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  • Chemistry  (75,074)
  • Physics  (5,220)
  • Plate tectonics
  • 2010-2014  (49)
  • 1980-1984  (36,501)
  • 1975-1979  (32,042)
  • 1945-1949  (3,659)
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  • 1
    Unknown
    Amsterdam ; New York : North-Holland Pub. Co
    Keywords: DDC 530.1 ; LC QC20 ; Mathematical physics ; Physics ; Quantum theory ; Relativity (Physics)
    ISBN: 9780444875853
    Language: English
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  • 2
    Publication Date: 2017-04-04
    Description: We re-evaluate the possibility that Earth's rotation contributes to plate tectonics on the basis of the following observations: 1) plates move along a westerly polarized flow that forms an angle relative to the equator close to the revolution plane of the Moon; 2) plate boundaries are asymmetric, being their geographic polarity the first order controlling parameter; unlike recent analysis, the slab dip is confirmed to be steeper along W-directed subduction zones; 3) the global seismicity depends on latitude and correlates with the decadal oscillations of the excess length of day (LOD); 4) the Earth's deceleration supplies energy to plate tectonics comparable to the computed budget dissipated by the deformation processes; 5) the Gutenberg–Richter law supports that the whole lithosphere is a self-organized system in critical state, i.e., a force is acting contemporaneously on all the plates and distributes the energy over the whole lithospheric shell, a condition that can be satisfied by a force acting at the astronomical scale. Assuming an ultra-low viscosity layer in the upper asthenosphere, the horizontal component of the tidal oscillation and torque would be able to slowly shift the lithosphere relative to the mantle.
    Description: Hungarian Scientific Research Fund OTKA in the framework of project K 60394
    Description: Published
    Description: 60-73
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: JCR Journal
    Description: reserved
    Keywords: Plate tectonics ; Earth's rotation ; Tidal despinning ; Earth's energy budget ; 04. Solid Earth::04.07. Tectonophysics::04.07.02. Geodynamics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 3
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    Accademia di Scienze Fisiche e Matematiche di Napoli
    Publication Date: 2017-04-04
    Description: This paper aims to trace the documentary history of the Royal Collection of Physics Apparatus,currently housed in the Physics Museum at the Federico II University of Naples...
    Description: Published
    Description: 47 - 59
    Description: 3.10. Storia ed archeologia applicate alle Scienze della Terra
    Description: N/A or not JCR
    Description: reserved
    Keywords: History of Science ; Physics ; Scientific Collection ; Naples ; 05. General::05.03. Educational, History of Science, Public Issues::05.03.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 4
    Publication Date: 2017-04-03
    Description: (extended abstract)
    Description: INGV, Regione Sicilia, Ministero Sviluppo Economico
    Description: Published
    Description: Ettore Majorana Foundation and Centre for Scientific Culture, Erice, Sicily
    Description: 5.9. Formazione e informazione
    Description: open
    Keywords: Inertia ; Physics ; Fluid Dynamics ; 05. General::05.03. Educational, History of Science, Public Issues::05.03.99. General or miscellaneous ; 05. General::05.05. Mathematical geophysics::05.05.99. General or miscellaneous ; 05. General::05.09. Miscellaneous::05.09.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: Extended abstract
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  • 5
    Publication Date: 2017-04-03
    Description: In this paper, we analyse the distributions of number of events (N) and seismic energy (E) on the Earth's surface and along its radius as obtained from the global declustered catalogue of large independent events (M≥7.0), dissipating about 95% of the Earth's elastic budget. The latitude distribution of the seismic event density is almost symmetric with respect to the equator and the seismic energy flux distribution is bimodal; both have their medians near the equator so that they are equally distributed in the two hemispheres. This symmetry with respect to the equator suggests that the Earth's rotational dynamics contributes to modulate the long-term tectonic processes. The distributions of number and energy of earthquakes versus depth are not uniform aswell: 76% of the total earthquakes dissipates about 60% of the total energy in the first ~50 km; only 6% of events dissipates about 20% of the total amount of energy in a narrow depth interval, at the lower boundary of the upper mantle (550–680 km). Therefore, only the remaining 20% of energy is released along most of the depth extent of subduction zones (50–550 km). Since the energetic release along slabs is a minor fraction of the total seismic budget, the role of the slab pull appears as ancillary, if any, in driving plate tectonics. Moreover the concentration of seismic release in the not yet subducted lithosphere suggests that the force moving the plates acts on the uppermost lithosphere and contemporaneously all over the Earth's outer shell, again supporting a rotational/tidal modulation.
    Description: Published
    Description: 80-86
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: JCR Journal
    Description: restricted
    Keywords: Global seismicity ; Declustered catalogue ; Earthquake energy distribution ; Plate tectonics ; 04. Solid Earth::04.06. Seismology::04.06.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 6
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    Verlag für Geowissenschaften, Berlin
    Publication Date: 2017-04-04
    Description: In this paper the theory of the plate tectonics is interpreted as a Tychonic conception. The expanding Earth is the more complete description of the geologic reality.
    Description: The Danish astronomer Tycho Brahe (1546–1601) developed a model of the universe – the Tychonic system – by combining the Ptolemaic system with the Copernican system. In the Tychonic (geocentric) system the Moon and the Sun were considered to revolve around the Earth, while the planets (Mercury, Venus, Mars, Jupiter and Saturn) revolve around the Sun. In this paper the theory of the plate tectonics is interpreted as a Tychonic conception because – making several compromises – fixism and mobilism are mixed in a unique pattern, in which the compression and the extension are unified in a compressional interpretation (see the coexistence of trenches and orogenic chains on the active continental margins), while, conversely, the fold-belts and the mid-oceanic ridges are separated into two different geodynamic domains. For all these cases, the extensional description could be more appropriate.
    Description: INGV - Roma1
    Description: Published
    Description: 19-34
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: N/A or not JCR
    Description: restricted
    Keywords: Expanding Earth ; Plate tectonics ; Global geodynamics ; Paradoxes in Earth Sciences ; 04. Solid Earth::04.01. Earth Interior::04.01.99. General or miscellaneous ; 04. Solid Earth::04.01. Earth Interior::04.01.02. Geological and geophysical evidences of deep processes ; 04. Solid Earth::04.04. Geology::04.04.99. General or miscellaneous ; 04. Solid Earth::04.07. Tectonophysics::04.07.02. Geodynamics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 7
    Publication Date: 2021-05-19
    Description: Daily topical application of the aqueous ethanolic extract of the marine sea grass, Thalassia testudinum, on mice skin exposed to UVB radiation resulted in a dose dependent recovery of the skin macroscopic alterations over a 6-day period. Maximal effect (90%) occurred at a dose of 240 μg/cm2, with no additional effects at higher doses. Bioassay-guided fractionation of the plant extract resulted in the isolation of thalassiolin B (1). Topical application of 1 (240 μg/cm2) markedly reduces skin UVB-induced damage. In addition, thalassiolin B scavenged 2,2-diphenyl-2-picrylhydrazyl radical with an EC50=100 μg/ml. These results suggest that thalassiolin B is responsible for the skin regenerating effects of the crude extract of T. testudinum
    Description: Published
    Description: Flavonoids, Thalassiolin B, DPPH scavenged, antioxidant activity, Skin regenerating activity, Thalassia testudinum
    Keywords: Chemistry ; Pharmacology ; Chemistry ; Pharmacology
    Repository Name: AquaDocs
    Type: Journal Contribution
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  • 8
    Publication Date: 2021-05-19
    Description: Bioguided fractionation of Agelas cerebrum crude extract resulted in isolation of four bromopyrrole and four bromopyrrole aminoimidazole alkaloids, identified as 5-bromopyrrole-2-carboxylic acid (1), 4-bromopyrrole-2-carboxylic acid (2), 3,4-bromopyrrole-2-carboxylic acid (3), 4,5-bromopyrrole-2-carboxylic acid (4), oroidin (5), bromoageliferin (6), dibromoageliferin (7) and dibromosceptrin (8) on the basis of spectroscopic data analyses (UV, IR, HRMS, 1D and 2D NMR) and comparison with literature data. This is the first report of compounds 2 and 3 in a marine sponge belonging to the Agelas genus and the first evidence of the presence of 1 from a natural source.
    Description: Published
    Description: Agelas cerebrum, bromopyrrole alkaloids, antitumoral, antiprotozoal activity
    Keywords: Chemistry ; Alkaloids ; Sponges ; Alkaloids ; Sponges ; Chemistry
    Repository Name: AquaDocs
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  • 9
    Publication Date: 2021-05-19
    Description: La velocidad de descomposición de tres fenólicos, el p-hidroxibenzoico, el protocatecúico y el gálico, los cuales se diferencian en el número de grupos OH, fue investigada en el suelo. Con el aumento de grupos OH aumenta también la velocidad de descomposición microbial. El ácido gálico se descompone más rápido que el protocatecúico y este a su vez más rápido que el phidroxibenzoico.
    Description: The rate of decomposition of the three phenolics, p-hydroxybenzoic acid, protocatechuic acid and gallic acid, whose difference is the amount of OH-groups, was investigated in the soil. With the increase in OH-groups increases the rate of microbial decomposition. Gallic acid decomposes faster than protocatecuic acid and this again faster than p-hydroxybenzoic acid.
    Description: Published
    Keywords: Chemical decomposition ; OH Groups ; Microbes ; Phenols ; Chemistry ; Phenols ; Chemistry
    Repository Name: AquaDocs
    Type: Journal Contribution
    Format: pp.141-143
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  • 10
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-25
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 1999
    Description: Changes in morphology of the Marquesas Fracture Zone are correlated with small changes in Pacific-Farallon relative motion. The simple flexural signal of a locked fracture zone may be obscured by tectonic effects, and there is no evidence for the release of shear stress on the fracture zone by vertical slip after leaving the active transform. One such small change in plate motion is documented in the South ern Austral Island region of the South Pacific. A twelve degree clock wise change in Pacific-Farallon relative motion occurred around fifty million years ago. This Eocene change in spreading direction and rate is locally constrained with observations of magnetic anomalies and spreading fabric orientation. At the southeastern end of the Cook-Austral Island chain, multiple episodes of volcanism have left a diverse population of seamounts. Volume estimates from geophysical data and modeling show that one-half to two-thirds of the volcanic material is over thirty million years old, while the remainder is less than five million years old. Seismic and bathymetric data imply the presence of abyssal basalt flows in the flexural moat of the Austral Islands, probably associated with Austral Islands volcanism, which may contribute a significant amount of material to the archipelagic apron.
    Description: The research presented in Chapter 2 was supported by National Science Founda tion grants OCE-9012949 and OCE-9012529. Chapters 3, 4 and 5 were supported by National Science Foundation grant OCE-9415930. A National Science Foundation graduate fellowship supported my first three years of graduate study.
    Keywords: Structural geology ; Plate tectonics ; Volcanism ; Maurice Ewing (Ship) Cruise EW9109 ; Maurice Ewing (Ship) Cruise EW9602 ; Roger Revelle (Ship) Cruise KIWI03
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
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  • 11
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-25
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution December 1996
    Description: Two-thirds of the surface of the Earth is created at mid-ocean ridges where magmas rise from the mantle and cool to form the oceanic crust. The objective of this Thesis is to examine the influence of magma supply and eruptive processes on axial morphology, crustal construction, and the properties of crustal magma chambers at intermediate and fast spreading ridges. Variations in magma supply on time scales of ~100 Kyr generate along-axis changes in crustal thickness and temperature. Magma sill properties and hydrothermal activity are closely linked to spreading events which occur on much shorter time scales (ca. 10-100 yr) than the longer-term variations in magma supply reflected in along-axis changes in ridge morphology. The seismically constrained depths of ridge crest magma sills (〉1-2 km) are considerably deeper than the level of neutral buoyancy (100-400 m). The apparent inverse relationship between magma sill depth and spreading rate suggests that a thermally controlled permeability boundary, such as the solidus horizon, controls the depth at which magma ponds beneath mid-ocean ridges. Recent thermo-mechanical models predict that, at intermediate spreading rates, rift valley and magma sill formation are sensitive to small changes in crustal thickness and mantle temperature. Analysis of gravity at an intermediate spreading ridge shows that small differences in crustal thickness (300-700 m) and mantle temperature (10-15°C) are indeed sufficient to produce major changes in lithospheric strength and axial morphology. A stochastic model for the emplacement of dikes and lava flows with a bimodal distribution of lava flows is required to satisfy geological and geophysical constraints on the construction of the extrusive section. Most dikes are intruded within a narrow zone at the ridge axis. Short flows build up approximately half the extrusive volume. Occasional flows that pond at a considerable distance off-axis build up the remainder of the extrusive section. This Thesis underlines the importance of eruption dynamics in the emplacement of the uppermost volcanic layer of the crust and of the crustal thermal structure in controlling local variations in magma sill depth and ridge morphology.
