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  • Polymer and Materials Science  (2,626)
  • 04. Solid Earth::04.04. Geology::04.04.03. Geomorphology
  • 04. Solid Earth::04.04. Geology::04.04.99. General or miscellaneous
  • 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology
  • Wiley-Blackwell  (2,627)
  • Società Geologica Italiana  (6)
  • American Geophysical Union  (5)
  • Springer Berlin Heidelberg  (3)
  • Springer  (2)
  • Gondawa Research Group  (1)
  • 2010-2014  (18)
  • 1995-1999
  • 1975-1979  (2,626)
  • 1950-1954
  • 2012  (18)
  • 1976  (2,626)
Collection
Keywords
Publisher
Years
  • 2010-2014  (18)
  • 1995-1999
  • 1975-1979  (2,626)
  • 1950-1954
Year
  • 1
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    Crustal changes at Mt. Etna volcano accompanying the 2002–2003 eruption as inferred from a repeating earthquake analysis (2012)
    American Geophysical Union
    Details
    Publication Date: 2017-04-04
    Description: In this work, waveform variations in repeating volcanotectonic earthquakes occurring from 2001–2009 in the northeastern flank of Mt. Etna were studied. Changes in waveform were found mainly during 2002–2003; and consisted of a decreasing similarity in the coda of events in earthquake families, as revealed by cross-correlation analysis, and delays, increasing proportionally to the lapse time, detected by coda wave interferometry. Such variations, mainly evident at stations located in the north-eastern flank of the volcano, were likely due to medium changes taking place within this region. Localized medium velocity decreases were inferred to occur in 2002–2003, followed by successive increases. The velocity decrease was interpreted as being caused by the opening or enlargement of cracks, produced by intruding magma bodies, intense ground deformation, and/ or VT earthquake activity that accompanied the 2002–2003 Mt. Etna eruption. On the other hand, subsequent velocity increases were interpreted as resulting from healing processes.
    Description: Published
    Description: L18311
    Description: 1.4. TTC - Sorveglianza sismologica delle aree vulcaniche attive
    Description: JCR Journal
    Description: restricted
    Keywords: coda wave interferometry ; Etna ; VT earthquakes ; Pernicana fault ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 2
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    Geometry and modeling of an active offshore thrust-related fold system: the Amendolara Ridge, Ionian Sea, southern Italy (2012)
    Società Geologica Italiana
    Details
    Publication Date: 2017-04-04
    Description: On the Ionian Sea coast of southern Italy, spanning the transition from the Calabrian Arc to the Apennines, NE-directed motion of the thin-skinned frontal thrust belt of the Apennines toward the Apulian foreland reportedly ceased during the Early-Middle Pleistocene. The submarine extension of the frontal thrust belt is represented by the Amendolara ridge, which stretches for over 80 km to the SE beneath the Taranto Gulf. High-resolution marine geophysical data collected on the Amendolara ridge during the TEATIOCA_2011 cruise provided unequivocal constraints to assert active fault-related fold growth. Single-channel seismic (sparker) and acoustic CHIRP profiles, corroborated by multibeam mapping and shallow coring, form the novel dataset to constrain the near-bottom evolution. The new data were benchmarked to the crustal geometry by means of interpretation of existing multichannel seismic profiles.
    Description: Published
    Description: Arcavacata di Rende (CS)
    Description: 3.2. Tettonica attiva
    Description: open
    Keywords: Active fault-propagation folds ; Blind faults ; Seismogenic sources ; Jonian Sea ; 04. Solid Earth::04.04. Geology::04.04.01. Earthquake geology and paleoseismology ; 04. Solid Earth::04.04. Geology::04.04.03. Geomorphology ; 04. Solid Earth::04.04. Geology::04.04.04. Marine geology ; 04. Solid Earth::04.04. Geology::04.04.09. Structural geology ; 04. Solid Earth::04.04. Geology::04.04.10. Stratigraphy
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: Extended abstract
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  • 3
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    Geological evolution of a complex basaltic stratovolcano: (2012)
    Società Geologica Italiana
    Details
    Publication Date: 2017-04-04
    Description: An updated geological evolution model is presented for the composite basaltic stratovolcano of Mount Etna. It was developed on the basis of the stratigraphic setting proposed in the new geological map that was constrained by 40Ar/39Ar age determinations. Unconformitybounded stratigraphy allows highlighting four main evolutionary phases of eruptive activity in the Etna region. The Basal Tholeiitic Supersynthem corresponds to a period, from about 500 to 330 ka, of scattered fissure-type eruptions occurring initially in the foredeep basin and then in a subaerial environment. From about 220 ka, an increase in the eruptive activity built a lava-shield during the Timpe Supersynthem. The central-type activity occurred at least 110 ka ago through the Valle del Bove Supersynthem. The earliest volcanic centres recognized are Tarderia, Rocche and Trifoglietto and later Monte Cerasa, Giannicola, Salifizio and Cuvigghiuni. During the Stratovolcano Supersynthem, from about 57 ka ago, the intense eruptive activity of Ellittico volcano formed a roughly 3600 m-high stratocone that expanded laterally, filling the Alcantara and Simeto paleovalleys. Finally, effusive activity of the last 15 ka built the Mongibello volcano. Its eruptive activity is mainly concentrated in three weakness zones in which the recurrent magma intrusion generates flank eruptions down to low altitude. The four main evolutionary phases may furnish constraints to future models on the origin of Etna volcano and help unravel the geodynamic puzzle of eastern Sicily.
