas lake sediments, respectively (75±76 μg CO2-C gdw-1, 19±29 μg CH4-C gdw-1). The highest CO2 production in the frozen Yedoma lake sediments likely results from decomposition of readily bioavailable OM, while highest CH4 production in the non-frozen top sediments of this core suggests that methanogenic communities established upon thaw. The lower GHG production in the non-frozen Alas lake sediments resulted from advanced OM decomposition during Holocene talik development. Furthermore, we found that drivers of CO2 and CH4 production differ following thaw. Our results suggest that GHG production from TOC-poor mineral deposits, which are widespread throughout the Arctic, can be substantial. Therefore, our novel data are relevant for vast ice-rich permafrost deposits vulnerable to thermokarst formation.
    Repository Name: EPIC Alfred Wegener Institut
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  • 33
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    Wiley-Blackwell
    In:  EPIC3Permafrost and Periglacial Processes, Wiley-Blackwell, 32(1), pp. 59-75, ISSN: 1045-6740
    Publication Date: 2024-01-31
    Description: Thermal erosion is a major mechanism of permafrost degradation, resulting in characteristic landforms. We inventory thermo-erosional valleys in ice-rich coastal lowlands adjacent to the Siberian Laptev Sea based on remote sensing, Geographic Information System (GIS), and field investigations for a first regional assessment of their spatial distribution and characteristics. Three study areas with similar geological (Yedoma Ice Complex) but diverse geomorphological conditions vary in valley areal extent, incision depth, and branching geometry. The most extensive valley networks are incised deeply (up to 35 m) into the broad inclined lowland around Mamontov Klyk. The flat, low-lying plain forming the Buor Khaya Peninsula is more degraded by thermokarst and characterized by long valleys of lower depth with short tributaries. Small, isolated Yedoma Ice Complex remnants in the Lena River Delta predominantly exhibit shorter but deep valleys. Based on these hydrographical network and topography assessments, we discuss geomorphological and hydrological connections to erosion processes. Relative catchment size along with regional slope interact with other Holocene relief-forming processes such as thermokarst and neotectonics. Our findings suggest that thermo-erosional valleys are prominent, hitherto overlooked permafrost degradation landforms that add to impacts on biogeochemical cycling, sediment transport, and hydrology in the degrading Siberian Yedoma Ice Complex.
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  • 34
    Publication Date: 2024-01-20
    Repository Name: EPIC Alfred Wegener Institut
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  • 35
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    American Association for the Advancement of Science (AAAS)
    In:  EPIC3Science, American Association for the Advancement of Science (AAAS), 383(6685), pp. 884-890, ISSN: 0036-8075
    Publication Date: 2024-03-21
    Description: Much of our understanding of Cenozoic climate is based on the record of δ18O measured in benthic foraminifera. However, this measurement reflects a combined signal of global temperature and sea level, thus preventing a clear understanding of the interactions and feedbacks of the climate system in causing global temperature change. Our new reconstruction of temperature change over the past 4.5 million years includes two phases of long-term cooling, with the second phase of accelerated cooling during the Middle Pleistocene Transition (1.5 to 0.9 million years ago) being accompanied by a transition from dominant 41,000-year low-amplitude periodicity to dominant 100,000-year high-amplitude periodicity. Changes in the rates of long-term cooling and variability are consistent with changes in the carbon cycle driven initially by geologic processes, followed by additional changes in the Southern Ocean carbon cycle. 〈/jats:p〉
    Repository Name: EPIC Alfred Wegener Institut
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  • 36
    Publication Date: 2024-03-22
    Repository Name: EPIC Alfred Wegener Institut
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  • 37
    Publication Date: 2024-04-05
    Description: Rayleigh wave ellipticity measurements from seismic ambient noise recorded on the Greenland Ice Sheet (GrIS) show complex and anomalous behavior at wave periods sensitive to ice (T 〈 3–4 s). To understand these complex observations, we compare them with synthetic ellipticity measurements obtained from synthetic ambient noise computed for various seismic velocity and attenuation models, including surface wave overtone effects. We find that in dry snow conditions within the interior of the GrIS, to first order the anomalous ellipticity observations can be explained by ice models associated with the accumulation and densification of snow into firn. We also show that the distribution of ellipticity measurements is strongly sensitive to seismic attenuation and the thermal structure of the ice. Our results suggest that Rayleigh wave ellipticity is well suited for monitoring changes in firn properties and thermal composition of the Greenland and Antarctic ice sheets in a changing climate.
    Description: Published
    Description: e2023GL103673
    Description: OST1 Alla ricerca dei Motori Geodinamici
    Description: JCR Journal
    Keywords: 04.06. Seismology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 38
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    American Association for the Advancement of Science (AAAS)
    In:  EPIC3Science Advances, American Association for the Advancement of Science (AAAS), 9(8), pp. eabq4632-eabq4632, ISSN: 2375-2548
    Publication Date: 2024-04-03
    Description: 〈jats:p〉Comprehensive sampling of natural genetic diversity with metagenomics enables highly resolved insights into the interplay between ecology and evolution. However, resolving adaptive, neutral, or purifying processes of evolution from intrapopulation genomic variation remains a challenge, partly due to the sole reliance on gene sequences to interpret variants. Here, we describe an approach to analyze genetic variation in the context of predicted protein structures and apply it to a marine microbial population within the SAR11 subclade 1a.3.V, which dominates low-latitude surface oceans. Our analyses reveal a tight association between genetic variation and protein structure. In a central gene in nitrogen metabolism, we observe decreased occurrence of nonsynonymous variants from ligand-binding sites as a function of nitrate concentrations, revealing genetic targets of distinct evolutionary pressures maintained by nutrient availability. Our work yields insights into the governing principles of evolution and enables structure-aware investigations of microbial population genetics.〈/jats:p〉
    Repository Name: EPIC Alfred Wegener Institut
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  • 39
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    American Geophysical Union
    In:  EPIC3Journal of Geophysical Research (JGR): Biogeosciences, American Geophysical Union, 129, ISSN: 2169-8953
    Publication Date: 2024-04-19
    Description: Arctic warming increases the degradation of permafrost soils but little is known about floodplain soils in the permafrost region. This study quantifies soil organic carbon (SOC) and soil nitrogen stocks, and the potential CH4 and CO2 production from seven cores in the active floodplains in the Lena River Delta, Russia. The soils were sandy but highly heterogeneous, containing deep, organic rich deposits with 〉60% SOC stored below 30 cm. The mean SOC stocks in the top 1 m were 12.9 ± 6.0 kg C m−2. Grain size analysis and radiocarbon ages indicated highly dynamic environments with sediment re-working. Potential CH4 and CO2 production from active floodplains was assessed using a 1-year incubation at 20°C under aerobic and anaerobic conditions. Cumulative aerobic CO2 production mineralized a mean 4.6 ± 2.8% of initial SOC. The mean cumulative aerobic:anaerobic C production ratio was 2.3 ± 0.9. Anaerobic CH4 production comprised 50 ± 9% of anaerobic C mineralization; rates were comparable or exceeded those for permafrost region organic soils. Potential C production from the incubations was correlated with total organic carbon and varied strongly over space (among cores) and depth (active layer vs. permafrost). This study provides valuable information on the carbon cycle dynamics from active floodplains in the Lena River Delta and highlights the key spatial variability, both among sites and with depth, and the need to include these dynamic permafrost environments in future estimates of the permafrost carbon-climate feedback.