    Keywords: Mid-ocean ridges ; Plumes ; Structural geology ; Plate tectonics ; Submarine geology
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
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  • 12
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    American Geophysical Union
    Publication Date: 2022-05-25
    Description: Author Posting. © American Geophysical Union, 2007. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Geochemistry Geophysics Geosystems 8 (2007): Q08012, doi:10.1029/2007GC001597.
    Description: Several models have been proposed to relate slab geometry to parameters such as plate velocity or plate age. However, studies on the observed relationships between slab geometry and a wide range of subduction parameters show that there is not a simple global relationship between slab geometry and any one of these other subduction parameters for all subduction zones. Numerical and laboratory models of subduction provide a method to explore the relative importance of different physical processes in determining subduction dynamics. Employing 2-D numerical models with a viscosity structure constrained by laboratory experiments for the deformation of olivine, we show that the observed range in slab dip and the observed trends between slab dip and convergence velocity, subducting plate age, and subduction duration can be reproduced without trench motion (i.e., slab roll-back) for locations away from slab edges. Successful models include a stiff slab that is 100–1000 times more viscous than previous estimates from models of plate bending, the geoid, and global plate motions. We find that slab dip in the upper mantle depends primarily on slab strength and plate boundary coupling, with a small dependence on subducting plate age. Once the slab sinks into the lower mantle the primary processes controlling slab evolution are (1) the ability of the stiff slab to transmit stresses up dip, (2) resistance to slab descent into the higher-viscosity lower mantle, and (3) subduction-induced flow in the mantle-wedge corner.
    Description: This research was partially supported by NSF award EAR0125919.
    Keywords: Subduction ; Rheology ; Mantle dynamics ; Plate tectonics ; Slab morphology
    Repository Name: Woods Hole Open Access Server
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  • 13
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-25
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution May 1998
    Description: Planktonic protozoan grazers have the potential to significantly affect the chemistry of particle-associated trace metals. This is due both to the importance of protists as consumers of bacterial-sized particles, and to the unique low-pH, enzyme-rich microenvironment of the grazer food vacuole. This thesis examines the role of protozoan grazers in the marine geochemistry of strongly hydrolyzed, particle-reactive trace metals, in particular Th and Fe. A series of tracer experiments was carried out in model systems in order to determine the effect of grazer-mediated transformations on the chemical speciation and partitioning of radioisotopes C9Fe, 234Th, 51Cr) associated with prey cells. Results indicate that protozoan grazers are equally able to mobilize intracellular and extracellular trace metals. In some cases, protozoan regeneration of trace metals appears to lead to the formation of metal-organic complexes. Protozoan grazing may generate colloidal material that can scavenge trace metals and, via aggregation, lead to an increase in the metal/organic carbon ratio of aggregated particles. Model system experiments were also conducted in order to determine the effect of grazers on mineral phases, specifically colloidal iron oxide (ferrihydrite). Several independent techniques were employed, including size fractionation ors9Fe-labeled colloids, competitive ligand exchange, and iron-limited diatoms as "probes" for bioavailable Fe. Experimental evidence strongly suggests that protozoan grazing can affect the surface chemistry and increase the dissolution rate of iron oxide phases through phagotrophic ingestion. In further work on protozoan-mediated dissolution of colloidal Fe oxides, a novel tracer technique was developed based on the synthesis of colloidal ferrihydrite impregnated with 133Ba as an inert tracer. This technique was shown to be a sensitive, quantitative indicator for the extent of ferrihydrite dissolution/alteration by a variety of mechanisms, including photochemical reduction and ligand-mediated dissolution. In field experiments using this technique, grazing by naturally occuring protistan assemblages was shown to significantly enhance the dissolution rate of colloidal ferrihydrite over that in non-grazing controls. Laboratory and field results indicate that, when integrated temporally over the entire euphotic zone, protozoan grazing may equal or exceed photoreduction as a pathway for the dissolution of iron oxides.
    Description: This work was financially supported by a Department of Defense ONR-NDSEG Graduate Fellowship, Office ofNaval Research AASERT Award (N00014-94-1-0711), and the National Science Foundation EGB Program (OCE-9523910).
    Keywords: Protozoa ; Water chemistry ; Trace elements in water ; Marine zooplankton ; Chemistry
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
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  • 14
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-25
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution September 1996
    Description: We analyze bathymetric and gravity anomalies at five plume-ridge systems to constrain crustal and mantle density structure at these prominent oceanic features. Numerical models are then used to explore the physical mechanisms controlling plume-ridge interaction and to place theoretical constraints on the temperature anomalies, dimensions, and fluxes of the Icelandic and Galapagos plumes. In Chapter 1 we analyze bathymetric and gravity anomalies along the hotspot-influenced Galapagos Spreading Center. We find that the Galapagos plume generates along-axis bathymetric and mantle-Bouguer gravity anomalies (MBA) that extend 〉500 km east and west of the Galapagos Islands. The along-axis MBA becomes increasingly negative towards the plume center, reaching a minimum of ~-90 mGal near 91°W, and axial topography shallows by ~1.1 km toward the plume. These variations in MBA and bathymetry are attributed to the combined effects of crustal thickening and anomalously low mantle densities, both of which are due to a mantle temperature anomaly imposed beneath the ridge by the Galapagos plume. Passive mantle flow models predict a temperature anomaly of 50±25°C is sufficient to produce the 2-4 km excess crust required to explain the along-axis anomalies. 70-75% of the along-axis bathymetric and MBA variations are estimated to arise from the crust with the remaining 25-30% generated by the anomalously hot, thus low-density mantle. Along Cocos-plate isochrons, bathymetric and MBA variations increase with increasing isochron age, suggesting the subaxial mantle temperature anomaly was greater in the past when the plume was closer, to the ridge axis. In addition to the Galapagos plume-ridge system, in Chapter 2 we examine alongisochron bathymetric and MBA variations at four other plume-ridge systems associated with the Iceland, Azores, Easter and Tristan hotspots. We show that residual bathymetry (up to 4.7 km) and mantle-Bouguer gravity anomalies (up to -340 mGal) are greatest at on-axis plumes and decreases with increasing ridge-hotspot separation distance, until becoming insignificant at a plume-ridge separation of ~500 km. Along-isochron widths of bathymetric anomalies (up to 2700 km) decrease with increasing paleo-spreading rate, reflecting the extent to which plume material flows along-axis before being swept away by the spreading lithosphere. Scaling arguments suggest an average ridgeward plume flux of -2.2x106 km/my. Assuming that the amplitudes of the MBA and bathymetric anomalies reflect crustal thickness and mantle density variations, passive mantle flow models predict maximum subaxial mantle temperature anomalies to be 150-225°C for ridge-center plumes, which decrease as the ridges migrate away from the plumes. The dynamics of mantle flow and melting at ridge-centered plumes are investigated in Chapters 3 using three-dimensional, variable-viscosity, numerical models. Three buoyancy sources are examined: temperature, melt depletion, and melt retention. The width W to which a plume spreads along a ridge axis depends on plume volume flux Q, full spreading rate U, buoyancy number B = (QΔρg)/(48η0U2), and ambient/plume viscosity contrast ϒ according to W=2.37(Q/U)l/2(Bϒ)0.04. Thermal buoyancy is first order in controlling along-axis plume spreading while latent heat loss due to melting, and depletion and retention buoyancy forces contribute second order effects. Two end-member models of the Iceland-Mid-Atlantic Ridge (MAR) system are examined. The first endmember model has a broad plume source of radius 300 km, temperature anomaly of 75°C, and volume flux of 1.2xl07 km3/my. The second model has a narrower plume source of radius 60 km, temperature anomaly of l70°C, and flux of 2.1 x106 km3/my. The first model predicts successfully the observed crustal thickness, topographic, and MBA variations along the MAR, but the second model requires substantial along-axis melt transport in order to explain the observed along-axis variations in crustal thickness, bathymetry, and gravity. We favor this second model because it predicts a mantle P-wave velocity reduction in the plume of ~2% as consistent with recent seismic observations beneath Iceland. Finally in Chapter 4 we use three-dimensional numerical models to investigate the interaction of plumes and migrating midocean ridges. Scaling laws of axial plume spreading width Ware derived first for stationary ridges and off-axis plumes, which yield results consistent with those obtained from independent studies of Ribe [1996]. Wand the maximum plume-ridge interaction distance Xmax again scale with (Q/U)l/2 as in the case of ridge-centered plumes and increase with ϒ and buoyancy number. In the case of a migrating ridge, Xmax is reduced when a ridge migrates toward the plume due to excess drag of the faster-moving leading plate, and enhanced when a ridge migrates away from the plume due to reduced drag of the slower-moving trailing plate. Thermal erosion of the lithospheric boundary layer by the previously ridge-centered plume further enhances Wand Xmax but to a degree that is secondary to the differential migration rates of the two plates. Model predictions are compared with observed along-isochron bathymetric and MBA variations at the Galapagos plume-ridge system. The anomaly amplitudes and widths, as well as the increase in anomaly amplitude with age are predicted with a plume source temperature anomaly of 80-120°C, radius of 80-100 km, and volume flux of 4.5x106 km3/m.y. Our numerical models also predict crustal production rates of the Galapagos Islands consistent with those estimated independently using the observed island topography. Predictions of the geochemical signature of the plume along the present-day ridge suggest that mixing between the plume and ambient mantle sources is unlikely to occur in the asthenosphere or shallow crust, but most likely deeper in the mantle possibly by entrainment of ambient mantle as the plume ascends through the depleted portion of the mantle from its deep source reservoir.
    Keywords: Mid-ocean ridges ; Plumes ; Structural geology ; Plate tectonics ; Submarine geology ; Mantle
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
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  • 15
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-25
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution March 1997
    Description: The formation of new oceanic crust is the result of a complex geodynamic system in which mantle rises beneath spreading centers and undergoes decompression melting. The melt segregates from the matrix and is focused to the rise axis, where it is eventually intruded and/or erupted to form the oceanic crust. This thesis combines surface observations with laboratory studies and geodynamic modeling to study this crustal-production system. Quantitative modeling of the crustal and mantle contributions to the axial gravity and topography observed at the East Pacific Rise shows that the retained melt fraction in the mantle is small (〈3%) and is focused into a narrow column extending up to 70 km beneath the ridge axis. Consistent with geochemical constraints, the extraction of melt from the mantle therefore appears to be efficiently focus melt toward the ridge axis. A combination of laboratory and numerical studies are used to constrain the pattern of mantle flow beneath highly-segmented ridges. Even when the buoyant component of mantle flow is constrained to be two-dimensional, laboratory studies show that a segmented ridge will drive three-dimensional mantle upwelling. However, using reasonable mantle parameters in numerical models, it is difficult to induce large-amplitude three-dimensional mantle upwelling at the relatively short wavelengths of individual segments (~50 km). Instead, a simple model of three-dimensional melt migration shows that the observed segment-scale variations in crustal thickness can be explained by focusing of melt as it upwells through a more two-dimensional mantle flow field. At the Reykjanes Ridge, the melt appears to accumulate in small crustal magma chambers, before erupting in small batches to form numerous overlapping hummocky lava flows and small volcanoes. This suggests that crustal accretion, particularly at slow-spreading centers, may be a highly discontinuous process. Long-wavelength variations in crustal accretion may be dominated by variations in mantle upwelling while short-wavelength, segment-scale variations are more likely controlled by a complex three-dimensional processes of melt extraction and magma eruption.
    Description: During my first three years in the Joint Program, I was supported by an National Science Foundation Graduate Student Fellowship. Other support has been derived from National Science Foundation grants OCE-9296017, OCE-9224738, OCE-9215544, and EAR grant 93-07400.