    Description: Published
    Description: 306-317
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: JCR Journal
    Description: reserved
    Keywords: Mount Etna, geological evolution, stratigraphy, ; 04. Solid Earth::04.04. Geology::04.04.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 4
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    Geological map of Etna volcano, 1:50,000 scale (2012)
    Società Geologica Italiana
    Details
    Publication Date: 2017-04-04
    Description: The new geological map of Etna volcano at 1:50,000 scale represents a significant progress in the geological studies of this volcano over the last 30 years, coming after Waltershausen’s map published around the mid of 19th century, the first geological map of a large active volcano, and the ROMANO et alii (1979) map published about a century later, both at 1:50,000 scale. Lithostratigraphy was used for mapping volcanic units and then Unconformity Bounded Units were applied to group lithostratigraphic units into synthems. In addition, lithosomes were exploited to better represent the spatial localization of different eruptive centres according to their morphology. On the whole, we identified 27 lithostratigraphic units, grouped into 8 synthems, and 9 volcanoes. In detail, effusive and explosive deposits generated by each eruption of Mongibello and, partially, Ellittico volcanoes were mapped as flow rank. This stratigraphic framework represents the best synthesis of the geological evolution of Etna volcano using the main unconformities recognized within its complex volcanic succession. In addition, we constrain the Etna volcanic succession and its lithostratigraphic units chronologically by radioisotope age determinations. On the basis of the outlined synthemic units, it was possible to divide Etna’s volcanic succession into 4 supersynthems, which correspond to 4 well-defined and spatially localized phases. The detailed reconstruction of the past eruptive activity allowed compiling the most accurate dataset in particular of the Holocene eruptions of Etna volcano, which will enable significantly improving the volcanic hazard assessment, together with petrological interpretation of erupted magmas and geophysical modelling of the volcano plumbing system.
    Description: Published
    Description: 265-291
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: JCR Journal
    Description: reserved
    Keywords: Mount Etna, geological map, basaltic composite ; 04. Solid Earth::04.04. Geology::04.04.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 5
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    Flank instability structure of Mt. Etna inferred by a magnetotelluric survey (2012)
    American Geophysical Union
    Details
    Publication Date: 2017-04-04
    Description: This paper presents a magnetotelluric (MT) survey of the unstable eastern flank of Mt. Etna. We take thirty soundings along two profiles oriented in the N-S and NW-SE directions, and from these data recover two 2D resistivity models of the subsurface. Both models reveal three major layers in a resistive-conductive-resistive sequence, the deepest extending to 14 km bsl. The shallow layer corresponds to the volcanic cover, and the intermediate conductive layer corresponds to underlying sediments segmented by faults. These two electrical units are cut by E-W-striking faults. The third layer (basement) is interpreted as mainly pertinent to the Apennine-Maghrebian Chain associated with SW-NE-striking regional faults. The detailed shapes of the resistivity profiles clearly show that the NE Rift is shallow-rooted ( 0–1 km bsl), thus presumably fed by lateral dikes from the central volcano conduit. The NW-SE profile suggests by a series of listric faults reaching up to 3 km bsl, then becoming almost horizontal. Toward the SE, the resistive basement dramatically dips (from 3 km to 10 km bsl), in correspondence with the Timpe Fault System. Several high-conductivity zones close to the main faults suggest the presence of hydrothermal activity and fluid circulation that could enhance flank instability. Our results provide new findings about the geometry of the unstable Etna flank and its relation to faults and subsurface structures.
    Description: This paper presents a magnetotelluric (MT) survey of the unstable eastern flank of Mt. Etna. We take thirty soundings along two profiles oriented in the N-S and NW-SE directions, and from these data recover two 2D resistivity models of the subsurface. Both models reveal three major layers in a resistive-conductive-resistive sequence, the deepest extending to 14 km bsl. The shallow layer corresponds to the volcanic cover, and the intermediate conductive layer corresponds to underlying sediments segmented by faults. These two electrical units are cut by E-W-striking faults. The third layer (basement) is interpreted as mainly pertinent to the Apennine-Maghrebian Chain associated with SW-NE-striking regional faults. The detailed shapes of the resistivity profiles clearly show that the NE Rift is shallow-rooted ( 0–1 km bsl), thus presumably fed by lateral dikes from the central volcano conduit. The NW-SE profile suggests by a series of listric faults reaching up to 3 km bsl, then becoming almost horizontal. Toward the SE, the resistive basement dramatically dips (from 3 km to 10 km bsl), in correspondence with the Timpe Fault System. Several high-conductivity zones close to the main faults suggest the presence of hydrothermal activity and fluid circulation that could enhance flank instability. Our results provide new findings about the geometry of the unstable Etna flank and its relation to faults and subsurface structures.