    Repository Name: EPIC Alfred Wegener Institut
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  • 40
    Publication Date: 2024-04-22
    Description: Large stocks of soil organic carbon (SOC) have accumulated in the northern hemisphere permafrost region, but their current mounts and future fate remain uncertain. By analyzing an unprecedented dataset combining 〉2,700 soil profiles with environmental variables in a geospatial framework, we generated spatially explicit estimates of permafrost-region SOC stocks, quantified spatial heterogeneity, and identified key environmental predictors. We estimated 1014−175+194 Pg C are stored in the top 3 m of permafrost region soils. The greatest uncertainties occurred in circumpolar toe-slope positions and in flat areas of the Tibetan region. We found that soil wetness index and elevation are the dominant topographic controllers and surface air temperature (circumpolar region) and precipitation (Tibetan region) are significant climatic controllers of SOC stocks. Our results provide the first high-resolution geospatial assessment of permafrost region SOC stocks and their relationships with environmental factors, which are crucial for modeling the response of permafrost affected soils to changing climate.
    Repository Name: EPIC Alfred Wegener Institut
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  • 41
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    Wiley-Blackwell
    In:  EPIC3Reviews in Aquaculture, Wiley-Blackwell, ISSN: 1753-5123
    Publication Date: 2024-05-06
    Description: Mass mortality events (MMEs) are defined as the death of large numbers of fish over a short period of time. These events can result in catastrophic losses to the Atlantic salmon aquaculture industry and the local economy. However, they are challenging to understand because of their relative infrequency and the high number of potential factors involved. As a result, the causes and consequences of MMEs in Atlantic salmon aquaculture are not well understood. In this study, we developed a structural network of causal risk factors for MMEs for aquaculture and the communities that depend on Atlantic salmon aquaculture. Using the Interpretive Structural Modeling (ISM) technique, we analysed the causes of Atlantic salmon mass mortalities due to environmental (abiotic), biological (biotic) and nutritional risk factors. The consequences of MMEs were also assessed for the occupational health and safety of aquaculture workers and their implications for the livelihoods of local communities. This structural network deepens our understanding of MMEs and points to management actions and interventions that can help mitigate mass mortalities. MMEs are typically not the result of a single risk factor but are caused by the systematic interaction of risk factors related to the environment, fish diseases, feeding/nutrition and cage-site management. Results also indicate that considerations of health and safety risk, through pre- and post-event risk assessments, may help to minimize workplace injuries and eliminate potential risks of human fatalities. Company and government assisted socio-economic measures could help mitigate post-mass mortality impacts. Appropriate and timely management actions may help reduce MMEs at Atlantic salmon cage sites and minimize the physical and social vulnerabilities of workers and local communities.
    Repository Name: EPIC Alfred Wegener Institut
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  • 42
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    American Association for the Advancement of Science (AAAS)
    In:  EPIC3Science Advances, American Association for the Advancement of Science (AAAS), 9(44), pp. eadg2639-eadg2639, ISSN: 2375-2548
    Publication Date: 2024-04-24
    Description: Paleoceanographic reconstructions show that the strength of North Atlantic currents decreased during the Little Ice Age. In contrast, the role of ocean circulation in climate regulation during earlier historical epochs of the Common Era (C.E.) remains unclear. Here, we reconstruct sea surface temperature (SST) and salinity in the Caribbean Basin for the past 1700 years using the isotopic and elemental composition of planktic foraminifera tests. Centennial-scale SST and salinity variations in the Caribbean co-occur with (hydro)climate changes in the Northern Hemisphere and are linked to a North Atlantic SST forcing. Cold phases around 600, 800, and 1400 to 1600 C.E. are characterized by Caribbean salinification and Gulf of Mexico freshening that implies reductions in the strength of North Atlantic surface circulation. We suggest that the associated changes in the meridional salt advection contributed to the historical climate variability of the C.E.
    Repository Name: EPIC Alfred Wegener Institut
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  • 43
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    American Association for the Advancement of Science (AAAS)
    In:  EPIC3Sci Adv, American Association for the Advancement of Science (AAAS), 10(20), pp. eadl5904-eadl5904, ISSN: 2375-2548
    Publication Date: 2024-05-22
    Description: Marine heatwaves are increasing in frequency and intensity as climate change progresses, especially in the highly productive Arctic regions. Although their effects on primary producers will largely determine the impacts on ecosystem services, mechanistic understanding on phytoplankton responses to these extreme events is still very limited. We experimentally exposed Arctic phytoplankton assemblages to stable warming, as well as to repeated heatwaves, and measured temporally resolved productivity, physiology, and composition. Our results show that even extreme stable warming increases productivity, while the response to heatwaves depends on the specific scenario applied and is not predictable from stable warming responses. This appears to be largely due to the underestimated impact of the cool phase following a heatwave, which can be at least as important as the warm phase for the overall response. We show that physiological and compositional adjustments to both warm and cool phases drive overall phytoplankton productivity and need to be considered mechanistically to predict overall ecosystem impacts.
    Repository Name: EPIC Alfred Wegener Institut
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  • 44
    Electronic Resource
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    New York : Wiley-Blackwell
    Biopolymers 10 (1971), S. 1049-1057 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ultrastructural morphology and x-ray and electron diffraction of poly (Gly-Gly-Ala) have been studied. The polymer has two forms; the first, form I possesses a super-folded cross-β structure, long fibers of which show some twisting and intertwining. Form II precipitates in a less distinct fibrous form from aqueous solution. The x-ray diffraction and oriented electron diffraction data suggest that form II is a polyglycine II helix situated in a monoclinic cell with dimensions a = 8.86 Å, b = 22.0 Å, c = 9.42 Å, and β = 90°. Combined with the morphological evidence it appears likely that form II is also in an antiparallel superfolded array.