    Keywords: Mid-ocean ridges ; Plumes ; Structural geology ; Plate tectonics ; Submarine geology ; Mantle
    Repository Name: Woods Hole Open Access Server
    Type: Thesis
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  • 16
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-25
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution February 1995
    Description: The global mid-ocean ridge system is one of the most striking geological features on the surface of the Earth. In this system, the East Pacific Rise (EPR) is the fastest spreading ridge and is thus considered as the most active magmatically among the plate boundaries. In January and February of 1988, an extensive survey by the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution was conducted along the EPR between 9°05' and 9°55'N to study the crustal structure of the axial region. This thesis, the result of that cruise, comprises four main topics: (1) characterization of normal faulting from Sea Beam bathymetric data, (2) application of mechanical models to explore the hypothesis that buoyancy arising from crustal magma chambers and gravitational spreading of the upper crust are the principal processes leading to the initiation and development of normal faults, (3) investigation of seafloor magnetization anomalies to constrain upper crustal structure, and (4) analysis of gravity anomalies to examine possible correlations between observed variations in seafloor manifestations of volcanism and deformation and underlying structure. Thus, each topic focuses on different levels of the mid-ocean ridge. Together with the results of seismic and other observations, the findings are woven into a better understanding of the tectonic processes and structure of fastspreading mid-ocean ridges. First, to understand the characteristics of normal faults at fast-spreading ridges, we utilized swaths of Sea Beam bathymetry and estimated the distribution and geometry of normal fault zones using the slope of the seafloor as the criterion for a faulted surface. In our survey area, nonnal fault activity begins 2-8 km off-axis and continues at least to 30-40 km from the axis, as indicated by an increase in the total and average throws of normal fault zones versus distance from the axis. There appears to be no significant difference in the plan-view area of inward- and outward-facing nonnal fault zones. The distance from the rise axis to the nearest large-offset fault zone (throw 〉 20 m) on either side of the axis is approximately symmetric to the north of 9°23'N, but the midpoint between nearest largeoffset fault zones is offset 2-3 km to the west of the bathymetric axis to the south of 9°23'N. The continued growth of nonnal fault zones suggests that significant extensional stress persists to greater distances from the axis than previously thought and that the rise axis possesses a finite strength. The argument that the rise axis has finite strength is consistent with recent evidence for solidified axial dikes along magmatically active portions of the EPR from near-bottom seismic refraction experiments, which suggests that, while eruption of magma at the rise axis weakens the axis, the persistence of such weak zones is short-lived and the emplacement zones at any given time are localized along the axis. We examined how the presence of a low-density, low-strength magma chamber within the crust and gravitational spreading of a mechanically strong upper crust over an underlying substrate contribute to the fonnation of faults at a fast spreading mid-ocean ridge by comparing the predicted stress field with the observed pattern of normal fault zones. We employed boundary element methods to incorporate buoyancy and gravitational spreading as body forces in an elastic medium, and we detennined stress and strain fields for a variety of rise axis conditions and a range of possible sets of material properties for different parts of the mid-ocean ridge. Our results show that the strength of the rise axis is one of the most crucial factors governing the near-axis stress field. If the rise axis is mechanically weak, the maximum extensional stress from buoyancy occurs at shallow depth off the rise axis. A weak rise axis may result from recent magmatism such as the intrusion of dikes into the upper crust. On the other hand, if the rise axis is mechanically strong, which may result after solidification and cooling of the dike zone, the maximum surface extensional stress occurs on the rise axis. However, the reduction in size of a magma chamber that would accompany cessation of dike injection would lead to less buoyancy and thus a lower likelihood of stress levels sufficient for faulting. For a given set of material strengths and a given magnitude of buoyancy force, the flexural rigidity of the upper crust plays an important role in detennining if a zone of extension will develop off axis and, if so, the position and horizontal extent of that zone. A thin or mechanically weak upper crust is more likely to develop a zone of extension than one that is thick or mechanically strong. The stress field resulting from gravitational spreading is similarly affected by the strength of the rise axis. While buoyancy can explain a consistent distance at which normal faults initiate off-axis, gravitational spreading can account for continued activity on normal faults to a greater distance from the axis than can buoyancy. The existence of a magma lens can play an important role in reducing the magnitude of the stress field for a weak rise axis, as the crust above the magma lens can slide and thus relieve the thickness-averaged extensional stress. Next, we inverted surface ship measurements of the scalar magnetic field along the EPR between 9°10' and 9°50'N. We examined whether the axial magnetization high, which increases in amplitude to the south in our area, can best be explained by variations in the thickness or in the magnetization intensity of the source layer. The variation in axial magnetization is too large to be explained solely by the variations in the depth to the top of the axial magma chamber indicated by reflection seismology. For a magnetic source layer that is 500 or 750 m thick, the observed along-axis variations in FeO and Ti02 explain only 36 and 60%, respectively, of the total variance of axial magnetization anomalies. Therefore, a combination of variations in magnetic layer thickness and in intensity of magnetization (by variations in the FeO and Ti02 contents of the source rock or by other mechanisms) is needed to explain the along-axis variation of axial magnetization. In addition to the increase in amplitude to the south, the axial magnetization high exhibits at least three marked changes in magnitude and offsets in its along-axis linearity ('magnetic devals') (at 9°25', 9°37', and 9°45'N) which appear to be related to boundaries or offsets between the segments of the axial summit caldera (ASC). Because the amplitudes of the axial magnetization anomalies are highest at the midpoints of the ASC segments, we speculate that midpoints of the ASC segments are the loci of more frequent lava eruptions, and the seafloor basalts at the midpoints are thus younger and more magnetic, than at the segment ends. The magnetization shows distinct short-wavelength (~ 5 km) banding to the north of 9°25'N over a region that does not appear to have been affected by an overlapping spreading center. Among the possible explanations for these off-axis magnetization anomalies are short geomagnetic reversal events within the Brunhes epoch, variations in the paleointensity of the Earth's field, variations in the magnetization intensity of the source rock due to variability in the magmatic supply, and variations in the degree of hydrothermal alteration at the rise axis. On the basis of comparisons of forward models and observations, short geomagnetic reversal events appear to be the most likely explanation of these anomalies. The analysis of sea-surface gravity field measurements shows an axial residual mantle Bouguer gravity anomaly too large to be explained by the anomalous temperature of the mantle or by changes in the thickness of the crust. The broad axial residual gravity low is interpreted as a signal arising largely from the upper mantle, presumably by presence of partial melt along the rise axis. A northward increase in the width of the low implies a greater melt fraction in the region to the north than to the south, especially on the Pacific plate side. The residual gravity anomaly also shows several short-wavelength local lows along the axis (e.g., 9°21', 9°32', and 9°42'N) which correlate with along-axis variations in axial magnetization and tomographic images of mid-crustal seismic velocities. Along axis the local lows have an amplitude of 1.5-3 mGal and appear at a nearly regular spacing (10- 15 km). Across the axis, however, the local lows show a greater variation (3-5 mGal), suggesting that there is an additional gravity anomaly signal arising from a low-density structure that is approximately continuous along the axis. The anomalous masses producing the local lows are interpreted as zones of relatively high melt concentration, formed within the crust by recent replenishment of magma from the upper mantle, that are surrounded by a region of lesser melt concentration corresponding to the low-velocity volume imaged by seismic tomography. If the zone of high melt concentration are modeled as circular rods of radius 1 km, along-axis length 10 km, and center of mass 2.25 km below the seafloor, density contrasts of 200-350 kg/m3 are needed to match the observed anomalies. For larger anomalous mass volumes, the density contrasts would be lower. The findings of this study support the hypothesis that the axis of the EPR can be divided into segments 10-15 km in length, with each segment defmed by the locus and timing of most recent emplacement of magma in the axial crust. The segments in the study area appear to be in different phases of a magmatic cycle, but the period of such a magmatic cycle is not known. By this view, the discrete emplacement of magma bodies gives rise to along-axis variations in crustal structure manifested as short-wavelength residual gravity anomalies and magnetic devals. Another consequence of a rise axis at which magma is emplaced at discrete locations is that the mechanical strength of the axial upper crust varies with position along the axis and over time. During active magmatism, the rise axis acts as a weak zone and the buoyancy of the axial magma chamber and surrounding low-velocity volume can lead to initiation of off-axis normal faulting. However, for a long segment of the rise bounded by transform faults, the axis will have sections with a solidified rucial injection zone as well as sections undergoing active magmatism, and thus the rise overall may appear to have finite strength. If such a finitestrength ridge axis is subject to significant extensional stress as a result of gravitational spreading, mantle convective tractions, or differential cooling, then continued normal fault activity would extend over a broad region to distances of at least several tens of kilometers from the spreading axis.
    Description: The work in this thesis was supported by the National Science Foundation under grants OCE-8615797, OCE-8615892, and OCE-9000177.
    Keywords: Geology ; Plate tectonics ; Faults ; Thomas Washington (Ship) Cruise
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  • 17
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-25
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution December 1996
    Description: The objective of this Thesis was to interpret the structural development of slowspreading ridge segments by: 1) delineating the nature, magnitude, and relative importance of primary tectonic and volcanic processes that control crustal morphology, 2) investigating the spatial and temporal variability of these processes, and 3) examining how rheological variations in the lithosphere control its structural configuration. To that end, this Thesis provides detailed documentation of faults and volcanoes (seamounts) at the Mid-Atlantic Ridge from 25°25'N to 27°10'N and extending from zero-age crust at the ridge axis to -29 Ma crust on the ridge flank. This information was used to analyze the evolution of ocean crust from initial formation in the rift valley to degradation by aging processes on the ridge flank. Accumulation of sediments affects the seafloor morphological expression of ocean crustal structure, and sediment thicknesses were also mapped to facilitate study of the morphological record of crustal accretion and tectonism. In addition, deformation conditions in the lithosphere were analyzed by study of microstructure and geothermometry of abyssal peridotite mylonites recovered from fault zones at slow-spreading ridges.
    Keywords: Sea-floor spreading ; Structural geology ; Plate tectonics ; Geodynamics ; Geology ; Maurice Ewing (Ship) Cruise EW9208 ; Knorr (Ship : 1970-) Cruise KN138
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  • 18
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    Giornale di Astronomia
    Publication Date: 2017-04-04
    Description: Nel corso della storia delle Scienze della Terra, nessun altro cambiamento di paradigma fu così drammatico come il passaggio dal fissismo al mobilismo. Finanche un analogo del famoso processo a Galileo Galilei (ma più moderato e senza esiti che limitassero la libertà personale di nessuno) fu tenuto con il congresso del 1926 (atti editi da van der Gracht nel 1928) in cui una seppur velata condanna fu impartita al contumace Alfred Wegener impegnato nelle sue campagne geofisiche nell’Artico. Il mobilismo continuò a farsi strada fino a prevalere, ma alcuni compromessi ed eredità del passato furono impiantati nella sua formulazione iniziale sotto l’influenza della vecchia comunità accademica.
    Description: Published
    Description: 4-10
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: N/A or not JCR
    Description: open
    Keywords: Paradigmi ; Plate tectonics ; Expanding Earth ; History of Geosciences ; Geodynamics ; Paradoxes ; 04. Solid Earth::04.07. Tectonophysics::04.07.02. Geodynamics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 19
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-26
    Description: Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution May 1988
    Description: Heat flow, tectonic subsidence and crustal thickness distributions in the Ligurian Basin are best explained by asymmetric lithospheric thinning mechanisms. Over 150 heat flow measurements are made on several transects between Nice, France and Calvi, Corsica on continental slope and rise settings. Thermal gradient determinations are improved using an optimization technique. Piston core data and surface sediment 3.5 kHz reflectivity patterns help constrain thermal conductivity obtained from over 100 in situ stations. Plio-Quaternary stratigraphy is revised using new seismic reflection profiles: a boundary fault system associated with postrift margin uplift, a Pleistocene-age Var Fan construction, and recent diapirism of Messinian salt are indicated. After assessing local thermal disturbances (mass-wasting, microtopography, and salt refraction), positive heat flow corrections are made for multi-lithologic sedimentation histories and glacial paleotemperatures. Using boundary-layer cooling models, equilibrium heat flow estimates support geologic evidence for Oligocene and early Miocene rifting. Heat flow maxima correlate well with two "oceanic" sub-basins, suggesting that the southeastern trough near Corsica is ~5 Myr younger, consistent with the southeastern progression of volcanism and back arc rifting in the Western Mediterranean. Tectonic subsidence-crustal thickness trends indicate lithospheric stretching, with heat flow supporting asymmetric sub-crustal lithospheric thinning during the conjugate margin formation.
    Keywords: Ocean temperature ; Plate tectonics
    Repository Name: Woods Hole Open Access Server
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  • 20
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    Massachusetts Institute of Technology and Woods Hole Oceanographic Institution
    Publication Date: 2022-05-26
    Description: Submitted in partial fulfillment of the requirements for the degree of Master of Science at the Massachusetts Institute of Technology and the Woods Hole Oceanographic Institution May 1988
    Description: The age of the Nazca plate where it enters the Peru and northern Chile trenches varies from 30 Ma in the north to 45 Ma in the south as its dip beneath the South American continent steepens from 13° to 30°. If the elastic thickness Te of oceanic lithosphere depends only on its age, and therefore thermal state, we would expect that Te determined from fitting the flexure of the lithosphere over the outer rise as revealed in the depth and geoid anomalies would increase from the Peru Trench in the north to the northern Chile Trench further south. We find that just the opposite is true: the lithosphere appears stiffer outboard of the Peru Trench than it does further south, and the isotherm controlling the elastic/ductile transition must be 600°C or greater if the thermal structure of the plate is that predicted by the standard thermal plate model. Because the decrease in plate stiffness to the south is correlated with a decrease in the minimum radius of curvature of the flexed plate over the outer rise and outer trench wall, we interpret our result in terms of inelastic yielding of the oceanic lithosphere when bent to high strains. The fact that the more highly bent segment of subducting lithosphere also dips at a steeper angle at greater depth beneath the continent might suggest that the amount of inelastic weakening of the lithosphere could be predicted from seismic images of the down going slab, but we find little support for this correlation worldwide. The forces and moments controlling the shallow deformation of the plate seaward of the trench do not appear to be linked to upper mantle processes which impose the dip at greater depth. Finally, we consider the possibility that the elastic thickness of the lithosphere would be reduced for trenches that are highly arcuate in map view, again due to inelastic yielding. If such a relationship exists, the effect for oceanic lithosphere is much smaller than what is documented for continental plates where they underthrust highly arcuate fold belts.