    Description: Published
    Description: B03216
    Description: 1.5. TTC - Sorveglianza dell'attività eruttiva dei vulcani
    Description: 3.2. Tettonica attiva
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: JCR Journal
    Description: restricted
    Keywords: Etna ; magnetotelluric ; flank instability ; volcano ; 04. Solid Earth::04.01. Earth Interior::04.01.99. General or miscellaneous ; 04. Solid Earth::04.02. Exploration geophysics::04.02.99. General or miscellaneous ; 04. Solid Earth::04.02. Exploration geophysics::04.02.04. Magnetic and electrical methods ; 04. Solid Earth::04.04. Geology::04.04.99. General or miscellaneous ; 04. Solid Earth::04.04. Geology::04.04.09. Structural geology ; 04. Solid Earth::04.05. Geomagnetism::04.05.99. General or miscellaneous ; 04. Solid Earth::04.07. Tectonophysics::04.07.99. General or miscellaneous ; 04. Solid Earth::04.07. Tectonophysics::04.07.07. Tectonics ; 04. Solid Earth::04.08. Volcanology::04.08.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 6
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    Spatial vent opening probability map of Etna volcano (Sicily, Italy) (2012)
    Springer Berlin Heidelberg
    Details
    Publication Date: 2017-04-04
    Description: We produce a spatial probability map of vent opening (susceptibility map) at Etna, using a statistical analysis of structural features of flank eruptions of the last 2 ky. We exploit a detailed knowledge of the volcano structures, including the modalities of shallow magma transfer deriving from dike and dike-fed fissure eruptions analysis on historical eruptions. Assuming the location of future vents will have the same causal factors as the past eruptions, we converted the geological and structural data in distinct and weighted probability density functions, which were included in a non-homogeneous Poisson process to obtain the susceptibility map. The highest probability of new eruptive vents opening falls within a N-S aligned area passing through the Summit Craters down to about 2,000 ma.s.l. on the southern flank. Other zones of high probability follow the North-East, East-North-East, West, and South Rifts, the latter reaching low altitudes (∼400 m). Less susceptible areas are found around the faults cutting the upper portions of Etna, including the western portion of the Pernicana fault and the northern extent of the Ragalna fault. This structuralbased susceptibility map is a crucial step in forecasting lava flow hazards at Etna, providing a support tool for decision makers.
    Description: This study was performed with the financial support from the V3-LAVA project (DPC-INGV 2007–2009 contract).
    Description: Published
    Description: 2083–2094
    Description: 1.5. TTC - Sorveglianza dell'attività eruttiva dei vulcani
    Description: 3.2. Tettonica attiva
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: 3.6. Fisica del vulcanismo
    Description: 4.3. TTC - Scenari di pericolosità vulcanica
    Description: JCR Journal
    Description: restricted
    Keywords: Flank eruption ; Dike ; Volcano structure ; Susceptibility map ; Spatial clustering ; Back analysis ; 04. Solid Earth::04.01. Earth Interior::04.01.99. General or miscellaneous ; 04. Solid Earth::04.04. Geology::04.04.99. General or miscellaneous ; 04. Solid Earth::04.04. Geology::04.04.09. Structural geology ; 04. Solid Earth::04.07. Tectonophysics::04.07.99. General or miscellaneous ; 04. Solid Earth::04.07. Tectonophysics::04.07.07. Tectonics ; 04. Solid Earth::04.08. Volcanology::04.08.99. General or miscellaneous ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk ; 05. General::05.01. Computational geophysics::05.01.99. General or miscellaneous ; 05. General::05.01. Computational geophysics::05.01.04. Statistical analysis ; 05. General::05.02. Data dissemination::05.02.03. Volcanic eruptions ; 05. General::05.08. Risk::05.08.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 7
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    How do volcanic rift zones relate to flank instability? Evidence from collapsing rifts at Etna (2012)
    American Geophysical Union
    Details
    Publication Date: 2017-04-04
    Description: Volcanic rift zones, characterized by repeated dike emplacements, are expected to delimit the upper portion of unstable flanks at basaltic edifices. We use nearly two decades of InSAR observations excluding wintertime acquisitions, to analyze the relationships between rift zones, dike emplacement and flank instability at Etna. The results highlight a general eastward shift of the volcano summit, including the northeast and south rifts. This steadystate eastward movement (1-2 cm/yr) is interrupted or even reversed during transient dike injections. Detailed analysis of the northeast rift shows that only during phases of dike injection, as in 2002, does the rift transiently becomes the upper border of the unstable flank. The flank's steady-state eastward movement is inferred to result from the interplay between magmatic activity, asymmetric topographic unbuttressing, and east-dipping detachment geometry at its base. This study documents the first evidence of steady-state volcano rift instability interrupted by transient dike injection at basaltic edifices.
    Description: Partially funded by INGV and the Italian DPC (DPC-INGV project V4 “Flank”). ERS and ENVISAT SAR data were provided by ESA through the Cat-1 project no. 4532 and the GEO Supersite initiative. The DEM was obtained from the SRTM archive. ERS-1/2 orbits are courtesy of the TU-Delft, The Netherlands. SAR data processing has been done at IREACNR, partially carried out under contract “Volcanic Risk System (SRV)” funded by the Italian Space Agency (ASI).