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  • 45
    Electronic Resource
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    Biopolymers 10 (1971), S. 1099-1101 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 46
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A statistical mechanical model was developed for use in connection with the problem of preferential binding of solvent components to proteins and of conformational transition in water-organic solvent systems. The model is a statistical one for the conformational transition of globular proteins induced by the adsorption of solutes in the solution, considered as a nearest-neighbor problem in statistical mechanics. Although a few illustrative examples are given, the actual interpretations of the experimental data using this theory are reserved for a later paper.
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  • 47
    Electronic Resource
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    Biopolymers 10 (1971), S. 1103-1103 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 48
    Electronic Resource
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    Biopolymers 10 (1971), S. 1121-1138 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The concept and representation of a logical tree as defined in computer science is applied to obtain a suitable representation of protein molecules in computer programs which handle or calculate atomic coordinates of protein molecules. On the basis of this analysis and of the analysis of the calculation and modification of the structure of a protein from bond lengths, bond angles, and dihedral angles, which is reproduced in an appendix, program modules which accomplish the various required computations are described. Three such modules are given in Iverson notation; in fact, it is hoped that this article will serve as a reasonably complete basis for the preparation of machine programs by moderately proficient programmers.
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  • 49
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    Biopolymers 10 (1971), S. 1207-1212 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism spectrum obtained from a dilute aqueous solution of poly (ala-gly-gly) resembles that described for charged polypeptides such as the salt form of poly glutamic acid. A similar spectrum is found for films cast from aqueous solution where x-ray studies reported elsewhere have indicated a poly-glycinc II conformation. Evidence is presented for a heat induced poly-glycine II to unordered state transition similar to that described for collagen. The interpretation of this, the first observation of the optical properties of a poly-amino acid in the poly glycine II conformation, is further rationalized on the basis of spectra obtained from a number of polypeptides whose conformation approaches that of a 31 helix.
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  • 50
    Electronic Resource
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    Biopolymers 10 (1971), S. 1229-1242 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effect of cupric ion on the emission of tryptophan, tyrosine, and serum albumins is studied by emission spectroscopy and lifetime measurements. It is found that whenever cupric ion is bound to tryptophan or tyrosine, their emissions are quenched completely. The quenching may be due to an electron transfer mechanism. The fluorescence of complexes of cupric ions with serum albumins is partially quenched; this is because energy is transferred from tryptophan to the complexed cupric ions by a dipolar energy transfer mechanism. It is deduced from the present study that the tryptophan in the human serum albumin molecule is between 11 and 16 Å from the nearest eupric ion binding sites (assumed to be at the surface of the protein) and that one of the tryptophan in the bovine serum albumin molecule is very close to the cupric ion binding sites and the other is near the center of the bovine serum albumin molecule. It is also found that the deuterium solvent effect on serum albumin fluorescence is very small, and that the quenching of bovine serum albumin fluorescence at the N-F transition is the result of quenching of the fluorescence of both tryptophans. The phosphorescence lifetime apparatus, capable of measuring decay times of signals with intensities changing over a few orders of magnitude, and the ratio spectrofluorometer, both of which were constructed in this laboratory, are also described.
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  • 51
    Electronic Resource
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    Biopolymers 10 (1971), S. 1253-1260 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The measurements were made for the volume and the sound velocity changes (ΔV and ΔU) on titrating the sodium salt of poly (S-carboxymethyl L-cysteine) with dilute HCl. For the reaction, —COO- + H+ → —COOH, ΔV per mole of H+ bound was + 12. 7 ml and +11. 4 ml in salt-free and 0. 2 M NaCl solutions, respectively. Corresponding ΔU was about -13 cm/sec in salt-free polymer solution where 11.5 mM carboxylate ion reacts with equimolar hydrogen ion. ΔV associated with the coil-to-β transition was found to be +2. 35 ml in H2O and +1. 90 ml in 0. 2 M NaCl per mole of amino acid residue, respectively. These values are larger than those obtained for the coil-to-helix transition of poly (L-glutamic acid). ΔU for the transition was about -30 cm/sec in salt-free solution of polymer concentration 0.0115 mole/liter. Possible sources of ΔV and ΔU for reaction; coil → β, are (1) the formation of void volume and (2) the changes in the extent of solvation in amide linkage and in side chain.
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  • 52
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    Biopolymers 10 (1971), S. 1317-1329 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding of three aromatic molecules to apomyoglobin has been investigated. In each case equilibrium dialysis studies and tryptophan fluorescence quenching studies indicate that a one to one complex has been formed. The fluorescence quenching studies further suggest that the binding of the aromatic molecules is at the heme site with possible involvement of the arginine CD3. Xenon, which is known to quench the fluorescence of aromatic hydrocarbons, is found to be bound to apomyoglobin-aromatic molecule complexes and quenches the emission of the aromatic molecule in the complexes. Oxygen quenches pyrene fluorescence in water solution but does not quench the pyrene fluorescence from the apomyoglobin-pyrene complex. This is explained by a slower rate of diffusion of oxygen to pyrene in the apomyoglobin-pyrene complex.
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  • 53
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    Biopolymers 10 (1971), S. 1365-1369 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rotor speed-dependent aggregation of T4 DNA in the analytical ultracentrifuge is studied in the presence of high pressure generated by compressed nitrogen gas in the cell. The extents of aggregation at various speeds are found to be practically the same in the presence and absence of pressure.
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  • 54
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    Biopolymers 10 (1971), S. 1331-1349 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The time-dependent theory developed in Part I is specialized to treat tetrameric hemoglobin, and the results of the theory for dimeric-and tetrameric hemoglobin are compared with data on the kinetics of the reactions of hemoglobin with carbon monoxide and oxygen at various salt concentrations for the case of large concentration of ligand relative to that of hemoglobin. The fit of the theoretical results to the data suggests that hemoglobin at a 2 M salt concentration is predominantly dimeric and that the tetramer should be taken as the functional unit to explain the kinetics of the reactions of normal hemoglobin. A relationship is established between the time-dependent theory arid Adair's Intermediate Compound Hypothesis (I.C.H.) for hemoglobin, as brought to its present state by Gibson and Roughton. A generalization (G.I.C.H.) of the I.C.H. is presented and is shown to be equivalent to the time-dependent theory in the limit of infinite ligand concentration. The I.C.H. is shown to be an excellent approximation to the centralized theory (G.I.C.H.) in this limit.