    Keywords: Plate tectonics
    Repository Name: Woods Hole Open Access Server
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  • 21
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    Calcified tissue international 23 (1977), S. 13-17 
    ISSN: 1432-0827
    Keywords: Dental calculus ; Glycopeptide ; Chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Summary A method is described for the isolation and purification of a sulphated glycopeptide from human supragingival calculus. The compound was isolated after using EDTA treatment, 2 M CaCl2 extraction, proteolytic digestion, ethanol precipitation, and finally purified by DEAE cellulose chromatography. It migrated as a single component on cellulose acetate electrophoresis, and chemical and infrared spectral analysis showed the presence of covalently attached sulphate groups. The sulphated glycopeptide was distinguished from being a sulphated glycosaminoglycan.
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  • 22
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    Journal of molecular evolution 15 (1980), S. 79-101 
    ISSN: 1432-1432
    Keywords: Molecules ; Interstellar ; Chemistry ; Isotopes ; Solar system
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary The study of interstellar molecules broadly includes two areas of interest. One area uses the unique ability of molecules to act as probes of the physical conditions in the cold, dense, visually opaque component of the interstellar medium. The physical properties of this and other components of the interstellar medium are summarized. The other area deals with the chemistry of interstellar molecules, recent aspects of which are emphasized in this review. Gas-phase chemistry, shock chemistry, and grain surface chemistry are discussed in the context of recent observations. No present observations suggest that surface reactions are relevant, but neither can they be ruled out. Ion-molecule reactions are clearly operative, at least for the simpler species. Chemical isotope fractionation is reviewed, andd it is concluded that the complexities of the chemistry allow no cosmological conclusions to be drawn from observations of deuterium in interstellar molecules, while the presence of13C in interstellar molecules permits an estimate of the12C/13C ratio which is consistent with the current concepts of the nucleosynthesis history of the Galaxy. Possible connections between interstellar molecules and the early molecular history of the solar system are discussed.
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  • 23
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    Pure and applied geophysics 116 (1978), S. 1231-1249 
    ISSN: 1420-9136
    Keywords: Plate tectonics ; Lithosphere ; Asthenosphere ; Convection ; Mantle flow ; Viscosity of the mantle
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract A one-dimensional model of flow between a fixed boundary at the bottom and a moving one on top with no net flow through vertical sections is tested for geophysically interesting mantle viscosity-depth functions. Such a model, although simplistic, may help in answering the question to what depth the return flow extends, at least in the case of moving plates measuring many thousand kilometers across, such as the Pacific plate. It the viscosity in the asthenosphere is less than three orders of magnitude smaller than that of the mantle below, the return flow extends to great depth and the asthenosphere is a zone of concentrated shear. If the viscosity contrast is greater, the return flow is concentrated in the asthenosphere. For a wide range of model parameters typical flow velocities below the asthenosphere are about one-tenth of the plate velocity. The pressure gradient required by the mantle flow may be manifest in gravity trends across moving plates, but no excessive gravity anomalies are required by the model if the absolute viscosity values conform to those inferred from post-glacial rebound data. A thinner and lower-viscosity layer is favored over a thicker and more viscous layer if both fit glacial rebound evidence. The present model may not be applicable if down to the core the viscosity is as low as about 1021 N s m−2 with a free-slip bottom boundary.
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  • 24
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    Pure and applied geophysics 116 (1978), S. 1284-1298 
    ISSN: 1420-9136
    Keywords: Adriatic Sea ; Apennines ; Mediterranean ; Plate tectonics ; Surface waves
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract Two new techniques in surface wave analysis, the modified moving window method and the method of stacking and cleaning, are used to determine average group and phase velocities over the area covering the Adriatic Sea and the Northern and Central Apennines, while avoiding the anomalous region under the Po plain. The data indicate that the lateral homogeneity of the region is sufficiently good to allow for an ‘averaged’ model of the lithosphere. Backus-Gilbert inversion of the data leads to an averaged model with a thick sedimentary cover (10–11 km), a normal continental Moho depth of about 35 km, and a velocity rise with depth below the crust. The extremely low group velocity data that are encountered both in the Apennine region and in the Adriatic Sea suggest a similarity between the crustal structure of this area and the Eastern Mediterranean.
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  • 25
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    Pure and applied geophysics 117 (1979), S. 1082-1147 
    ISSN: 1420-9136
    Keywords: Seismic gaps ; Earthquake prediction ; Plate tectonics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract The theory of plate tectonics provides a basic framework for evaluating the potential for future great earthquakes to occur along major plate boundaries. Along most of the transform and convergent plate boundaries considered in this paper, the majority of seismic slip occurs during large earthquakes, i.e., those of magnitude 7 or greater. The concepts that rupture zones, as delineated by aftershocks, tend to abut rather than overlap, and large events occur in regions with histories of both long- and short-term seismic quiescence are used in this paper to delineate major seismic gaps. In detail, however, the distribution of large shallow earthquakes along convergent plate margins is not always consistent with a simple model derived from plate tectonics. Certain plate boundaries, for example, appear in the long term to be nearly aseismic with respect to large earthquakes. The identification of specific tectonic regimes, as defined by dip of the inclined seismic zone, the presence or absence of aseismic ridges and seamounts on the downgoing lithospheric plate, the age contrast between the overthrust and underthrust plates, and the presence or absence of back-arc spreading, have led to a refinement in the application of plate tectonic theory to the evaluation of seismic potential. The term seismic gap is taken to refer to any region along an active plate boundary that has not experienced a large thrust or strike-slip earthquake for more than 30 years. A region of high seismic potential is a seismic gap that, for historic or tectonic reasons, is considered likely to produce a large shock during the next few decades. The seismic gap technique provides estimates of the location, size of future events and origin time to within a few tens of years at best. The accompanying map summarizes six categories of seismic potential for major plate boundaries in and around the margins of the Pacific Ocean and the Caribbean, South Sandwich and Sunda (Indonesia) regions for the next few decades. These categories range from what we consider high to low potential for being the site of large earthquakes during that period of time. Categories 1, 2 and 6 define a time-dependent potential based on the amount of time elapsed since the last large earthquake. The remaining categories, 3, 4, and 5, are used for areas that have ambiguous histories for large earthquakes; their seismic potential is inferred from various tectonic criteria. These six categories are meant to be interpreted as forecasts of the location and size of future large shocks and should not be considered to be predictions in which a precise estimate of the time of occurrence is specified. Several of the segments of major plate boundaries that are assigned the highest potential, i.e., category 1, are located along continental margins, adjacent to centers of population. Some of them are hundreds of kilometers long. High priority should be given to instrumenting and studying several of these major seismic gaps since many are now poorly instrumented. The categories of potential assigned here provide a rationale for assigning prorities for instrumentation, for future studies aimed at predicting large earthquakes and for making estimates of tsunami potential.
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  • 26
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    Pure and applied geophysics 117 (1978), S. 172-179 
    ISSN: 1420-9136
    Keywords: Coast Plutonic Complex ; Quaternary volcanism ; Plate tectonics ; Heat flow ; Heat production
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract In southern British Columbia the terrestrial heat flow is low (44 mW m−2) to the west of the Coast Plutonic Complex (CPC), average in CPC (50–60 mW m−2),and high to the east(80–90 mW m−2). The average heat flow in CPC and the low heat generation (less than 1 μW m−3) indicate that a relatively large amount of heat flows upwards into the crust which is generally quite cool. Until two million years ago the Explorer plate underthrust this part of the American plate, carrying crustal material into the mantle. Melted crustal rocks have produced the inland Pemberton and Garibaldi volcanic belts in the CPC. Meager Mountain, a volcanic complex in the CPC 150 km north of Vancouver, is a possible geothermal energy resource. It is the product of intermittent activity over a period of 4 My, the most recent eruption being the Bridge River Ash 2440 y B.P. The original explosive eruption produced extensive fracturing in the granitic basement, and a basal explosion breccia from the surface of a cold brittle crust. This breccia may be a geothermal reservoir. Other volcanic complexes in the CPC have a similar potential for geothermal energy.
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  • 27
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    Pure and applied geophysics 115 (1977), S. 441-458 
    ISSN: 1420-9136
    Keywords: Earthquake stress drops ; Plate tectonics ; Stress in lithosphere
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract A variety of geophysical observations suggests that the upper portion of the lithosphere, herein referred to as the elastic plate, has long-term material properties and frictional strength significantly greater than the lower lithosphere. If the average frictional stress along the non-ridge margin of the elastic plate is of the order of a kilobar, as suggested by the many observations of the frictional strength of rocks at mid-crustal conditions of pressure and temperature, the only viable mechanism for driving the motion of the elastic plate is a basal shear stress of several tens of bars. Kilobars of tectonic stress are then an ambient, steady condition of the earth's crust and uppermost mantle. The approximate equality of the basal shear stress and the average crustal earthquake stress drop, the localization of strain release for major plate margin earthquakes, and the rough equivalence of plate margin slip rates and gross plate motion rates suggest that the stress drops of major plate margin earthquakes are controlled by the elastic release of the basal shear stress in the vicinity of the plate margin, despite the existence of kilobars of tectonic stress existing across vertical planes parallel to the plate margin. If the stress differences available to be released at the time of faulting are distributed in a random, white fasbion with a mean-square value determined by the average earthquake stress drop, the frequency of occurrence of constant stress drop earthquakes will be proportional to reciprocal faulting area, in accordance with empirically known frequency of occurrence statistics.
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  • 28
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    Pure and applied geophysics 115 (1977), S. 655-666 
    ISSN: 1420-9136
    Keywords: Seismology ; Greece ; Plate tectonics ; Focal mechanism
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Summary An attempt has been made to interpret the striking difference, in focal properties, between the intermediate and shallow earthquakes in Central Greece and an observed time sequence of these shocks by a lithospheric model. This model consists of a lithospheric slab descending from the Ionian to the Aegean and a back-arc expanding Aegean lithosphere. Thrust faulting near the top surface of the slab, caused by the sinking of the slab, triggers spreading and normal faulting in the back-arc Aegean region.
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  • 29
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    Pure and applied geophysics 117 (1979), S. 958-987 
    ISSN: 1420-9136
    Keywords: Mantle convection ; Plate tectonics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Summary An approximate method of calculating the stability of two-dimensional convection rolls to cross-roll disturbances is evaluated by comparison with the results from exact analyses and good agreement is obtained. In particular, investigation of the second mode of the disturbance provides a qualitative estimate of the terms excluded in making the approximation. We conclude that this approximate method, sensibly used, gives a good indication of the stability of rolls to cross-roll disturbances. Application of this method is made to convection rolls heated partially or wholly from within, and to rolls in the presence of a longitudinal shear flow. The approximation indicates that, at high Rayleigh Numbers, growth rates are underestimated and so the amount of shear calculated to stabilise longitudinal rolls is a lower bound. Our results suggest that two-dimensional rolls are unlikely to be a stable flow pattern beneath even the fastest moving plates.
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  • 30
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    Pure and applied geophysics 118 (1980), S. 128-151 
    ISSN: 1420-9136
    Keywords: Galactic cosmic rays ; Solar proton events ; Particle precipitation ; Chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Geosciences , Physics
    Notes: Abstract An assessment is made of the relative contribution of certain classes of energetic particle precipitation to the chemical composition of the middle atmosphere with emphasis placed on the production of odd nitrogen and odd hydrogen species and their subsequent role in the catalytic removal of ozone. Galactic cosmic radiation is an important source of odd nitrogen in the lower stratosphere but since the peak energy deposition occurs below the region where catalytic removal of O3 is most effective, it is questionable whether this mechanism is important in the overall terrestrial ozone budget. The precipitation of energetic solar protons can periodically produce dramatic enhancement in upper stratospheric NO. The long residence time of NO in this region of the atmosphere, where catalytic interaction with O3 is also most effective, mandates that this mechanism be included in future modelling of the global distribution of O3. Throughout the mesosphere the precipitation of energetic electrons from the outer radiation belt (60°≲Λ≲70°) can sporadically act as a major local source of odd hydrogen and odd nitrogen leading to observable O3 depletion. Future satellite studies should be directed at simultaneously measuring the precipitation flux and the concomitant atmosphere modification, and these results should be employed to develop more sophisticated models of this important coupling.
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  • 31
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    Calcified tissue international 23 (1977), S. 39-44 
    ISSN: 1432-0827
    Keywords: Dental cementum ; Collagen ; Protein ; Chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Summary Cyanogen bromide (CNBr) peptides were prepared of the insoluble collagen of bovine dental cementum. Following chromatographic separation, the peptides were identified by their amino-acid composition. Type I collagen ([α1(I)]2α2) accounted for more than 90% of the organic matrix, while Type III collagen ([α1(III)]3) was present at a level of approximately 5%. Amino-acid analyses revealed that the CNBr peptides from α1(I) and α2 chains of cementum closely resembled the corresponding peptides from calf skin. The only systematic difference was a higher level of hydroxylation of prolyl and lysyl residues of the cementum peptides.