    Description: Published
    Description: L20311
    Description: 1.3. TTC - Sorveglianza geodetica delle aree vulcaniche attive
    Description: 1.5. TTC - Sorveglianza dell'attività eruttiva dei vulcani
    Description: 1.10. TTC - Telerilevamento
    Description: 3.2. Tettonica attiva
    Description: 3.5. Geologia e storia dei vulcani ed evoluzione dei magmi
    Description: 3.6. Fisica del vulcanismo
    Description: 4.3. TTC - Scenari di pericolosità vulcanica
    Description: JCR Journal
    Description: restricted
    Keywords: flank instability ; rift zones ; 04. Solid Earth::04.03. Geodesy::04.03.99. General or miscellaneous ; 04. Solid Earth::04.03. Geodesy::04.03.01. Crustal deformations ; 04. Solid Earth::04.03. Geodesy::04.03.06. Measurements and monitoring ; 04. Solid Earth::04.03. Geodesy::04.03.07. Satellite geodesy ; 04. Solid Earth::04.03. Geodesy::04.03.09. Instruments and techniques ; 04. Solid Earth::04.04. Geology::04.04.99. General or miscellaneous ; 04. Solid Earth::04.04. Geology::04.04.06. Rheology, friction, and structure of fault zones ; 04. Solid Earth::04.04. Geology::04.04.09. Structural geology ; 04. Solid Earth::04.07. Tectonophysics::04.07.99. General or miscellaneous ; 04. Solid Earth::04.07. Tectonophysics::04.07.02. Geodynamics ; 04. Solid Earth::04.07. Tectonophysics::04.07.05. Stress ; 04. Solid Earth::04.07. Tectonophysics::04.07.07. Tectonics ; 04. Solid Earth::04.08. Volcanology::04.08.99. General or miscellaneous ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques ; 04. Solid Earth::04.08. Volcanology::04.08.08. Volcanic risk ; 05. General::05.08. Risk::05.08.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 8
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    Active extension in Val d’Agri area, Southern Apennines, Italy: implications for the geometry of the seismogenic belt. (2012)
    Wiley-Blackwell
    Details
    Publication Date: 2020-02-24
    Description: Integration of geologic, geomorphologic and seismologic data sets is used to reconstruct the recent tectonic evolution and active deformation pattern in the Val d’Agri area, located in the seismically active axial sector of the Southern Apennines (Italy). The western portion of the Apennines thrust belt has been affected by Pliocene–Quaternary extension during easterly roll-back and crustal delamination of the Adriatic slab. The bulk of Quaternary extension has been accommodated bySW-dipping oblique and normal faults,which have attained mature morphologic and structural features and, nowadays, separate mountain ranges from intermontane basins. However, in the present seismogenic belt, coseismic faulting locally occurs on NE-dipping structures, which might cut the inherited Pleistocene landscape. In theVal d’Agri basin, in spite of the large Early–Middle Pleistocene, displacement occurred on SW-dipping faults bordering its eastern flank, our investigations show that the recent basin evolution has been controlled by a NE-dipping fault system (Monti della Maddalena fault system, MMFS). This fault system cuts across the Monti della Maddalena range, west of the Agri valley and has not yet created an evident tectonic landscape. Notwithstanding, fault motion since the Middle Pleistocene might explain geomorphologic and hydrographic anomalies of the Agri river and its valley, where fault-controlled subsidence has captured the river course and produced an aggrading plain within a regional uplift context. Recent and ongoing motion is documented by fault scarplets in loose deposits, 14C ages of palaeosols and the spatial relation with low to moderate instrumental seismicity. Results from fault kinematic analysis are compatible with fault-plane solutions of local and regional seismic events, and indicate ∼NE–SW oriented extension. Recognition of the MMFS as a potential seismogenic fault increases the longitudinal extent of the NE-dipping, morphologically immature seismic sources in the Southern Apennines and argues against the range-bounding fault model for active extension in the region. The regional size of the NE-dipping seismogenic belt may result from impingement of a mantle wedge beneath the Apenninic chain and possibly track the external front of crustal delamination.
    Description: Published
    Description: 591-609
    Description: 3.2. Tettonica attiva
    Description: JCR Journal
    Description: reserved
    Keywords: active tectonics ; crustal deformation ; earthquakes ; geomorphology ; normal faulting ; Southern Italy ; 04. Solid Earth::04.04. Geology::04.04.01. Earthquake geology and paleoseismology ; 04. Solid Earth::04.04. Geology::04.04.03. Geomorphology ; 04. Solid Earth::04.04. Geology::04.04.09. Structural geology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 9
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    Source mechanism of long-period events recorded by a high-density seismic network during the 2008 eruption on Mount Etna (2012)
    American Geophysical Union
    Details
    Publication Date: 2017-04-04
    Description: One hundred twenty-nine long-period (LP) events, divided into two families of similar events, were recorded by the 50 stations deployed on Mount Etna in the second half of June 2008. During this period lava was flowing from a lateral fracture after a summit Strombolian eruption. In order to understand the mechanisms of these events, we perform moment tensor inversions. Inversions are initially kept unconstrained to estimate the most likely mechanism. Numerical tests show that unconstrained inversion leads to reliable moment tensor solutions because of the close proximity of numerous stations to the source positions. However, single forces cannot be accurately determined as they are very sensitive to uncertainties in the velocity model. Constrained inversions for a crack, a pipe or an explosion then allow us to accurately determine the structural orientations of the source mechanisms. Both numerical tests and LP event inversions emphasise the importance of using stations located as close as possible to the source. Inversions for both families show mechanisms with a strong volumetric component. These events are most likely generated by cracks striking SW–NE for both families and dipping 70° SE (family 1) and 50° NW (family 2). For family 1 events, the crack geometry is nearly orthogonal to the dikelike structure along which events are located, while for family 2 the location gave two pipelike bodies that belong to the same plane as the crack mechanism. The orientations of the cracks are consistent with local tectonics, which shows a SW–NE weakness direction. The LP events appear to be a response to the lava fountain occurring on 10 May 2008 as opposed to the flank lava flow.