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  • 55
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    Biopolymers 10 (1971), S. 1421-1425 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 56
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    Biopolymers 10 (1971), S. 1427-1428 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 57
    Electronic Resource
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    Biopolymers 10 (1971), S. 1429-1454 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The ability of oligodesoxyribonucleotides of various chain lengths to form complexes has been compared with that of oligoribonucleotides. Four series of oligonucleotidcs were prepared and investigated, i.e., dCn at acid pH versus rCn, dAn and dTn versus. rAn and rUn at neutral pH. The results indicate that in dilute solution, the formation of complexes is greatly facilitated in the case of desoxyoligomers and occurs for shorter oligomere than in the corresponding ribooligomers. The spectrophotometric titration of deoxyribooligo C indicates the appearance of two pK values in the 4-5 pH region characteristic of the double-stranded form, which occurs for much shorter dCn than rCn. The circular dichroism (CD.) spectra of deoxycytidylies in dilute solution starting from the trimer are conservative, characteristic of the double-stranded helical form of poly C at acid pH. In contrast, the CD spectra of a series of corresponding ribo Cn, under identical conditions is of nonconservative character similar to that of the single-stranded form of poly C at neutral pH, but differs in the band position. This spectrum is called intermediate. Only at higher concentrations of oligonucleotidcs (i.e., 10-3Minstead of 10-4M) does the circular dichroism spectrum of longer ribocytidylics assume conservative character. Thermal denaturation of deoxycytidylces at acid pH are strongly dependent on chain length and concentration, its one would expect for a cooperative helix-coil transition. The circular dichroism spectra measured at different temperatures shows one isosbestic point. In dilute solution, the standard-state enthalpy change found was 5-6 kcal/mole for higher oligomers (dC7). These properties are all in agreement with a structural transition from the d-Cn double-stranded form to a coil for n 〉 3. Studies of dAn and dTn in solutions of high ionic strength at low temperature indicate that complex formation occurs already at the level of trimer and for high oligomers. Under identical conditions a complex between rAn and rUn is detected only for oligomers longer than the hexamer. The nature of the “intermediate” form of oligoribo C at acid pH and low temperature was investigated by sedimentation and circular dichroism. A model of rCn is proposed of linear molecules which are partially double-stranded and partially single-stranded, which probably are slowly rearranged by “slippage” into a regular-double-stranded helical form.
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The number average molecular weight, Mn, of low molecular weight dextran was determined through endgroup analysis, and the intrinsic, viscosities of these materials in aqueous solution were determined at 25°C. The ultrasonic velocities in their aqueous solutions were also measured at 25 and 45°C. As concerns the molecular weight dependence of the intrinsic viscosity, partial specific compressibility of solute and the hound water around the solute, the following results were obtained. (1) log [η]-log Mn and [η]/Mn0.5 - Mn0.5 plots were in accord with the Mark-Houwink and Stockmayer-Fix-man equations respectively for Mn 〉 2, 000, but these plots deviated from the equations for Mn 〈 2, 000. (2)The partial specific compressibility, β1°, of dextran is expressed by following equation for Mn 〈 2,000: β1° = 10-12 × (13.6 log Mn - 51.7) (cm2/dyne). In contrast, it, becomes the constant value, -- 7.3 × 10-12 cm2/dyne, for Mn 〉 2,000. (3) The amount of bound water of dextran calculated from the sound velocity measurement lakes constant value of 0.17 ml g for Mn 〉 2, 000, but the amount of hydration increase with decreasing molecular weight for Mn 〈 2,000. From these results, a dextran molecule in aqueous solution is expected to change its conformation from random coiling to uncoiling stretched form at the molecular weight of around 2, 000 or about 12 glucose units.
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    Biopolymers 10 (1971), S. 1559-1581 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Optical rotation studies were performed on five compounds containing two peptide groups. Four of the molecules were confined to restricted regions of conformational space by the presence of closed rings. Solvent and temperature were varied, and theoretical calculations were done for each compound covering the appropriate conformational space. The interpretation which results is qualitatively successful over the conformational regions covered by the compounds. Quantitative correlation between theory and experiment will require compounds of high rigidity.
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    Biopolymers 10 (1971), S. 1617-1623 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational energy maps have been calculated for α-D-mannuronic acid (1-4) α-L-guluronic acid and for α-L-guluronic acid (1-4) β-D-mannuronic acid. These have been used, together with maps previously calculated for the homomonomeric dimers, to estimate the characteristic ratios and Kuhn lengths of the alternating copolymer and of a stochastic copolymer similar in composition to that extracted from L. digitata.The results show that the alternating copolymer is less extended than either homopolymer. Kuhn lengths calculated for the stochastic copolymer agree well with experimental results on high ionic strength solutions of alginate isolated from L digitata.
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    Biopolymers 10 (1971), S. 1635-1648 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-S-carboxyethyl-L-cysteine, a higher side-chain homolog of poly-S-carboxymethyl-L-cysteine, has been prepared from poly-S-carbobenzoxyethyl-L-cysteine with hydrogen bromide in chloroform or acetic acid. The polymer is found to be in the β-conformation of an antiparallel arrangement of polypeptide chains in solid films, both in acid and salt forms, when examined by infrared spectra. Aqueous solutions of t he polymer have been investigated by measurements of rotatory dispersion and circular dichroism as well as by infrared spectra in D2O. These properties show sharp changes around pH 5.5, as the pH of solution is varied. At higher ionization the polymer is randomly coiled, but at lower ionization it is in the β-conformation. Dependence of the rotatory properties upon polymer concentration as well as on ionic strength has been observed even at the lowest degree of ionization attained, and this has been attributed to the formation of intermolecular β-conformation in solutions. The β-structure is characterized by a negative circular dichroic band at 223 mμ and a positive dichroic band at a wavelength lower than 200 mμ, and furt her by a negative bo value, -140°. The pH-induced coil-β transition of the polymer is compared with that of poly-S-carboxymethl-L-cysteine.
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    Biopolymers 10 (1971), S. 1681-1699 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The specific heat, of rat tail tendon at various water contents was measured as a function of temperature. The resulting graphs showed peaks arising from the melting, near 50°C, of helical material in the collagen, and from the melting of absorbed water in the range -40°C to 0°C. The heat of melting of helical material was 11.7 cal per gram of dry tendon. Determination of the heat and temperature of fusion of the absorbed water allowed resolution of the water into four states in the case of tendon before denaturation, and three states after denaturation. The four states are (1) water not freezable on cooling to - 70°C, (2) freezable water with-both heat and temperature of fusion different from the values for ordinary water, (3) freezable water with the heat of fusion of ordinary water, but a different temperature of fusion, and (4) water not distinguished from ordinary water. The fourth state was absent in denatured tendon. The results are discussed in terms of increasing size of clusters of absorbed water molecules.