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  • 32
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    Calcified tissue international 23 (1977), S. 87-94 
    ISSN: 1432-0827
    Keywords: Calcium ; Osteoporosis ; Lactation ; Chemistry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Summary The calcium homeostatic mechanism was challenged in adult female rats by feeding them a calcium-deficient diet containing oxalate, and by subjecting them to pregnancy and lactation. The regimen caused a substantial weight loss, especially in those animals which reared their young well. Severe hypocalcaemia was observed in the lactating rats. Serum-P was slightly elevated. The content of hydroxyproline in serum was considerably elevated, reflecting the degree of calcium deprivation. Serum proteins were least influenced. The calcium depriving regimen reduced the growth of long bones, but did not stop it. The ash content of the bones was considerably reduced, the degree of reduction depended on the degree of calcium deprivation. Ash as percentage of total bone organ was reduced, but not to the same extent as total ash. Analyses of different parts of femur showed that the proximal and distal parts had lost more bone mineral than the diaphyseal shaft. The ash content of cortical bone tissue from the femur was estimated by a volumetric method. No differences were observed between test groups and controls, indicating that no measurable amounts of bone mineral had been removed from the walls of the vascular canals or by osteocytic osteolysis. Planimetric determinations on cross sections from femora disclosed that a great amount of bone had been removed from the endosteal surface of the diaphysis, while the periosteal surface demonstrated reduced bone apposition.
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  • 33
    ISSN: 1432-0827
    Keywords: Bacterial amphophile ; Purification ; Chemistry ; Resorption ; Ca influx ; Cyclic AMP
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Summary The bone resorptive factor and amphipathic antigen (AcA) previously identified by us in preparations fromActinomyces viscosus have been partially purified, characterized chemically, and compared. They elute at the same location on chromatography with Ac 22. The fatty acid composition of AcA and the bone resorptive factor is the same. Some differences in carbohydrate composition are observed. TheActinomyces factor does not affect calcium influx or cyclic AMP in isolated bone cells. Therefore it is concluded that AcA stimulates resorption either by gaining entrance into bone cells or by way of a yet undetermined second messenger.
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  • 34
    ISSN: 1432-0878
    Keywords: Milk ; Fat globule membrane ; Carbohydrates ; Chemistry ; Ruthenium red ; Ultrastructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine
    Notes: Summary The fat globules of the cream fractions of human and rat milk were stained with ruthenium red. Under the electron microscope, discrete granules and an amorphous coat of lesser density are seen at the surface of the milk fat globules. Since ruthenium red binds anionic groups selectively, it is probable that the granules containe the greatest concentration of these groups. The cream fraction of rat milk contains hexoses, hexosamines, methylpentoses and sialic acid. Methylpentoses and hexosamines are significantly enriched in the cream fraction. It is concluded that the finding of a surface coat in milk fat globules is in keeping with the Bargmann-Knoop model and suggests a distinct mechanism for carrying certain complex carbohydrates in milk. The role of the negative charges at the outer surface of the membrane coat in maintaining fat globules in suspension and in binding certain cations such as calcium is suggested.
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  • 35
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    Biopolymers 14 (1975), S. 1841-1846 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformational phase diagram of poly(L-lysine) (4.6 × 10-4 M, residue) in sodium dodecyl sulfate (1.6 × 10-2 M) solution was constructed from circular dichroism results at various temperatures and pH's. Poly(L-lysine)-sodium dodecyl sulfate complexes undergo a β-helix transition upon raising the pH of the solution. The transition pH tends to shift downward at elevated temperatures. No helix-β transition can be detected for poly(L-lysine) in sodium dodecyl sulfate solution (pH 〉 11) even after 1-hr heating at 70°C. This is in marked contrast with uncharged poly(L-lysine) solution without sodium dodecyl sulfate, which is converted into the β-form upon mild heating of the solution above 50°C.
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  • 36
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    Biopolymers 14 (1975), S. 1885-1903 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A normal coordinate analysis of V-amylose has been performed for an isolated 61 helical chain. Negligible splitting from interactions of vibrations of successive residues is expected between A and E vibrational species due to the large size of the monomer unit. As a result, calculation of only the totally symmetric A modes represents an adequate approximation to the vibrational spectrum of helical polysaccharides. Using this method together with a valence force field we have obtained good agreement between the observed and calculated frequencies. In addition, the computed potential energy distribution and Cartesian displacement coordinates match previous experimental assignments, based on deuterium exchange. The analysis also supports the proposed mechanism for conversion of V-amylose to the more extended B-form. This conversion results in an observed frequency shift for the Raman line at 946 cm-1 which is predicted by the calculations.
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  • 37
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    Biopolymers 14 (1975), S. 2025-2033 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The circular dichroism of Ac-(Ala)x-OMe and H-Lys-(Lys)x-OH with x = 1, 2, 3, and 4 has been measured in aqueous solutions. The oligomers with x = 4 show similar circular dichroism spectra in water when the lysyl amino groups are protonated, and they respond in similar fashion to heating and to sodium perchlorate. Both oligomers at 15°C exhibit a positive circular dichroism band at 217-218 nm, which is eliminated by the isothermal addition of 4 M sodium perchlorate or by heating. The positive circular dichroism of the lysine oligomer is also eliminated when the pH is elevated to deprotonate the amino groups. Positive circular dichroism is still observed for Ac-(Ala)4-OMe at elevated pH. Circular dichroism spectra have been estimated for poly(L-alanine) and poly(L-lysine) as statistical coils under the above conditions, based on the trends established with the oligomers. Poly(L-lysine) and poly(L-alanine) are predicted to exhibit similar circular dichroism behavior in aqueous solution so long as the lysyl amino groups are protonated. The circular dichroism of the statistical coil of poly(L-lysine), but not poly(L-alanine), is predicted to change when the pH is elevated sufficiently to deprotonate the lysyl amino groups. These results suggest that the unionized lysyl side chains participate in interactions that are not available to poly(L-alanine). Hydrophobic interactions may occur between the unionized lysyl side chains. Protonation of the lysyl amino groups is proposed to disrupt these interactions, causing poly(L-alanine) and protonated poly(L-lysine) to have similar circular dichroism properties.
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  • 38
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Synthesis of nonapeptide hydrazide (sequence 93-101), [Thr107]-decapeptide (sequence 99-108), [Thr107]-tridecapeptide (sequence 96-108), [Thr107]-hexadecapeptide (sequence 93-108), [Thr107]-heptacosapeptide (sequence 82-108), and Nα-benzyloxycarbonyl-[Thr107]-dotetracontapeptide (sequence 67-108) of the proposed primary structure of baker's yeast iso-1-cytochrome c are described. Evidence is presented to indicate that these materials are sequentially homogeneous.
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  • 39
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    Biopolymers 14 (1975), S. 2115-2135 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-β-benzyl-L-aspartate (poly[Asp(OBzl)]) forms either a lefthanded α-helix, β-sheet, ω-helix, or random coil under appropriate conditions. In this paper the Raman spectra of the above poly[Asp(OBzl)] conformations are compared. The Raman active amide I line shifts from 1663 cm-1 to 1679 cm-1 upon thermal conversion of poly[Asp(OBzl)] from the α-helical to β-sheet conformation while an intense line appearing at 890 cm-1 in the spectrum of the α-helix decreases in intensity. The 890 cm-1 line also displays weak intensity when the polymer is dissolved in chloroform-dichloroacetic acid solution and therefore is converted to the random coil. This line probably arises from a skeletal vibration and is expected to be conformationally sensitive. Similar behavior in the intensity of skeletal vibrations is discussed for other polypeptides undergoing conformational transitions.The Raman spectra of two cross-β-sheet copolypeptides, poly(Ala-Gly) and poly(Ser-Gly), are examined. These sequential polypeptides are model compounds for the crystalline regions of Bombyx mori silk fibroin which forms an extensive β-sheet structure. The amide I, III, and skeletal vibrations appeared in the Raman spectra of these polypeptides at the frequencies and intensities associated with β-sheet homopolypeptides. Since the sequential copolypeptides are intermediate in complexity between the homopolypeptides and the proteins, these results indicate that Raman structure-frequency correlations obtained from homopolypeptide studies can now be applied to protein spectra with greater confidence.The perturbation scheme developed by Krimm and Abe for explaining the frequency splitting of the amide I vibrations in β-sheet polyglycine is applied to poly(L-valine), poly-(Ala-Gly), poly(Ser-Gly), and poly[Asp(OBzl)]. The value of the “unperturbed” frequency, V0, for poly[Asp(OBzl)] was significantly greater than the corresponding values for the other polypeptides. A structural origin for this difference may be displacement of adjacent hydrogen-bonded chains relative to the standard β-sheet conformation.
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    Biopolymers 14 (1975) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 41
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Circular dichroism studies on synthetic peptides related to the C-terminal region of yeast iso-1-cytochrome c were carried out and compared with conformational studies on horse cytochrome c fragments. Evidence is presented for a weaker predisposition for ordered structure in the former peptides when compared with the corresponding region in horse cytochrome c. These findings agree with theoretical predictions and with observations that yeast and other mammalian type cytochromes c differ in several minor respects.
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  • 42
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    Biopolymers 14 (1975), S. 2107-2114 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A polarimetric electric-field-jump relaxation apparatus is described and used to determine the relaxation spectrum for the helix-coil transition of poly(α,L-glutamic acid) in water at 24°C. A maximum relaxation time of 1.7 μc occurs at the transition midpoint (pH = 5.9) yielding a rate constant for helical growth of 6 × 107 sec-1.
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  • 43
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    Biopolymers 14 (1975), S. 2181-2195 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mixtures of a weak polybase (polyethylenimine) and a weak polyacid acrylamide-acrylic acid copolymer in aqueous solutions at several ionic strengths and polymer concentrations are studied potentiometrically. When the concentrations of the polyethylenimine and acrylamide-acrylic acid copolymer charges are not too different, phase separation into two liquid phases (“complex coacervation”) is observed. In the pH region where no phase separation occurs, potentiometric titrations are performed on mixtures of both polymers. From the titrations of polyethylenimine solutions, acrylamide-acrylic acid copolymer solutions, and the mixtures, the free energy of interaction has been evaluated according to the theory of Litan. The dependence of the free energy of interaction on pH, polymer concentrations, and ionic strength is explained quantitatively with a model of cooperative electrostatic physical association.
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  • 44
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The problem of deducing the DNA structure with correct base pairing and specific symmetry is formulated in the form of algebraic equations. In this way the number of independent variables determining double-helix conformation can be reduced from six to four. The effectiveness of the method is illustrated by the computations for A-DNA and B-DNA. The method allows one to predict all possible conformations of the complementary nucleic acids.
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  • 45
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    Biopolymers 14 (1975), S. 2211-2230 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis and characterization of a series of sequential polypeptides with the repeating sequences Aze-Pro-Aze, Pro-Aze-Pro, Pro-Aze-Gly, Aze-Pro-Gly, Ala-Aze-Gly, Aze-Ala-Gly, and Pro-Pro-Gly are reported. The polymers were prepared by the active ester method, using the p-nitrophenyl, pentachlorophenyl, and N-hydroxysuccinimide esters as the polymerizable tripeptide derivatives. Except for poly(Ala-Aze-Gly) obtained via the N-hydroxysuccinimide ester, all polymers were isolated in good yields and have weight-average molecular weights in the range 10,000-30,000. The molecular weights have been determined by applying the calibrated gel chromatography system described by Fairweather et al. [J. Chromatogr. (1972) 67, 157] and by viscometry. All di- and tripeptide intermediates were chemically and optically pure.
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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: Synthetic regular polytripeptides of the type (Gly-R2-R3) where R2, R3, or both, are imino acids have been widely studied as model compounds for collagen. One such polytripeptide is poly(Gly-Pro-Hyp), since triplets with this sequence constitute about 10% of collagen. Recently, a new model has been proposed for this polytripeptide in which one of the three peptide bonds in the tripeptide unit is in the cis conformation, and the γ-hydroxyl group of hydroxyproline forms a direct interchain hydrogen bond within the triple helix. We have confirmed this structure by model building using computer techniques, and the helical parameters obtained by us are close to the experimentally observed values. The model is also found to be comparable in stability with other models from energy considerations.
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  • 47
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Several globular proteins have values of the Scheraga-Mandelkern β parameter significantly below the theoretical minimum value, β0 = 2.112 × 106, for an impermeable sphere. Using the Felderhof-Deutch generalization of the Debye-Bueche-Brinkman theory of hydrodynamics of porous spheres, we have shown that values of β slightly below this supposed minimum are theoretically expected. A porous sphere of uniform density has a minimum β of 2.084 × 106 at a Debye shielding ratio of 6.5, corresponding, for example, to a sphere radius of 11 Å and an inverse hydrodynamic shielding length of 0.6 Å-1, values not far from those of small proteins. A two-layer porous sphere model gives similar results. Although this is the first theoretical explanation of values of β below β0, the theory is incomplete since β values as low as 2.03 × 106 are observed.