    Description: Published
    Description: B01304
    Description: 1.4. TTC - Sorveglianza sismologica delle aree vulcaniche attive
    Description: 3.1. Fisica dei terremoti
    Description: JCR Journal
    Description: reserved
    Keywords: Etna Volcano ; long-period events ; source mechanism ; location ; plumbing systems ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 10
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    New geophysical insight into the dynamics of Stromboli volcano (Italy) (2012)
    Gondawa Research Group
    Details
    Publication Date: 2017-04-04
    Description: A 56-hour gravity sequence, recorded in the crater area of Stromboli volcano, is presented. Data were acquired during a period of “normal” strombolian activity. High-frequency gravity anomalies (up to 20 microGal; T = tens of seconds) are observed. Comparison with independent data reveals that these changes reflect the response of the gravimeter excited by seismic waves during strombolian explosions. Correlated changes in the energy distribution over time appear in the continuous wavelet transforms of gravity and RMS-tremor, but over different scales, corresponding to periods centered at about 50 and 25 minutes, for gravity and tremor, respectively. We infer that the rate of fresh magma supply to the shallow feeding system controls the energy distribution over time of the coupled components in gravity and RMS-tremor signals. In particular, the gravity signal (with an average amplitude of 1-2 microGal) could be induced by temporary accumulations, at shallow depth, of the volatiles discharged by quiescent degassing. Changes in the rate of explosions from the summit craters correlate with changes in the amplitude of the coupled gravity and volcanic tremor oscillations, implying that, even though the slug-genesis process behind the explosions occurs at deeper levels, it is also controlled by the rate of gas-rich magma supply from below. Negative gravity anomalies of about 20 microGal, over intervals of some hours, are also observed, separated by intervals of about 24 hours. They could be induced by increases in magma vescicularity in the uppermost part of the conduit plexus, a view supported by (i) changes in the time/space distribution of tremor amplitudes and (ii) increases in spattering activity from a summit vent, both occurring during the development of the negative gravity anomalies. The processes behind mild Strombolian explosions do not trigger measurable gravity changes. Nevertheless, the slug ascent before a major explosion could induce a precursory gravity signal.
    Description: Published
    Description: 290-299
    Description: 3.6. Fisica del vulcanismo
    Description: JCR Journal
    Description: reserved
    Keywords: Stromboli ; Gravity changes ; Volcanic tremor ; Explosion rate ; 04. Solid Earth::04.03. Geodesy::04.03.05. Gravity variations ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 04. Solid Earth::04.08. Volcanology::04.08.07. Instruments and techniques
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 11
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    Slug Flow: Modeling in a Conduit and Associated Elastic Radiation (2012)
    Springer
    Details
    Publication Date: 2017-04-03
    Description: Among the eruptive styles, the Strombolian activity is one of the more easy to study because of its repetitive behavior. For this reason large amount of data can be comfortably collected. Strombolian volcanoes are like natural laborato- ries repeating the same experiment (individual explosions) many times each day. The development of quantitative models of eruptive dynamics is driven by the comparison of experimental ob- servations and synthetic data obtained through mathemat- ical, numerical or analogue modeling. Since Strombolian activity offers a profuse amount of interesting seismic signals, during the last decades there has been growing attention on seismological techniques aimed at retrieving the conduit geometry and the eruption dynamics from the seismological recordings. One of these techniques, the source function inversion, is able to re- trieve a summary of the forces acting on the volcanic con- duit during the VLP event generation [5]. The comparison of observed source functions with synthetic ones, obtained through numerical modeling, allow us to put constraints on the proposed models. Quantitative models, able to fit seismological observa- tions, are a powerful tool for interpreting seismic record- ings and therefor the seismological monitoring of active volcanoes.
    Description: Published
    Description: 1.4. TTC - Sorveglianza sismologica delle aree vulcaniche attive
    Description: restricted
    Keywords: Strombolian activity ; Slug flow ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring ; 05. General::05.01. Computational geophysics::05.01.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: book chapter
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  • 12
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    Multiparametric Approach in Investigating Volcano-Hydrothermal Systems: the Case Study of Vulcano (Aeolian Islands, Italy) (2012)
    Springer
    Details
    Publication Date: 2017-04-04
    Description: Seismic activity, ground deformation, and soil and fumarole temperatures acquired during 2004–2007 at Vulcano (Aeolian Islands) are analysed and the time relations among the different time series are discussed. Changes in temperature of fumarolic gases took place during four ‘‘anomalous’’ periods (November 2004–March 2005; October 2005–February 2006; August–October 2006; July–December 2007) at the same time as an increasing number of volcano-seismic events. In particular, the temperatures at high temperature vents and at steam heated soil ranged in time from 180 to 440 C and from 20 to 90 C, respectively. The maximum daily number of volcano-seismic events was 57, reached during the second anomalous period. This seismicity, characterised by focal depth generally lower than 1 km below sea level (b.s.l.) and composed of different kinds of events associated to both resonance and shear failure processes, is related to the shallow dynamics of the hydrothermal system. During the analysed period, very few volcano-tectonic earthquakes took place and tilt recordings showed no sharp or important changes. In light of such observations, the increases in both temperature and volcano-seismic events number were associated to increases in the release of gas from a deep and stable magma body, without magma intrusions within the shallow hydrothermal system. Indeed, a greater release of gas from depth leads to increased fluid circulation, that can promote increases in volcano-seismic events number by both fracturing processes and resonance and vibration in cracks and conduits. The different trends observed in the measured geochemical and geophysical series during the anomalous periods can be due to either time changes in the medium permeability or a changing speed of gas release from a deep magma body. Finally, all the observed variations, together with the changing temporal distribution of the different seismic event kinds, suggest that the hydrothermal system at Vulcano can be considered unsteady and dynamic.