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    Biopolymers 10 (1971) 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 10 (1971), S. 1743-1757 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The absorption and rotatory properties of acridine orange-poly-S-carboxymethyl-L-cysteine system in water and in 0.2 M NaCl have been measured at different pH and polymer-to-dye mixing ratios. The absorption spectra indicate that the dyes are bound to the polymer in dimeric or highly aggregated forms. At neutral pH where the polymer is randomly coiled, no optical activity is induced on the absorption bands of bound acridine orange. At acid pH where the polymer has the β-conformation, a pair of positive and negative circular dichroic bands occur at each of the absorption bands, centered around 458 and 261 mμ. The signs of those bands are opposite to those found for α-helical poly-L-glutamic acid. A model for the binding of dye to the β-form polymer is presented, in which dimeric dyes are attached to ionized carboxyl groups and slack one another to form linear arrays on both sides of an extended polypeptide chain. The observed circular dichroism spectra can be explained by the Tinoco's exciton mechanism, based on this model. Low molecular weight poly-S-carboxymethyl-L-cysteine induces quite a different circular dichroism on bound acridine orange.
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    Biopolymers 10 (1971), S. 1853-1863 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dicrosim (CD) spectra of complexes of DNA with ethidiun bromnide, profiavine, 9-aminoacridine and 4-etliyl-9-amino-acridine have been determined between 220 and 450 nm, the range lieing extended to 600 nm for ethidiufm bromide. The variation of the magnitude of the visible and near - ultraviolet CD spectra of ethidium bromide - DNA complexes with the amount of ligand bound (r) suggests a common binding position with profiavine. On the other hand, 4-ethyl-9-aminoacndine complexed to DNA shows CD spectra not distinguishable from those of 9-aminnoacnidmc in both the visible and ultraviolet. The interpretation of these results with respect to the stereochemistry of the DNA-ligand complexes is discussed.
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    Biopolymers 10 (1971), S. 1901-1924 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The various treatments of sedimentation equilibrium are compared on a theoretical and an experimental basis. Particular attention is paid to the polyelectrolyte nature of the problem and the choice of a neutral component. The effective density gradients of several cesium salts for DNA are measured. Two previous theories for the effective density gradient are shown to be equivalent, and the experimental values are interpreted with respect to these theories. It is clear t hat sedimentation equilibrium in a density gradient may be used for the determination of unambiguous molecular weights.
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    Biopolymers 10 (1971), S. 1949-1972 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The theory of friction-limited DNA unwinding is developed explicitly for moderate tind large perturbations. This extension of the earlier theory of the relaxation kinetics is necessary because of the complex nature of the rate limitation for small perturbations. The assumption of the theory that is violated under relaxation conditions is that base pairing reactions occurring at a constant local degree of twist of the strands are fast compared to the net unwinding of the molecule. However, these reactions that are slow for small perturbations have a large activation energy, and become faster than friction-limited un winding for large enough temperature jumps and sufficiently large DXA molecules. Thus only the rate for moderate and large perturbations is clearly limited by frictional resistance to turning the molecule in solution. The model used is a diffusional unwinding of the two strands, driven by the accompanying decrease in free energy. For large perturbations a numerical solution of the diffusion equation is required, since the diffusion coefficient is not constant. Two new parameters must be introduced into the equilibrium statistical theory to describe friction-limited unwinding kinetics. These are the force constant b, for winding up coil regions and the frictional coefficient per base pair βcfor rotating coil regions in solution. We find by fitting the theory to experiment that b = 1.8 × 10-13 ergs/ rad2- and βc = 3.5 × 10-21 erg see/base pair, both for DNA melted in alkali at 0.4.M Na + and ∼30 °C. The latter value is in agreement with predictions based on the viscosity of single stranded DNA in alkali. The quoted value of bcan be interpreted to mean that the number of conformational states of a nucleolide is reduced by an average factor of 1.55 when it is wound around another strand to the degree of twist in a double helix, but without forming a base pair.
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    Topics: Chemistry and Pharmacology
    Notes: The properties of oligonucleotide helices of adeuylic- and uridylic acid oligomers have been investigated by measurements of hypo-and hyperchromieity. High ionic strengths favor the formation of triple helices. Thus, the double helix-coil transition can be studied (without interference by triple helices) only at low ionic-strength. A “phase diagram” is given representing the Tm-values of the various transitions at different ionic strengths for the system A(pA)17 + U(pU)17. Oligonucleolides of chain lengths 〈8 always form both double and triple helices at the nucleotide concentrations required for base pairing. For this reason the double helix-coil transition without coupling of the triple helix equilibrium can only be measured for chain lengths higher than 7. Melting curves corresponding to this transition have been determined for chain lengths 8, 9, 10, 11, 14 and 18 at different concentrations. An increase in nucleotide concentration leads to an increase in melting temperature. The shorter the chain length the lower the Tm-value and the broader the helix-coil transition. The experimental transition curves have been analysed according to a staggering zipper model with consideration of the stacking of the adeuylic acid single strands and the electrostatic repulsion of tlip phosphate charges on opposite strands. The temperature dependence of the nucleation parameter has been accounted for by a slacking factor x. The stacking factor expresses the magnitude of the stacking enthalpy. By curve fitting xwas computed to be 0.7, corresponding to a stacking enthalpy of about S kcal/mole. The model described allows the reproduction of the experimental transition curves with relatively high accuracy. In an appendix the thermodynamic parameters of the stacking equilibrium of poly A and of the helix-coil equilibria of poly A + poly U at neutral pH are calculated (ΔHA = -7.9 kcal/mole for the poly A stacking and ΔH12 = -10.9 kcal/mole for the formation of the double helix from the randomly coiled single strands). A formula for the configurational entropy of polymers derived by Flory on the basis of a liquid lattice model is adapted to calculate the stacking entropies of adenylic oligomers.
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    Biopolymers 10 (1971), S. 2049-2049 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 10 (1971), S. 2071-2077 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The data on the band widths and band shapes of several DNA's at various concentrations in sedimentation equilibrium in a CsCl density gradient have recently become available. In the present report, these literature data are treated in the following manner: (1) based on a theory of isotope-substitution, calculations are made of the molecular weights at infinite dilution, and (2) to explain the concentration dependence of band widths and band shapes, a theory of charge and hydration is put forth, and it is shown that by retaining the terms involving the charge of the macromolecules, it is possible to account for most of the concentration dependence.
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    Biopolymers 10 (1971), S. 2083-2094 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The mechanism of the unique and specific association of a given amino acid to its t-RNA is investigated by theoretical methods. Several possible schemes are proposed to explain specificity. The physical forces which act within these mechanisms are illustrated by the computer simulation of probable interactions between glycine and nucleotide bases and base pairs. It is demonstrated that glycine has direct and selective affinities for the nucleotide bases and that these interactions are principally determined by the polar groups. Energies have been calculated for the interaction of glycine with several base pairs. From these, the possibility that specificity arises through direct complexing of an amino acid with its anticodon is evaluated.