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  • 48
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    Biopolymers 14 (1975), S. 2489-2506 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: NMR measurements of poly(γ-benzyl-L-glutamate) are reported in several different strengths of magnetic field to determine the relaxation time of the helix-coil transition. Nmr spectra of various samples had line shapes varying from the double to single, depending on the extent of the polydispersity of the sample. This result indicated that the correct line shape of a polypeptide is obscured in the overlapping of multipeaks, which are due to the heterogeneity of the molecular weight in the sample. Thus, the conventional line-shape analysis could not be applied to the kinetic study of the helix-coil transition of polypeptides without consideration of this polydispersity effect on the line shape.To overcome this difficulty, we measured linewidths of nmr spectra for fairly monodisperse samples, using various nmr spectrometers, having field strengths from 60 to 220 MHz. The results were analyzed by a quadratic equation, which involves an additional term proportional to the frequency difference of two sites. The equation differs from the conventional quadratic equation, usually utilized in the case of the fast-exchange limit, only in this additional term. This modification is required to evaluate correctly the unusual broadening of the linewidth resulting from the polydispersity effect and to determine the relaxation time reflected in nmr.Nmr spectra of three samples (DP-35, 85, and 250) were measured by 220-, 100-, and 60-MHz spectrometers in trifluoroacetic acid/chloroform at 28°C and linewidths were analyzed. Relaxation times of the helix-coil transition obtained at the transition midpoint are 2.5 × 10-4, 7 × 10-4, and 1.1 × 10-3 sec, for DP-35, 85, and 250, respectively.
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  • 49
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Theoretical expressions are derived for the change in the polarized components of the fluorescence, resulting from the orientation of a rigid molecule bearing a chromophore with arbitrary angles for the absorption and transition moments \documentclass{article}\pagestyle{empty}\begin{document}$ \vec \mu _a $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ \vec \mu _e $\end{document} with respect to the molecular axis. The break in the symmetry relation HV = VH is related to the tilt angle between \documentclass{article}\pagestyle{empty}\begin{document}$ \vec \mu _a $\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ \vec \mu _e $\end{document}. The theory is applied to a sonicated DNA-2-hydroxy-4,4′-diamidinostilbene complex, in the blue and red emission bands of this peculiar dye. Simultaneous measurements of linear dichroism and fluorescence lead to the determination of an angle of 47° between a fluorescent bound dye and the DNA axis, with no difference for the blue- and red-emitting species, but confirm the presence of nonfluorescent bound dye in a more perpendicular arrangement.
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    Biopolymers 14 (1975), S. 2613-2623 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The translational drag, rotational drag, and intrinsic viscosity of spherical multisubunit structures have been calculated analytically using the Felderhof-Deutch theory of polymer frictional properties. The structures considered were hollow shells, spheres with uniform subunit density, and spheres covered with a subunit layer of different density. Changes in the transport coefficients resulting from the random removal of subunits and from the variation of subunit size are calculated. For the case of the shell, the results agree with the numerical computations of Bloomfield, Dalton, and Van Holde [Biopolymers 5, 135, 149 (1967)].
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  • 51
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Interactions of glutaraldehyde with either n-butylamine, poly(α,L-lysine), or collagen resulted in a fast release of protons in dilute aqueous solutions at various pH values, followed by much slower changes. The latter reactions, which extended over hours and days, were followed spectrophotometrically and revealed the formation of distinct absorption bands in the visible and near-ultraviolet regions in all the above systems. The visible-range bands disappeared upon treatment with sodium borohydride. A qualitative relationship between oxygen uptake by the system n-butylamine-glutaraldehyde and the slow formation of colored products has been established, while the chemical nature of the reaction products has not been determined.Sedimentation velocity, viscosity, and optical rotation measurements on the products of interaction between poly(L-lysine) and glutaraldehyde in aqueous solution indicated large conformational changes in the polyamino acid present in excess (in residues) over the dialdehyde. In particular, the intrinsic viscosity dropped considerably after interaction, indicating intramolecular crosslinking. At molar ratios of 1:1 between polylsine residues and aldehyde groups, intermolecular crosslinking of polylysine was obtained at pH 8.6.Electron microscopic examinations of collagen samples treated by glutaraldehyde at various pH values indicated changes from unordered to more ordered structures upon treatment with glutaraldehyde, in particular at pH 10.The present structural and optical investigations are considered to be relevant to tanning processes of hides and to fixation procedures.
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  • 52
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    Biopolymers 15 (1976), S. 1-14 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The template directed synthesis of poly[d(A-T)] from the nucleoside triphosphates in the presence of DNA polymerase I is carried out continuously in a stirred flow reactor for the first time. The initial objective is to test the kinetic stability of the established steady states at various flow rates. Graphical analysis predicts instable steady states for certain high flow rates. As a consequence of instabilities multiple steady states and steady-state hysteresis may occur. Steady-state hysteresis has now been found experimentally. For a different enzyme fraction of low exonuclease activity we found the steady-state absorbance at 260 nm to be almost invariant with flow rate at high enzyme concentrations even if the flow rate was increased by a large factor. We call this phenomenon kinetic buffering. Relaxation of a large flow perturbation approaches the steady state in a sigmoidal fashion. Concentration oscillations at 260 nm occurred in one experiment using an enzyme fraction of low exonuclease activity after perturbing the steady state by monomer (dATP). Advantages of the stirred flow reactor method over serial transfer are discussed.
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  • 53
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The far-ultraviolet circular dichroic spectrum of the 39-residue peptide hormone porcine corticotropin and the biologically active fragment corticotropin 1-24 is negative from 250 nm to 195 nm in water, but in 6M guanidinium chloride a positive band appears at about 225 nm. The temperature and guanidinium chloride dependence of this spectral transition indicates the absence of any stable ordered secondary structure in corticotropin and the spectrum is seen to be in only partial agreement with results using the model peptide chromophore, Ala-Ala-Ala. Using oligopeptides containing aromatic amino acid residues sandwiched between glycyl residues, it is shown that the shape and intensity of the corticotropin 225 nm positive band which appears in 6M guanidinium chloride is in agreement with the far-ultraviolet transitions of the aromatic chromophores in the hormone. Curve resolution of the near-ultraviolet circular dichroic spectrum of corticotropin and comparison of the rotational strengths of the phenylalanyl and tyrosyl bands reveals no evidence for increased rotational freedom in 6M guanidinium hydrochloride. Spectral changes are observed, however, in the transitions arising from the single tryptophan. This study suggests that corticotropin in aqueous solution may serve as a better model for the circular dichroic spectrum of the aperiodic regions in globular proteins than either synthetic homopolypeptides or reference proteins for which spectral and X-ray diffraction data are available.
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    Biopolymers 15 (1976), S. 131-152 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An all-order classical coupled oscillator theory in which monomer band shapes are explicity taken into account is applied to the calculations of polynucleotide circular dichroism. Calculations are shown for ApA and oligoadenylic acid of varying chain lengths, in both RNA and B-DNA geometry, and the advantages of this theory are assessed. By introducing an effective dielectric constant, good agreement with measured spectra is obtained. Variations in monomer parameters are tested in an attempt to eliminate remaining discrepancies between calculated and measured spectra.
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    Biopolymers 15 (1976), S. 203-218 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Raman Spectra of bovine serum albumin have been obtained in the solute state, in alkaline and acidic solutions, and in the gel. The reversible denaturations of bovine serum albumin solutions by heat, acid's, and alkali were studied and a new mechanism for heat denaturation has been proposed based on a continuous unfolding of the α-helices.
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    Biopolymers 15 (1976), S. 219-225 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New techniques in laser Raman spectroscopy are used to obtain spectra of aqueous solutions of lysozylme for frequency shifts as small as 5 cm-1. In addition, Raman measurements are made on two crystalline forms of hen egg white lysozyme. The spectra obtained from the solution and from the crystal are found to be similar for frequencies above 100 cm-1. However, a low-frequency band at 25 cm-1 observed in crystalline lysozyme is not found in the solution, indicating that this band cannot be attributed to an internal molecular vibration.
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    Biopolymers 15 (1976), S. 257-263 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The adsorption of protein films on polystyrene latex spheres was studied by optical mixing spectroscopy. With this technique, we show that both the hydrodynamic thickness of protein films and their optical density can be measured. Thus, we found that films of the glycoproteins isolated from the human erythrocyte membrane were four times as thick as films of either human serum albumin or bovine serum albumin for about the same surface coverage. This result suggests an end-on orientation for the adsorbed glycoprotein molecules, which is consistent with the model proposed by others for the orientation of these molecules at the surface of the red blood cell itself.
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    Biopolymers 15 (1976), S. 293-299 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Solvent binding to bovine serum albumin in 2-chloroethanol-water mixed solvents of different composition, measured previously by Inoue and Timasheff (Biopolymers (1972) 11, 737-43) is applied to a hydrodynamic study of the solvated protein.From sedimentation and diffusion data, the apparent molecular weight of the solvated protein particle can be calculated, provided an average partial specific volume, computed from the composition of the particle, is introduced in Svedberg's equation. The unsolvated molecular weight of the protein can than be calculated by subtraction of the bound solvent. Further data on the hydrodynamic particle (f/fmin and axial ratio of the equivalent ellipsoid) are readily calculated from these experiments, and reinforce the supposition that 2-chloroethanol is a strong helix-inducing solvent.
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    Biopolymers 14 (1975), S. 2625-2637 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to obtain a molecular picture of the A and B forms of a DNA subunit, potential energy calculations have been made for dGpdC with C(3′)-endo and C(2′)-endo [or C(3′)-exo] sugar puckerings. These are compared with results for GpC. The global minima for dGpdC and GpC are almost identical. They are like A-form duplex DNA and RNA, respectively, with bases anti, the ω′, ω angle pair near 300°, 280°, and sugar pucker C(3′)-endo. For dGpdC, a B-form helical conformer, with sugar pucker C(2′)-endo and ω′ = 257°, ω = 298°, is found only 0.4 kcal/mol above the global minimum. A second low-energy conformation (2.3 kcal/mol) has ω′ = 263°, ω = 158° and ψ near 180°. This has dihedral angles like the original Watson-Crick model of the double helix. In contrast, for GpC, the C(2′)-endo B form is 6.9 kcal/mol above the global minimum. These theoretical results are consistent with experimental studies on DNA and RNA fibers. DNA fibers exist in both A and B forms, while RNA fibers generally assume only the A form. A low-energy conformation unlike the A or B forms was found for both dGpdC and GpC when the sugars were C(3′)-endo. This conformation - ω′,ω near 20°,80° - was not observed for C(2′)-endo dGpdC. Energy surface maps in the ω′,ω plane showed that C(2′)-endo dGpdC has one low-energy valley. It is in the B-form helical region (ω′ ∼ 260°, ω ∼ 300). When the sugar pucker is C(3′)-endo, dGpdC has two low-energy regions: the A-form helical region and the region with the minimum at ω′ = 16°, ω = 85°.
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    Biopolymers 15 (1976) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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  • 61
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    Biopolymers 15 (1976), S. 403-414 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have carried out a detailed study of ligand binding of ferrihemoglobins under various conditions. Our results show that n varies with time and that this variation is paralleled by changes in the spectrum of methemoglobin. This suggests some form of structural perturbation. The time-dependent value of n is discussed in terms of the observed spectral changes accompanying prolonged equilibration.
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  • 62
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    Topics: Chemistry and Pharmacology
    Notes: The nmr titration curves of chemical shifts versus pH were observed for the protons of various histidine-containing di- and tripeptides. With these results, the macroscopic pKa values and the chemical shifts intrinsic to each ionic species were determined by a computer curve-fitting based on a simple acid dissociation sequence. The pKa value of the imidazole ring in N-acetyl-L-histidine methylamide was assumed to represent the intrinsic (or unperturbed) pKa of the imidazole rings of histidine having peptide linkages at both the CO and NH sides. The pKa values of the imidazole rings observed for most di- and tripeptides were reasonably reproduced by simple calculations using the intrinsic value and the perturbations due to the CO2- and NH3+ groups located at various positions. Some other factors affecting the pKa value of the imidazole ring are also discussed.
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  • 63
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    Biopolymers 15 (1976) 
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  • 64
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    Topics: Chemistry and Pharmacology
    Notes: The hyperchromic and hypochromic changes in the intensity of the amide-I and amide-III lines of polypeptides and certain ring vibrations of the bases of polynucleotides are shown to be related to similar changes in the lower energy uv absorption bands. The selection rules strictly limit the pairs of excited electronic states that can contribute to the elements of the polarizability matrix. An energy-dependent term in this equation weights the contribution of the pairs of electronic transitions in favor of those involving the lower energy transitions. For both polypeptides and polynucleotides, there is a large hypochromic inensity change in the first π → π* exciton band upon the coil-to-helix transition. Through the selection rules, certain conformationally sensitive Raman lines are shown to derive their intensity predominantly from this band and hence also display hypochromism. Again, through an application of the selection rules, certain Raman lines can be demonstrated to depend predominantly for their intensity upon the n → π* transition, and consequently have the opposite hyperchromic intensity change upon the same conformational transition.