    Description: Published
    Description: 167–182
    Description: 1.5. TTC - Sorveglianza dell'attività eruttiva dei vulcani
    Description: JCR Journal
    Description: reserved
    Keywords: Volcano seismolog ; soil and fumarole temperatures ; tilt data ; hydrothermal system ; Vulcano Island ; volcanic unrest ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.08. Volcanology::04.08.01. Gases ; 04. Solid Earth::04.08. Volcanology::04.08.06. Volcano monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 13
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    Inferences on the source of long-period seismicity at Campi Flegrei from polarization analysis and reconstruction of the asymptotic dynamics (2012)
    Springer Berlin Heidelberg
    Details
    Publication Date: 2017-04-04
    Description: In the present paper, we analyse long-period (LP) events and seismic noise recorded at Campi Flegrei during the uplift episode of 2004–2006. The results of a detailed polarization analysis indicate that the large number of LPs detected during the seismic crisis were accompanied by a sustained activity consisting of very low-energy volcanic signals. These weak volcanic signals, which are usually absent in ambient noise recorded in the studied area, and LP events have similar properties, namely they are radially polarized towards the same LP source. The large dataset analysed allows us to study the statistics of the polarization, leading to the extraction of the average properties of the volcanic signals. An estimate of the complexity of the system can be provided by the degrees of freedom necessary to describe the asymptotic dynamics in a reconstructed phase space. This analysis shows that both LPs and low-energy signals can be described by a low-dimensional dynamical system, while ambient noise unrelated to volcanic activity is higher dimensional. Based on these observations, we interpret the phenomena observed during the seismic crisis in the framework of the theory of self-oscillating systems, in which LPs and low-energy signals represent self-oscillations generated by a persistent hydrothermal source.
    Description: Published
    Description: 1537-1551
    Description: 1.4. TTC - Sorveglianza sismologica delle aree vulcaniche attive
    Description: JCR Journal
    Description: restricted
    Keywords: Campi Flegrei, Long-period events, Self-sustained oscillations ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 14
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    Morphometric analysis in the offshore of the southern Taranto Gulf: unveiling the structures controlling the Late Pleistocene-Holocene bathymetric evolution (2012)
    Società Geologica Italiana
    Details
    Publication Date: 2017-04-04
    Description: The present study is focused on a morphometric analysis of high resolution multibeam data (10m, 5m and, locally, 2m resolution), that were acquired during the oceanographic TEATIOCA 2011 campaign along a sector of the Ionian margin of northern Calabria. The integration of morphometric analysis with sparker and chirp data allowed to unveil basic but robust information about: 1. hierarchy of the fault systems controlling the bathymetric evolution; 2. the interplay between tectonic and erosional processes in sea-floor modeling; 3. uplift rates; 4. tilting processes.
    Description: Published
    Description: Arcavacata di Rende (CS)
    Description: 3.2. Tettonica attiva
    Description: open
    Keywords: fault modeling ; erosional marine terraces ; 04. Solid Earth::04.04. Geology::04.04.01. Earthquake geology and paleoseismology ; 04. Solid Earth::04.04. Geology::04.04.03. Geomorphology ; 04. Solid Earth::04.04. Geology::04.04.04. Marine geology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: Extended abstract
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  • 15
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    Deformed Pleistocene marine terraces along the Ionian sea margin of southern Italy: Unveiling blind fault-related folds contribution to coastal uplift (2012)
    Società Geologica Italiana
    Details
    Publication Date: 2017-04-04
    Description: Morphotectonic analysis and fault numeric modeling of uplifted marine terraces along the southern half of the Taranto Gulf , between the Sibari and San Nicola plains (Fig. 1), allow us to place quantitative constraints on Middle Pleistocene-Holocene deformation in the Southern Apennines.
    Description: Published
    Description: Arcavacata di Rende (CS)
    Description: 3.2. Tettonica attiva
    Description: open
    Keywords: Marine terraces ; Regional uplift ; Fault propagation folds ; Fault modeling ; 04. Solid Earth::04.04. Geology::04.04.01. Earthquake geology and paleoseismology ; 04. Solid Earth::04.04. Geology::04.04.02. Geochronology ; 04. Solid Earth::04.04. Geology::04.04.03. Geomorphology ; 04. Solid Earth::04.04. Geology::04.04.09. Structural geology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: Extended abstract
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  • 16
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    Correlation of welded ignimbrites on Pantelleria (Strait of Sicily) using paleomagnetism (2012)
    Springer Berlin Heidelberg
    Details
    Publication Date: 2017-10-06
    Description: Although the oldest volcanic rocks exposed at Pantelleria (Strait of Sicily) are older than 300 ka, most of the island is covered by the 45–50 ka Green Tuff ignimbrite, thought to be related to the Cinque Denti caldera, and younger lavas and scoria cones. Pre-50 ka rocks (predominantly rheomorphic ignimbrites) are exposed at isolated sea cliffs, and their stratigraphy and chronology are not completely resolved. Based on volcanic stratigraphy and K/Ar dating, it has been proposed that the older La Vecchia caldera is related to ignimbrite Q (114 ka), and that ignimbrites F, D, and Z (106, 94, and 79 ka, respectively) were erupted after caldera formation. We report here the paleomagnetic directions obtained from 23 sites in ignimbrite P (133 ka) and four younger ignimbrites, and from an uncorrelated (and loosely dated) welded lithic breccia thought to record a caldera-forming eruption. The paleosecular variation of the geomagnetic field recorded by ignimbrites is used as correlative tool, with an estimated time resolution in the order of 100 years. We find that ignimbrites D and Z correspond, in good agreement with recent Ar/Ar ages constraining the D/Z eruption to 87 ka. The welded lithic breccia correlates with a thinner breccia lying just below ignimbrite P at another locality, implying that collapse of the La Vecchia caldera took place at ~130–160 ka. This caldera was subsequently buried by ignimbrites P, Q, F, and D/Z. Paleomagnetic data also show that the northern caldera margin underwent a ~10° west–northwest (outwards) tilting after emplacement of ignimbrite P, possibly recording magma resurgence in the crust.