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    Biopolymers 10 (1971), S. 2147-2160 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Equations are developed to describe the shift in the temperature of the helix-coil transition when small molecules bind to nucleic acids. Included are high polymers, oligonucleotides, and oligomer-polymer interactions. The equations prescribe simple ways of plotting experimental data to evaluate transition and binding parameters.
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    Biopolymers 10 (1971), S. 2181-2197 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The helix-coil transitions for poly-L-lysine (PL) were investigated by the methods of spectropolarimetry, viscometry and potentiometric titration in 0.2M NaCl at different temperatures as well as in 0.2MNaBr, 1MKCl, and in mixtures of 0.2MNaCl or NaBr with methanol at room temperature. The enthalpy and entropy differences between the helical and coillike states of uncharged PL molecules in 0.2.M NaCl were determined from the potentiometric titration curves. The cooperativity parameters σ for PL in different solvents were determined by two methods (from the sharpness of the transition and from the dependence of the intrinsic viscosity on the helical content in the transition region). In 0.2MNaCl σ has a value of (2.3 ± 0.5) × 10-4 and does not depend on temperature, i.e., the cooperativity of the helix-coil transition, as for PGA, is mainly of an entropy origin (the initiating of the helical region is accompanied by the entropy decrease ΔSi = -12 eu/mole of helical regions). A comparison of the obtained results for PGA and PL with the molecular theories of the helix-coil transitions shows that the role of dipole-dipole interactions of nonneighboring peptide groups is greatly overestimated in these theories, leading to a considerable enthalpy contribution to the free energy of initiating helical regions which is not observed in the experiment.
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    Biopolymers 10 (1971), S. 2029-2037 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The variation of the polarized components of fluorescence of a rodlike particle bearing a fluorescent label upon partial orientation is calculated for some special geometry of the dye macromolecules complexes. Explicit expressions are given for the case where the energy of the molecule in the field depends only on one angle θ, showing that the result is a function of both 〈sin2θ〉 and 〈sin4θ〉. For the case of orientation in an electric field through an anisotropic induced moment, the expressions allow the calculation of this anisotropy of polarizability. The method is applied to the measurement of the polarizability of rodlike fragments of DNA labeled by intercalated molecules of Acridine Orange.
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    Biopolymers 10 (1971), S. 2039-2048 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As the temperature of solid poly(β-benzyl-L-aspartate) (PBLA), (CO.NH.CH.-CH2COOCH2C6H5)n, in the α-helieal form is raised from -150 °C, tlie line width and second moment of the proton magnetic resonance (PMR) signal decrease in stages until the conformational transition to the ω-helix occurs at about 90 °C. A similar temperature dependence of the PMR parameters is observed as the transformed polymer is cooled. Below -100°C (where the lattice is presumed to be rigid), the measured second moments are 9.5 Oe2 and 10.7 Oe2 for the α and ω forms, respectively. Second moments, calculated from the Van Vleck formula for the rigid lattice and also estimated for possible motional cases in which the polymer is taken to be in the ω form, are compared with the PMH data. By combination with the results of X-ray diffraction and infrared spectroscopic measurements, a tentative explanation can be made of the types of motion occurring in PBLA.
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    Biopolymers 10 (1971), S. 2133-2145 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have performed potentiometric titrations of poly-L-lysine. From these data we have calculated the free energy and enthalpy changes for the folding of the random coil to the α-helix in 10% ethanol (-120 and -120 cal/mole) and from the random coil to the β-structure in water (-140 and 870 cal/mole) and in 10% ethanol (-180 and 980 cal mole). Comparison of these values with each other and with values for the coil → α- helix transition in water (-78 and -880 cal/mole) led to the following conclusions. The stabilization by ethanol of ethanol of the α-helix with respect to the coil is that predicted from the known free energy of transfer of the peptide group from water to 10% ethanol. Similar data to explain the enthalpy difference are not available. The thermodynamic functions for the transition from α-helix to β-structure, obtained by subtracting those for the coil → α-helix and coil → β-structure transitions, are explained from a consideration of the structural differences: non bonded interactions of the polypeptide backbone are less favorable in the β-structure than in the α-helix, causing an increase in the energy, while hydrophobic contacts between side chains raise the entropy of the β-structure as compared with the α-helix, so that the free energy difference between the two structures is small, but enthalpy and entropy differences are large. The observation of only small differences in the free energy and enthalpy changes for the transition from coil β-structure upon going from water to 10% ethanol is expected by considering both the free energy of transfer of the peptide group (as for the α-helix) and the free energy and enthalpy of transfer of the apolar part of the side chain involved in hydrophobic bond formation.
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    Biopolymers 10 (1971), S. 2209-2221 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Valine specific transfer RNA (tRNAVal) was isolated from Bacillus stearothermophilus and Escherichia coli by chromatography on benzoylated DEAE-cellulose (BD-cellulose). Likewise isoleucine specific transfer RNA (tRNAIle) was isolated from B. stearothermophilus and from Mycoplasma sp. Kid. The thermal denaturation profiles (melting curves) of the two tRNAVal species in the presence of Mg+ + were nearly identical. However, the Tm for the Kid tRNAIle was about 10°C lower than that for the B. stearothermophilus tRNAIle. A nuclease and tRNA-free aminoacyl-tRNA synthetase (AA-tRNA synthetase) preparation from B. stearothermophilus was able to function efficiently at temperatures up to 80°C in the aminoacylation of all four tRNA species. Determination of the amino acid-acceptor activity of each tRNA species as a function of temperature of the aminoacylation reaction showed in each case a strong correlation between the loss of acceptor activity and the thermal denaturation profile of the tRNA. Evidence is presented that the loss in acceptor activity is most likely due to a change in structure of the tRNA as opposed to denaturation of the enzyme. These results further support the idea that correct secondary and/or tertiary structure must be maintained for tRNA to be active as a substrate for the AA-tRNA synthetase.
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    Biopolymers 10 (1971), S. 2275-2281 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Cotton effects of N-acetoacetyl amino acids and derivatives were examined by a circular dichroism technique. A correlation has been established between the sign of the Cotton effect and the absolute configuration of the asymmetric center. The L derivatives show, in dioxane, negative circular dichroism curves, whereas the D antipodes present positive curves. The effect of solvent and pH and influence of alkylation at the amide nitrogen are also discussed.
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    Biopolymers 10 (1971), S. 2345-2358 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The anisotropy of electrical polarizability of rodlike fragments of DNA has been studied by a number of electro-optical methods: Kerr effect (combined with flow birefringence), light scattering, diehroism, and fluorescence in an electric field. The most sensitive technique (Kerr effect) has been used to study the variation of the polarizability with the nature and concentration of counteroins. DNA fragments constitute a truly rigid polyelectrolyte of known structure. The value obtained can then be quantitatively compared to the predictions of those of the theories of the longitudinal polarizability of rigid polyelectrolytes which are based on true molecular parameters. The comparison emphasizes the role of the counterion-counterion repulsion. Oosawa's theory seems to represent the best approach but fails to explain the differences observed between monovalent and divalent ions.