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  • 65
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    Biopolymers 15 (1976), S. 301-315 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transient electric birefringence experiments have been performed on well-characterized highly monodisperse samples of tobacco mosaic virus (TMV). Experiments and calculations are presented that show that the sensitivity and accuracy of the traditional transient electric birefringence technique can be enhanced by several orders of magnitude through the use of a low-powered laser and crystal polarizing optics, signal averaging, and digital data processing. Measurements of the field-free decay of the birefringence yield for the rotational diffusion coefficient, DR = 318 ± 3 sec-1. The length of the rodlike virion, calculated from the Broersma equation with this value of DR and a rod diameter of 15 nm, is 292.5 ± 1.0 nm. Measurements of the growth of the birefringence when an electric field is applied across the sample yield μ2/kT(α∥ - α⊥) = 0.47 ± 0.07, where μ is the permanent dipole moment (assumed parallel to the symmetry axis of the virus) and α∥ - α⊥ is the electrical polarizability anistropy of the virus. Using the value of α∥ - α⊥ measured by O'Konski et al., we then obtain μ = 2.5 × 10-14 esu cm.
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  • 66
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    Topics: Chemistry and Pharmacology
    Notes: The high-resolution nmr spectrum of baker's yeast tRNACUALeu, a recently sequenced non-denaturable tRNA, has been compared with the spectra of the native and denatured conformers of the closely related species tRNAUUGLeu. Because of the presence of many common base pairs in the different tRNA's, it is possible to assign most of the low-field resonances to specific secondary-structure base pairs. A comparison of the observed positions of the various resonances with those predicted by a semiempirical ring-current shift theory shows a root-mean-square deviation of 0.14, 0.11, and 0.12 ppm for tRNAUUGLeu (native), and tRNAUUGLeu (denatured), respectively. These results support the ring-current shift theory currently used to interpret the low-field nmr spectra of the tRNA molecules. Differences between the predicted and observed positions of some resonances provide new evidence for higher order effects such as shifts from second nearest neighbors, anomalous shifts exerted by G·U base pairs, and tertiary-structure effects. A model that was previously proposed for the denatured conformer of tRNAUUGLeu is also supported.
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  • 67
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    Biopolymers 14 (1975), S. 319-334 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The properties of apomyoglobin were examined in aqueous solutions and various helix- and random-coil-forming solvents by solvent perturbation, optical rotation, circular dichroism, and viscosity measurements. The solvent perturbation data obtained in neutral aqueous solutions suggest 25-40% exposure of the two tryptophyl residues and 50-60% exposure of the three tyrosyls. The estimates of burial of these groups are in the ranges expected for myoglobin based on its X-ray structure. In the helicogenic alcohols, methanol, ethanol, 2-chloroethanol, trifluoroethanol, and 1-propyl alcohol, as well as in acidic solutions, 8 M urea and 6M guanidine hydrochloride, essentially all the tryptophyl and tyrosyl residues are found to be exposed to solvent based on this method. Analysis of the ORD and CD data indicates that in the alcohols the α-helix content of apomyoglobin has in most cases changed from 58-59% to about 80-95%. Analysis of the intrinsic viscosity data based on the equations of Simha and Kirkwood and Auer indicates that the polypeptide chain in these solvents has the dimensions of fully extended α-helical rods, with lengths of 221-251 Å and mean diameters of 12.8-13.6 Å. It is concluded that apomyoglobin in the various alcohols must have an extended but somewhat irregular rodlike structure, having a few bend or irregular sequences between the α-helical segments due largely to the presence of the four proline residues, 37, 88, 100, and 120 in the amino acid sequence.
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    Biopolymers 14 (1975), S. 335-351 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The fluorescence parameters, lifetime, relative quantum yield, maximum and mean wavelength, half-width, and polarization, of bovine serum albumin (BSA) were measured at 15°C in aqueous solutions containing varying concentrations of different chemical perturbants, glycerol, Cu2+ ions, guanidine hydrochloride, and urea. By considering a quenching mechanism as being either dynamic or static, depending upon whether the quenching is or is not accompanied by a change in the fluorescence lifetime, we were able to correlate the changes produced in the various fluorescence parameters by the different chemical perturbants with changes in macromolecular structure as the concentration of perturbant was gradually increased. The addition of glycerol and of Cu2+ ions indicated that in aqueous BSA both tryptophan residues are below the surface of the macromolecule, out of contact with solvent water, and, as a consequence, they are statically quenched. “Ultra-Pure” guanidine hydrochloride at 2.4 M or more caused a drastic conformation change, which resulted in the emergence of a visible tyrosine peak at 304 nm in the BSA fluorescence spectrum when either 260- or 270-nm excitation was employed. With the same excitation, the enhancement of BSA tyrosine fluorescence by 6-8 M ultra-pure urea produced only a shoulder near 304 nm in the BSA fluorescence spectrum. We have introduced the use of a new relative quantum yield for protein fluorescence, q′, referenced to the quantum yield of unquenched free tryptophan, which eliminates the quenching action of water from the reference.
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    Biopolymers 15 (1976) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 70
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    Topics: Chemistry and Pharmacology
    Notes: The molecular theory of the previous paper in this series is extended to determine the effect of divalent metal ions on helix stability relative to coil at fixed ionic strength and nucleotide phosphate concentration. Specification of the state of condensed counterions, as well as their concentration, is essential for the solution of this problem, and it is assumed that they translate freely within a thin cylindrical shell close to the polynucleotide. As a function of divalent counterion concentration mB2+ the relative stability of the helix is highly nonlinear. Although the overall trend is that the helix stability increases with addition of divalent metal ion, there is a narrow concentration range for which it decreases slightly. The behavior of the relative stability as a function of mB2+ is determined by the translational degrees of freedom of the counterions, both univalent and divalent, both condensed and uncondensed. Detailed comparison of the theory with data is not given here, but it is pointed out that the calculated values of the relative stability are consistent with the order of magnitude of the observed effect Mg2+ on the melting temperature.
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    Biopolymers 15 (1976), S. 503-506 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: X-ray diffraction studies have been made on the polytripeptide poly(L-prolyl-L-α-phenylglycyl-L-proline). Its structure has been found to be helical, with a poly(L-proline) II conformation, packed in an orthorhombic lattice, space group P21212, with a = 14.3 Å, b = 13.5 Å, and c = 9.4 Å.
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    Biopolymers 15 (1976), S. 591-594 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 15 (1976) 
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    Biopolymers 15 (1976), S. 649-653 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The stability constant of the complex of tRNA with 50S subunits of ribosomes was compared in ordinary and heavy water. A considerable effect (about fourfold) was observed, showing the importance of hydrogen bonds in this interaction. In addition, the isotope effect of complementary polynucleotide interaction was measured for two examples. In the case of the binary complex of heptainosinic acid oligomers with poly(C) in the presence of 10-3 M MgCl2, the transfer from ordinary to heavy water gave an increase of the stability constant of about 5%. But in the case of a ternary complex of hexaadenylic acid with poly(U) under the same conditions, the stability constant in D2O increased threefold. The isotope effect depends strongly on magnesium ion concentration and is possibly due to some specific mechanism of magnesium ion complexing involving water molecules.
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    Biopolymers 14 (1975), S. 409-417 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The storage and loss shear moduli, G′ and G″, have been measured for dilute solutions of unaggregated and aggregated tobacco mosaic virus samples in glycerol-water mixtures, by the Birnboim-Schrag multiple-lumped resonator modified for use with aqueous solvents. The frequency range was 100-5800 Hz, the concentration range 0.6-2.1 × 10-3 g/ml, and the temperatures 25.0° and 37.8°C. The number-average and weight-average molecular weights of the aggregated sample were estimated as 1.4 and 2.0 × 108, respectively, from electron microscopy. The extrapolated intrinsic moduli [G′] and [G″] were compared with the predictions of the Kirkwood-Auer theory for rigid rodlike molecules. For the unaggregated sample, the frequency dependence of [G′] and [G″] agreed well with the theory assuming the intrinsic viscosity to be 27 ml/g, though the asymptotic limit of [G′]M/RT at higher frequencies was slightly larger than the theoretical value of 3/5. For the aggregated sample, the data agreed with theory for rigid rods as modified to account for molecular-weight distribution.
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    Biopolymers 15 (1976), S. 999-1000 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 15 (1976), S. 1009-1013 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 15 (1976), S. 1061-1080 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Monte-Carlo calculations of geometric and thermodynamic characteristics of the α-helix and the β-structure of polypeptides have been carried out. To describe a hydrogen bond both the Lippincott-Schroeder and Morse potentials were used. The internal rotation angles ϕ and ψ in the α-helix have been shown to fluctuate in the range of ±7°. The distribution functions on angles ϕ and ψ and on hydrogen bond lengths and angles in the α-helix have been computed and compared with those in myoglobin and lysozyme. Thermodynamic characteristics of the α-helix calculated in different approximations with the two forms of the hydrogen bond potentials have also been compared. The data obtained are close to the experimental values for polypeptides in neutral solution.Some geometric and thermodynamic characteristics of the regular parallel and antiparallel and irregular antiparallel β-structure have been found. In the β-structure the internal rotation angles vary within the interval ±15-20°. An increase in the cross and longitudinal dimensions of the β-structure only slightly influence both the geometric and thermodynamic characteristics.
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  • 80
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    Topics: Chemistry and Pharmacology
    Notes: The preparation of the co-oligopeptides of the series H-Gly-Phe-(Gly)n-Trp-Gly-OH (n = 0, 1, 2) and of other free peptides of glycine, L-tryptophan, and L-phenylalanine is reported. The syntheses have been carried out by conventional methods, using N-hydroxysuccinimide esters for the coupling steps. The ultraviolet absorption properties of the free peptides have been investigated in water. No hypo- or hyperchromicity was found for the aromatic chromophores, with the exception of H-Gly-Phe-Trp-OH, which shows a small but significant hypochromicity. The contribution of the peptide bond to the molar absorptivity in the far ultraviolet has been separated from that of the side chain plus the —COO- group by plotting the measured molar absorptivity ∊ of the farthest accessible uv maximum as a function of the number of peptide bonds (nA). The peptide bond contribution proved to be independent of nA in the range nA = 1-5, thus ruling out the onset of helical conformations in the longer chain peptides.
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  • 81
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    Topics: Chemistry and Pharmacology
    Notes: The properties of the electron distribution in amides, peptides, and carboxylic acids, obtained from ab-initio molecular orbital calculations using both minimal and extended basis sets have been studied. These properties are discussed in terms of some of the common assumptions made in empirical conformational calculations of biomolecules. In particular, population analyses of 15 compounds in these families were carried out with both the minimal and extended basis sets, and compared with results of CNDO/2 calculations. It is suggested that population analysis is a useful tool for recognizing patterns of charge distributions, and investigating the transferability of parameters of different functional groups. However, its use for providing partial charges for conformational analysis is a questionable procedure.A more detailed analysis of the charge distribution was carried out by calculating the spatial electron distribution in the four compounds, N-methylacetamide, acetic acid, diketopiperazine, and N-acetyl-N′-methylalanine. Both total electron-density maps and differencedensity maps are presented. The properties of the overall shape of the molecule and the atoms in the molecule, are discussed in terms of the former along with three-dimensional shape plots of the total density. The distortion accompanying molecular formation, resulting in such features as the lone pair orbital and “bonding deensities” is discussed in terms of the difference maps. Semiquantitative estimates of the bonding and orbital densities resulting from the integration of the densities are also presented. Finally, one of the novel features of the study is the presentation of three-dimensional surfaces of constant difference densities from which the shapes of the orbitals and bonding densities emerge.
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    Biopolymers 15 (1976), S. 1233-1242 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The lack of the positive band at around 226 nm in the CD spectra of poly(prolyl-azetidine-2-carbonyl-proline) in trifluoroethanol and of poly(azetidine-2-carbonyl-prolyl-azetidine-2-carboxylic) acid in F3EtOH and water, the hyperchromism of the absorption maximum at about 202 nm, and the extremely small intensity of the Cβ-Pro, Cγ-Pro, and Cβ-Aze signals for the cis peptide bonds in the 13C nmr spectrum of poly(Pro-Aze-Pro) in F3EtOH indicate that both polyproline analogs exist as disordered chains in this solvent, the trans peptide group being maintained. The disordering of the chains is attributed to an increase in the accessible range of ψ due to the reduced dimensions of the square ring of L-azetidine-2-carboxylic acid residue relative to the pyrrolidine ring of proline and to strong interactions of the haloalcohol with the peptide groups of the chains.