    Description: Published
    Description: 341-357
    Description: 1V. Storia eruttiva
    Description: JCR Journal
    Description: restricted
    Keywords: Pantelleria ; Ignimbrite ; Caldera formation ; Paleomagnetism ; Paleosecular variation of the geomagnetic field ; 04. Solid Earth::04.04. Geology::04.04.99. General or miscellaneous ; 04. Solid Earth::04.04. Geology::04.04.08. Sediments: dating, processes, transport ; 04. Solid Earth::04.04. Geology::04.04.10. Stratigraphy ; 04. Solid Earth::04.04. Geology::04.04.11. Instruments and techniques ; 04. Solid Earth::04.05. Geomagnetism::04.05.99. General or miscellaneous ; 04. Solid Earth::04.05. Geomagnetism::04.05.02. Geomagnetic field variations and reversals ; 04. Solid Earth::04.05. Geomagnetism::04.05.03. Global and regional models ; 04. Solid Earth::04.05. Geomagnetism::04.05.06. Paleomagnetism ; 04. Solid Earth::04.05. Geomagnetism::04.05.07. Rock magnetism ; 04. Solid Earth::04.05. Geomagnetism::04.05.08. Instruments and techniques
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 17
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    Erosion of the continental lithosphere at the cusps of the Calabrian arc: Evidence fromSreceiver functions analysis (2012)
    American Geophysical Union
    Details
    Publication Date: 2022-05-04
    Description: Mediterranean tectonics has been characterized by an irregular, complex temporal evolution with episodic rollback and retreat of the subducted plate followed by period of slow trench-migration. To provide insight into the geodynamics of the Calabrian arc, we image the characteristics and lithospheric structure of the convergent, Apulian and Hyblean forelands at the cusps of the arc. Specifically we investigate the crustal and lithospheric thicknesses using teleseismic S-to-p converted phases, applied to the Adria-Africa plate margin for the first time. We find that the Moho in the Apulian foreland is nearly flat at ∼30 km depth, consistent with previous P receiver functions results, and that the Hyblean crustal thickness is more complex, which can be understood in terms of the nature of the individual pieces of carbonate platform and pelagic sediments that make up the Hyblean platform. The lithospheric thicknesses range between 70–120 km beneath Apulia and 70–90 km beneath Sicily. The lithosphere of the forelands at each end of the Calabrian arc are continental in nature, buoyant compared to the subducting oceanic lithosphere and have previously been interpreted as mostly undeformed carbonate platforms. Our receiver function images also show evidence of lithospheric erosion and thinning close to Mt. Etna and Mt. Vulture, two volcanoes which have been associated with asthenospheric upwelling and mantle flow around of the sides the slab. We suggest that as the continental lithosphere resists being subducted it is being thermo-mechanically modified by toroidal flow around the edges of the subducting oceanic lithosphere of the Calabrian arc.
    Description: Published
    Description: L23301
    Description: JCR Journal
    Description: restricted
    Keywords: continental lithosphere ; 04. Solid Earth::04.04. Geology::04.04.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 18
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    New insights on the Holocene marine transgression in the Bahía Camarones (Chubut, Argentina) (2012)
    Società Geologica Italiana
    Details
    Publication Date: 2022-06-10
    Description: The stratigraphic reconstruction of the northern sector of the Bahía Camarones (Chubut, Argentina) allowed to improve our understanding of the Holocene marine transgression in the area. The first phase of the maximum of the transgression, is interpreted as dominated by the high rate of eustatic rise of sea level until ca. 6-7 ka BP possibly associated to sedimentary starvation as suggested by fossil accumulation. After this first phase, the general trend indicates a progressive fall of the relative sea level after the Middle Holocene high stand as documented in other parts of south America Atlantic coast. Our data, coupled with the robust radiocarbon data set available for the area from literature, indicate three main local steps of coastal aggradation between ca. 6600 and 5400 yr BP (ca. 7000-5600 yr cal BP), ca. 3300 and 2000 yr BP (ca. 3100-1700 yr cal BP), and ca. 1300-500 yr BP (ca. 1000-300 yr cal BP). A significant age gap in coastal aggradation is present between ca. 5300 and 4400 yr BP (ca. 5600-4500 yr cal BP), and perhaps between ca 2000 and 1300 yr BP (ca. 1700-1000 yr cal BP). These can be linked to phases of local sea level fall and/or phases of sedimentary starvation and/or changes in drift transport which can have produced local coastal cannibalization. However, no conclusive data can be advanced. Data obtained from careful measurements of sea level markers represented by the top of marsh and fluvial terraces indicate lower values for the sea level estimation compared with the data set previously proposed for the area. This stigmatizes the fact that field-oriented works are still the priority in the Patagonia coast along with accurate age measurement, especially for obtaining the fundamental information we need for predicting the environmental impact, in these coastal areas, from accelerate sea level rise as effect of global warming.