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    Biopolymers 10 (1971) 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 9 (1970), S. 811-824 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The root-mean-square end-to-end distance has been calculated for a model allowing free rotation about glycoside bonds for the general case of polysaccharides having a disaccharide repeating unit. Numerical estimates are given for several naturally occurring structures based on an idealized pyranose unit in the C1 chair conformation. Extrapolation procedures which make use of the intrinsic viscosity [η] in good solvents to obtain unperturbed dimensions do not represent, data for hyaluronic acid very well, especially at low molecular weights. However, order-of-magnitude estimates suggest that this polymer behaves similarly to other polysaccharides, and probably has stiffer local structure than typical non-ionic synthetic polymers. A double logarithmic plot of the product of [η] and M̄w, the weight-average molecular weight, against the degree of polymerization in the range for M̄w of 104 to 2 × 104 permits a straight-line fit of available data for all the glycosaminoglycans, including heparin and the chondroitin sulfates, as well as sodium carboxymethyl cellulose. This result suggests similarity of short-chain hydrodynamic behavior of these polymers.
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    Biopolymers 9 (1970), S. 875-875 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 9 (1970) 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 9 (1970), S. 865-874 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A common approximation for deriving solutions to the Lamm equation is to neglect diffusion. This paper presents a singular perturbation technique that allows one to estimate the band spreading due to nonzero diffusion coefficient. We illustrate the general mathematical technique by its application to sedimentation when pressure effects are important. Comparison of the approximate solution with accurate numerical solutions shows that the relative errors are of the order of 1% both for concentration and concentration gradient for parameters of chemical interest.
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    Biopolymers 9 (1970), S. 891-896 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Glycogen acquires a negative charge in both alkaline and acidic solutions and can move in an electrical field, its mobility being related to the degree of alkalinity or acidity. There is a slight increase in relative viscosity at both ends of the pH spectrum. These effects and the changes in nuclear magnetic resonance as a function of pH are interpreted.
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  • 86
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The viscosity of bovine liver glutamate dehydrogenase solutions was studied at 10 and 20° C in 0.2.M sodium phosphate buffer at pH 7, in the concentration range 0.1-8 mg/ml. A method for the study of the viscosity of very dilute solutions of associating enzymes is described. It was found that the reduced specific viscosity ηsp/c of glutamate dehydrogenase continuously increases with increasing enzyme concentration, from about 4 ml/g at the lowest concentrations to about 16 ml/g at 8 mg/ml. In the presence of 10-3M GTP and 10-3M NADH the viscosity increase is much smaller and the results can be extrapolated to zero enzyme concentration to yield an intrinsic viscosity [η] = 3.2. The values of ηsp/c in phosphate buffer alone apparently extrapolate to the same value of [η], or to a value close to it. We also observe that, in the presence of toluene ηsp/c increases very much more with enzyme concentration: ηsp/c already equals 16 ml/g at a concentration of 0.75 mg/ml. These observations are in good agreement with the hypothesis that the active oligomer of glutamate dehydrogenase (MW = 312,000) associates with increasing enzyme concentration to form linear rodlike polymers of indefinite length. This association is strongly diminished by the addition of 10-3M GTP, 10-3M NADH. Toluene, on the other hand, promotes reversible association to linear polymers of very high molecular weight. The transverse and axial rotary frictional coefficients of macroscopic bodies, similar to a physical model for the structure of glutamate dehydrogenase recently advanced, were determined. Assuming that the viscosity of the model is equal to that of an ellipsoid of rotation with identical frictional coefficients, we calculate [η] = 3.26 ml/g according to Kuhn and 3.20 ml/g according to Simha, for the glutamate dehydrogenase oligomer, in good agreement with the result derived from the study of enzyme solutions.
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  • 87
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    Biopolymers 9 (1970), S. 911-922 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular monolaycrs of poly(β-benzyl L-aspartate) spread at. an air-water interface have been studied. The results obtained both by direct observations on the monlayer and from examination of collapsed films with polarized infrared spectroscopy and electron diffraction are consistent with the presence of right handed α-helices in the mono-layer when the molecular weight is high. When 1% (v/v) isopropanol is present in the subphase the right-handed helix prevails, provided that the monolayer is first spread on water. Monolayers of low molecular weight polymer appear to form the crossed-β structure. Orientated collapsed films of high molecular weight polymer can be converted to the left-handed α-helical and to the ω-conformation, and the mechanisms are discussed. The surface chemistry of this polymer is compared with that of related polymers and a consistent pattern of behavior emerges.
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  • 88
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    Biopolymers 10 (1971), S. 2537-2553 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The MCD (magnetic circular dichroism) spectra of Ap, ApA, ApApA, poly A, Up, UpU, poly U and double-stranded poly A:U alternating copoly A-U and alternating deoxyribopoly A-T were measured with a Cary 61 spectropolarimeter fitted with a Varian superconducting magnet at a field strength of 50 Kgauss. The MCD spectra of T2 and T5 DNA at various stages of heal denaturation were measured as a function of hyperchromicity of the sample. MCD spectra of the intact and degraded T2 and T5 phages were used to study the degree of alteration of the DNA inside the phages versus the DNA in vitro. The results for the adenine polymers show that the main MCD bands, B2u(271 nm), B1u(252 nm), and E1u(212 nm), show a decrease in specific magnitude as the length of the polymer is increased, reflecting the degree of stacking of the polymer. In contrast, the uridine series of polymers shows little change of the MCD bands, indicating that there is little interaction between the bases regardless of the length of the polymers. The MCD spectra of poly A:U, alternating poly r(A-U): (A-U), and alternating poly d(A-T):(A-T) show significant differences among themselves in the magnitude of the B2u band and when compared with the sum of the spectrum for the poly A plus poly U. This may indicate the selective effect of hydrogen bonding on the B2u band. Alternatively, the difference may be due to the absence of an n → π* transition in the double-stranded polymer. Measurements of denatured T2 and To DNA's show increases in all MCD bands. The T2 DNA internally packed in phage shows an increase of the B2u and E1ubands, the B2u remaining unchanged. The internal T5 DNA shows an increase of the B1u band only. Thus, the internal DNA structure is altered in a manner quite different from a simple denaturation caused by hydrogen bond breaking. Furthermore, different MCD bands indicate that different modes of DNA packing exist for T2 and T5 phages.