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    Biopolymers 15 (1976), S. 1283-1299 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Two methods for the characterization of protein molecular weights from their diffusion coefficients are discussed. These measurements can be made quickly and reliably at low concentrations using quasielastic light-scattering techniques. First, an empirical calibration of the diffusion coefficient at infinite dilution of denatured random coils against molecular weight is reported. The second method combines the measurement of D0 with the intrinsic viscosity [η]. This D0-[η] relationship proves to be very insensitive to polymers structure or solvent type. The data indicate that the ratio of the hydrodynamic radius measured by viscosity to the hydrodynamic radius measured by diffusion is about 15% smaller than that predicted by theoretical models. The nature of the molecular-weight average obtained for polydisperse systems is defined for a Schulz distribution. These hydrodynamic methods have also been used to demonstrate the presence of chain branching in the glycoprotein ovomucoid. In addition, a method is proposed by which the effective segment length and an excluded volume parameter for random coils may be evaluated for diffusion measurements.
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    Biopolymers 15 (1976), S. 1425-1430 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 15 (1976), S. 1431-1435 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Topics: Chemistry and Pharmacology
    Notes: The influence of one DNA region on the stability of an adjoining region (telestability) was examined. Melting curves of three block DNA's, d(C15A15)·d(T15G15), d(C20A15)·d(T15G20), and d(C20A10)·d(T10G20) were analyzed in terms of the nearest neighbor Ising model. Comparisons of predicted and experimental curves were made in 0.01 M and 0.1 M sodium ion solutions. The nearest neighbor formalism was also employed to analyze block DNA transition in the presence of actinomycin, a G·C specific molecule. The results show that nearest neighbor base-pair interaction cannot predict the melting curves of the block DNA's. Adjustments in theoretical parameters to account for phosphate repulsion assuming a B conformation throughout the DNA's do not alter this conclusion. Changes in the theoretical parameters, which provide good overall agreement, are consistent with a substantial stabilization of the A·T region nearest the G·C block. The melting temperature T A·T for the average A·T pari in d(C20A10)·d(T10G20), with 10 A·T pairs, appears to be 4°C greater than TA·T for d(C15A15)·d(T15G15) and d(C20A15)·d(T15G20), both with 15 A·T pairs. Actinomycin bound to the G·C end effectively stabilizes the A·T end by 9°C. These results indicate a long-range contribution to the interactions governing DNA stability. A possible mechanism for these interactions will be discussed.
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    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Dielectric relaxation studies in the frequency range 100 Hz to 2 MHz of poly(γ-benzyl-L-glutamate) in dioxane have been carried out over a range of concentration 10-4-10-2g/g. The structure of aggregates is analyzed in terms of dipole moment and relaxation time. A critical concentration (≃ 10-3 g/g for the studied molecular weights) has been determined below which the aggregates are found to have linear head to tail type structure. Above the critical concentration a different structure of aggregates is apparent which could not be fully analyzed by these measurements alone. Possible forms of aggregation above the critical concentration are discussed. Formation of long range order which would lead to nematic liquid crystalline phase at higher concentrations has been discussed as one of the possible explanations for the observed behavior above the critical concentration.Maximum length of linear head to tail type aggregates for poly(γ-benzyl-L-glutamate) in dioxane as determined from these results correspond to an α-helix of molecular weight 210,000. A slight difference in the purity of dioxane has been shown to have an influence on the reproducibility of the state of aggregation as well as on the rate of disaggregation on dilution.
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  • 88
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    Biopolymers 15 (1976), S. 1585-1590 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Racemization in the synthesis of peptide intermediates and their polymers was investigated, using L-amino acid oxidase. The formation of N-hydroxysuccinimide esters from N-protected peptide acids yielded optically pure products in contrast to p-nitrophenyl and pentachlorophenyl active esters. The racemization in the polymerization step was found to be base sensitive. Partially racemized polymer can result from optically homogeneous monomer. Thus, the optical integrity of active monomer species carries no guarantee for that of the polymer.
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  • 89
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    Biopolymers 15 (1976), S. 1623-1635 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformations containing all trans peptide bonds have previously been proposed for N-methylleucine gramicidin-S and (di-N-methylleucine) gramicidin-S based on an evaluation of proton nuclear magnetic resonance parameters in a series of solvents. These gramicidin-S derivatives exhibit full biological activity despite the fact that the proposed solution conformations differ in backbone topology and relative orientation of the Phe and Orn side chains compared to gramicidin-S. The present authors discuss conformations for N-methylleucine gramicidin-S and (di-N-methylleucine) gramicidin-S which incorporate cis peptide bonds at L-Orn-L-N-MeLeu, where the gramicidin-S backbone is essentially retained, and the relative orientation of the Pro, Orn, Val, and Phe side chains correspond to those observed for gramicidin-S. A novel hydrogen-bond arrangement involving one carbonyl group interacting with two peptide protons (1 ←4 and 1 ←5 types) is proposed to stabilize the backbone conformation in the gramicidin-S derivatives. A recent report on the cyclic heptapeptide antibiotic, Ilamycin B1, shows the presence of cis peptide bonds at N-CH3 amino acids, as well as the novel hydrogen-bond arrangement presented above.
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  • 90
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The morphology of fibrin strongly depends on solvent medium, as shown by clotting experiments carried out in the presence of different salts. The clots were characterized by electron microscopy and spectrophotometric methods; the kinetics of gelation were determined.In the presence of electrolytes which strongly delay clotting, the strands are thin and few branching points are observed; opposite morphological changes are induced by salts which act as accelerating agents. On the basis of this correlation, and of previous data on the structure of fibrin, a kinetic model of the self-assembly process is outlined. It accounts well for the observed solvent effects on the morphology of the network.An important result emerging from our experiments is that the fibers undergo branching prior to gelation. Branching points arise from the defective growth of the fibers; a simple explanation of the occurrence of branching may be obtained by our self-assembly model.
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  • 91
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    Biopolymers 15 (1976), S. 2025-2041 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The equilibrium between the cis and trans forms of X-Pro peptide bonds can readily be measured in the 13C nmr spectra. In the present paper we investigate how observation of this equilibrium could be used as an nmr probe for conformational studies of flexible polypeptide chains. The experiments include studies by 13C nmr of a series of linear oligopeptides containing different X-L-Pro peptide bonds, with X = Gly, L-Ala, L-Leu, L-Phe, D-Ala, D-Leu, and D-Phe. Overall the study confirms that X-Pro peptide bonds can generally be useful as 13C nmr probes reporting the formation of nonrandom conformation in flexible polypeptide chains. It was found that the cis-trans equilibrium of X-Pro is greatly affected by the side chain of X and the configuration of the α-carbon atom of X. On the basis of these observations some general rules are suggested for a practical applications of the X-Pro nmr probes in conformational studies of polypeptide chains.
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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
    Notes: Random copolymers of L-glutamic acid and ortho-nitrobenzyl-L-glutamate were synthesized with different percentages of nitrobenzyl-L-glutamate, from 3 to 22%. These copolymers were studied by circular dichroism (CD) and potentiometric titrations in aqueous solutions in order to determine the variation of the stability of the secondary structure when the concentration of nitrobenzylglutamate varies in the copolymer. We observed that the stability increases with the concentration of glutamate. Such a stabilization could be due to either side-chain interactions or interactions between the aromatic side chain with the backbone. An intermolecular aggregation was observed when the percentage of nitrobenzylglutamate was sufficently important, but such an aggregation may be avoided if a dioxane/water mixture is used as a solvent.
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  • 93
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    Biopolymers 15 (1976), S. 2185-2199 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of γ-benzyl-L-glutamate NCA's polymerizations in dioxane as solvent are discussed. The partial orders respective to [A], the NCA concentration and [I0], the initial initiator concentration are given; the rate constants are deduced and a mechanism is proposed to justify a rate of polymerization Vp = k[A][I0]2.The dependence of the rate constants on the conformation of the growing chains is demonstrated; the acceleration is attributed to the ordered structures favorable to hydrogen bonding. The kinetics of aging have also been examined and discussed; it is shown that they cannot modify the kinetics of polymerization.The DPn were obtained on the same samples before and after debenzylation; it is proved that at any concentration, DPn ≃ [A0]/[I0].The molecular-weight distributions were obtained by chromatography and a polydispersity lower than 1.3 was deduced for each sample. The trimodal distribution, appearing as soon as [A0]/[I0] is larger than 3, is attributed to the existence of the three structures σ, β, and α. The weight fraction of each of the structures was correlated to the kinetics of polymerization.
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  • 94
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    Biopolymers 15 (1976), S. 1903-1915 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The crystal structure of native cellulose (Valonia) has been analyzed by electron diffraction. Possible models for the structure were refined by rigid-body least squares methods, which incorporated parameters defining the preferred orientation of the fibrils around their long axes in the cell wall lamellae. The structure was found to consist of an array of chains having the same sense (i.e., parallel), with packing parameters similar to those recently determined by X-ray diffraction. The eight-chain unit cell could be approximated adequately by a two-chain monoclinic unit cell with dimensions a = 8.18 Å, b = 7.84 Å, c = 10.38 Å (fiber axis), and γ = 97.04°; the space group is P21.
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  • 95
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    Biopolymers 15 (1976), S. 1939-1950 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The coil-to-helix transition temperatures of hydrogen bearing and deuterated poly(γ-benzyl-L-glutamate) in 1,3-dichlorotetrafluoroacetone/H2O and/D2O mixtures, respectively, have been determined. Together with previously obtained data for the conformational transition of this polypeptide in normal and deuterated dichloroacetic acid, these results have been used in an analysis of the effect of deuterium substitution on the intrinsic stability of the α-helical form of poly(γ-benzyl-L-glutamate). The findings, consistent for both solvent systems, showed that the deuterated polypeptide is some 5% more stable than the normal protonated poly(γ-benzyl-L-glutamate), while the polypeptide-active solvent interaction enthalpy is also slightly increased by deuterium substitution in the respective molecules. A consideration of available data for poly(β-benzyl-L-aspartate) reveals an anomaly with respect to the present analysis.
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  • 96
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    Biopolymers 15 (1976), S. 1669-1676 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Transient electric birefringence measurements on poly(L-lysine hydrobromide) in methanol-water mixtures have been carried out at various solvent compositions in the vicinity of the helix-coil transition region (from 87 to 98 vol % methanol). Anomalous birefringence transients were observed between 90 and 95 vol % methanol above a threshold field strength. A distinct difference between the responses to weak and strong electric fields was noticed over a narrow range of the solvent composition. The effects of polymer concentration and temperature on the field-strength dependence of the birefringence were studied at a solvent composition of 90 vol % methanol where the anomalous transients appeared most clearly. The double logarithmic plots of the steady-state specific birefringence versus the square of field strength for different concentrations and temperatures could be superimposed by shifting them horizontally along the abscissa. The threshold field strength which was determined from the shift factor decreased with decreasing concentration. The results provide further evidence that strong electric fields can cause a helix-coil transition in this system under favorable conditions.
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  • 97
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    Biopolymers 15 (1976), S. 1701-1715 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Derivatives of tetrapeptide sequences considered likely to form β-turns were investigated by the study of their proton magnetic resonances in methanol and in water. Differential broadening of N - H resonances by an added nitroxyl was used to indicate the presence of the sequestered N - H proton expected in β-turn conformations. Transfer of magnetic saturation from solvent water protons to N - H protons was also examined. The evidence is consistent with significant contributions by β-turn-like backbones to the conformational averages in methanol of the sequences Gly-L-Pro-D-Val-Gly, D(or L)-Val-L-Pro-Gly-Gly, and Gly-L-Pro-L-Asn-Gly, but not the sequence Gly-D-Ala-L-Val-Gly. It is suggested that a Type I turn, Likely in Gly-L-Pro-L-Asn-Gly derivatives, is characterized by sequestered N - H protons of both the third and fourth residues. For all of the peptide derivatives, save possibly Ac-L-Val-L-Pro-Gly-Gly-NHNH2, contributions from folded structures in water are not detectable by line-broadening experiments. However, the transfer of saturation experiments may be interpreted as indicating some degree of chain folding in water.
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  • 98
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    Biopolymers 15 (1976), S. 1717-1739 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper we use probabilistic arguments to derive and discuss the spatial distribution of molecules which are undergoing electrophoresis or centrifugation while at the same time they are switching back and forth between two configurational states. An exact solution is obtained for arbitrary values of the diffusion coefficients of the two isomerizing states. The traditional analytic method of solving this problem, namely, by use of “master equations,” is not completely satisfactory because one can find only the Fourier transform of the solution rather than the solution itself. Our treatment yields the answer one would get if it were feasible to perform the inversion of the Fourier transform.
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  • 99
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    Biopolymers 15 (1976), S. 1815-1824 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of sequential oligopeptides having simple nonpolar side chains, Nps-(L-Ala-L-Leu-Gly)n- OEt has been prepared by a stepwise fragment-condensation method using Nps-L-alanyl-L-leucylglycine N-hydroxysuccinimide ester, which was prepared by the Nps-N-carboxy α-amino-acid-anhydride method. The success of the synthesis of the peptide having a high-molecular weight, such as octadecapeptide, results from the highest solubility of the tripeptide unit, L-alanyl-L-leucylglycine. The sequential polypeptide having the same tripeptide sequence was also prepared by polycondensation of the tripeptide N-hydroxy-succinimide ester.
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  • 100
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    Biopolymers 15 (1976), S. 1841-1844 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
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