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  • 89
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    Biopolymers 10 (1971), S. 2591-2596 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The infrared absorption of poly-L-proline in concentrated aqueous salt solutions was measured in the fundamental region. Of primary interest were the carbonyl absorption of the peptide linkage and the methylene C-H bending absorption of the pyrrolidine ring. These spectral regions each show an additional component in the concentrated salt solutions. Using the position of the absorptions of poly-L-proline I (cis) and II (trans) as models, we conclude that both cis-trans linkages are present in the peptide in salt solutions. Increasing the temperature shifts the equilibrium slightly in favor of cis.
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  • 90
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    Biopolymers 10 (1971), S. 2619-2621 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 91
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    Biopolymers 10 (1971), S. 2635-2638 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 92
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 93
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A simplified scheme for treating the spatial configurations of polynucleotide chains is developed using the rotational isomeric state approximation and statistical methods applicable to linear systems of interacting subunits. As a consequence of geometric constraints imposed by the skeletal structure and of the severity of certain steric interactions, it is possible to represent the repeat unit comprising six skeletal bonds by two virtual bonds of fixed length. The configuration of the polynucleotide chain as a whole may be conveniently described by an alternating succession of these two virtual bonds. Moreover, analysis of steric interactions suggests that bond rotations governing the mutual orientation of a given pair of successive virtual bonds should be sensibly independent of the rotations affecting the mutual orientation of other pairs. The statistical mechanical treatment of configuration-dependent properties is much simplified in consequence of this mutual independence. Mean-square dimensions calculated by giving equal weights to all sterically allowed conformations are much smaller than values determined by Felsenfeld and co-workers. The calculated dimensions are markedly increased, however, by placing certain arbitrary restrictions on the rotations about selected pairs of skeletal bonds. It is thus demonstrated that steric interactions alone are insufficient to account for the spatial characteristics of polynucleotide chains. The dimensions are also found to be sensitive to the conformation of the ribose ring of each nucleotide unit, but, insofar as the influences of steric interactions are concerned, the dimensions do not depend on the heterocyclic base attached to the ribose ring.
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  • 94
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    Biopolymers 11 (1972), S. 119-126 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theory is presented concerning the possible arrangements of protomers in tetrameric molecules. Isoenzymes may exist even in the case of homotetramers if the asymmetry of the identical protomers is detectable. The number of tetrahedral isoenzymes that can be isolated depends on the nature of the intersubunit bonds and on the level of the asymmetry of the protomers. Five isoenzymes can be distinguished only if two different types of protomers form tetrahedral tetramers and the asymmetry of protomers is not detectable with the method used. If the two types of protomers can bind each other by any pairs of binding sets and the asymmetry of both protomer types reaches the level of detection with the method used, we obtain 117 isoenzymes: 15 individual ones, and 51 stereoisomeric pairs.
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  • 95
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    Biopolymers 11 (1972), S. 197-214 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Our previous paper described graphical procedures for evaluating the mode of association in ideal discrete and indefinite cases. This paper concerns the application of such procedures in cases where the non-ideality term BM1 must be considered. Bovine liver L-glutamate dehydrogenase and lysozyme are used as model systems. Several graphical procedures for dealing with cases of 1 - m, 1 - m - n, or indefinite association are developed. The procedure is based on the evaluation of the weight-fraction monomer with-out prior calculation of BM1, using graphical analysis to evaluate the non-ideality term.
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  • 96
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    Biopolymers 11 (1972), S. 271-278 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 97
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    Biopolymers 9 (1970), S. 1017-1028 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Low-angle light scattering results reported previously demonstrated that measurements on high molecular weight native DNA must be made at angles below 30° in order to obtain correct molecular weights. Earlier light-scattering data obtained on denaturated DNA at angles above 30° showed no change in molecular weight upon denaturation, even though other techniques clearly showed that strand separation occurred. This paper reports low-angle measurements on solutions of calf thymus and T7 DNA denatured under acidic conditions. The results demonstrate that a halving of molecular weight consistent with strand separation is detected by light scattering only when low-angle data are used to obtain correct molecular weights for native material. As expected from theoretical considerations, the scattering from denatured DNA is a linear function of sin2(θ/2), where θ is the angle of observation. This result shows that anticipated experimental artifacts have no significant effect on the low-angle measurements and demonstrates that the curvature in the scattering envelope observed for native DNA below 30° is an inherent property of the native molecule.
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  • 98
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics for the cis-trans isomerization of long-chain poly-L-proline has been studied as a function of pressure, temperature, and solvent composition in the acetic acid + n-propanol solvent system. Our complete kinetic curves were fitted by Monte Carlo techniques, and rate constants for nucleation, growth, and termination were estimated. It was found that for the formation of a cis-helix, high pressure, low temperature, and increased acetic acid content of the solvent, lowered the rate of nucleation relative to growth. The inverse seems to be t rue for the formation of a trans-helix. Molecular models suggest that this behavior of the kinetic constants can be due to the exposure of peptide units to solvent in the transition state for trans nucleation, and the burying of peptide units in the transition state for cis nucleation. It is further suggested from our analysis of complete kinetic curves that at least one of the assumptions usually made in the analysis of relaxation kinetics is invalid for poly-L-proline.
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  • 99
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    Biopolymers 9 (1970), S. 1039-1047 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solutions of amylose in ethylenediamine yield a crystalline film complex upon evaporation of solvent. The x-ray analysis indicates the presence of a tetragonal-shaped cell with a symmetry approximating that of space group P212121. The amylose sixfold helix has a diameter of 13.3 Å and a translation period of 8.0Å. Chemical and physical analyses support a complexing ratio of one ethylenediamine molecule to every two glucose units. The structure is nearly identical to any amylose-dimethyl sulfoxide complex previously examined. The square mode of packing arrangement appears to result from complexation between amylose chains. Such complexing indicates a much greater degree of amylose interaction than is observed in amylose complex structures having a hexagonal close-packing arrangement.
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  • 100
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    Biopolymers 9 (1970), S. 1049-1058 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: pH titration measurements of poly- S-carboxymethyl-L-cysteine were undertaken in the aqueous Nacl solution in relation to the β form-random coil transition. The titration curves show a marked molecular weight dependence because of the shortened chain length of materials. Comparison of the optical rotatory dispersion parameter a0 with the titration curve reveals that the titration curve apparently reflects a β structure-random coil transition. The β form of this polymer is assumed to be an intramolecular β form, rather than a β structure stabilized by an intermolecular hydrogen bond, at least in the polymer concentration range considered here. The standard free energy change per amino acid residue for the transition from un-ionized random coil to un-ionized β form is estimated to be about -750 cal/mole residue in the range of 0.005-0.2M NaCl concentration.
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