    Description: Published
    Description: 19-31
    Description: 1.10. TTC - Telerilevamento
    Description: 3.7. Dinamica del clima e dell'oceano
    Description: JCR Journal
    Description: reserved
    Keywords: Relative sea level ; sea level markers ; Patagonia ; Holocene ; 03. Hydrosphere::03.01. General::03.01.06. Paleoceanography and paleoclimatology ; 04. Solid Earth::04.04. Geology::04.04.02. Geochronology ; 04. Solid Earth::04.04. Geology::04.04.03. Geomorphology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 19
    Electronic Resource
    Electronic Resource
    Stability of steady states in nucleic acid poly[d(A-T)] synthesis and the stirred flow reactor (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1-14 
    Details
    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.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1976.360150102
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  • 20
    Electronic Resource
    Electronic Resource
    Circular dichroism of corticotropin, fragment 1-24, and model compounds. An assessment of the contributions of the peptide chromophore and aromatic residues (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 43-59 
    Details
    ISSN: 0006-3525
    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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1976.360150106
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  • 21
    Electronic Resource
    Electronic Resource
    Polynucleotide circular dichroism calculations: Use of an all-order classical coupled oscillator polarizability theory (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 131-152 
    Details
    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.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1976.360150110
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  • 22
    Electronic Resource
    Electronic Resource
    Raman studies of bovine serum albumin (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 203-218 
    Details
    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.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1976.360150114
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  • 23
    Electronic Resource
    Electronic Resource
    Low-frequency Raman spectra of lysozyme (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 219-225 
    Details
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1976.360150115
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  • 24
    Electronic Resource
    Electronic Resource
    Thickness and density of protein films by optical mixing spectroscopy (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 257-263 
    Details
    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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1976.360150204
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  • 25
    Electronic Resource
    Electronic Resource
    Preferential solvent binding and change in conformation of bovine serum albumin in 2-chloroethanol-water mixed solvents (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 293-299 
    Details
    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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1976.360150207
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  • 26
    Electronic Resource
    Electronic Resource
    Masthead (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976) 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1976.360150101
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  • 27
    Electronic Resource
    Electronic Resource
    Cooperative ligand binding by ferrihemoglobin: An experimental artifact? (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 403-414 
    Details
    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.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1976.360150216
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  • 28
    Electronic Resource
    Electronic Resource
    1H Nuclear magnetic resonance studies of histidine-containing di- and tripeptides. Estimation of the effects of charged groups on the pKa value of the imidazole ring (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 393-401 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1976.360150215
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  • 29
    Electronic Resource
    Electronic Resource
    Masthead (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976) 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1976.360150201
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  • 30
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    Interpretation of hypochromic and hyperchromic intensity changes in the Raman spectra of polypeptides and polynucleotides undergoing transition (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 241-255 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1976.360150203
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  • 31
    Electronic Resource
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    Length and dipole moment of TMV by laser signal-averaging transient electric birefringence (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 301-315 
    Details
    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.
    Additional Material: 6 Ill.
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    High-resolution nmr study of yeast tRNACUALeu and the native and denatured conformers of yeast tRNAUUGLeuSubmitted by BFR in partial fulfillment of the requirements for the Ph.D. degree in chemistry at the University of California, Riverside. (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 325-336 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Masthead (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976) 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/bip.1976.360150301
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    On the application of polyelectrolyte limiting laws to the helix-coil transition of DNA. IV. Dependence of helix stability on the concentration of divalent metal ions (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 457-468 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    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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  • 35
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    An X-ray study of poly(L-prolyl-L-α-phenylglycyl-L-proline) (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 503-506 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 1 Ill.
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    Effect of saturation of the ion atmosphere polarization on the orientation factor of the electric birefringence of rodlike polyelectrolytes (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 583-587 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1976.360150313
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    Measurement of circular dichroism using a thin cell (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 591-594 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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  • 38
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    Masthead (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976) 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/bip.1976.360150401
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  • 39
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    Molecular forces in ribosomes and polynucleotide complexes (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 649-653 
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    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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    The effect of binding on the melting temperature of biopolymers (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 999-1000 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 41
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    Calculations of the conformation of mono-, di-, and regular polynucleotides (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1009-1013 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1976.360150516
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  • 42
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    Calculation of the molecular parameters of the α-helix-coil and β-structure-coil transitions (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1061-1080 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 16 Ill.
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    Co-oligopeptides of aromatic amino acids and glycine with a variable distance between the aromatic residues. III. Co-oligopeptides of L-phenylalanine, L-tryptophan, and glycine: Synthesis and ultraviolet absorption properties (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1103-1117 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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.
    Additional Material: 3 Ill.
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    Spatial electron distribution and population analysis of amides, carboxylic acid, and peptides, and their relation to empirical potential functions (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1167-1200 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    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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    Conformational properties of the sequential polyproline analogs poly(Pro-Aze-Pro) and poly(Aze-Pro-Aze) (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1233-1242 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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.
    Additional Material: 7 Ill.
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  • 46
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    Rapid characterization of protein molecular weights and hydrodynamic structures by quasielastic laser-light scattering (1976)
    New York : Wiley-Blackwell
    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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    Conformations of protected oligo(γ-methyl-L-glutamates) at the air-water interface (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1425-1430 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 5 Ill.
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    The role of alcohols in the polymerization of NCA's by alkaline alkoxides. Dualism of the polymerization mechanism (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1431-1435 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    Evidence for long-range interactions in DNA. Analysis of melting curves of block polymers d(C15A15)·d(T15G15), d(C20A15)·d(T15G20), and d(C20A10)·d(T10G20) (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1461-1479 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
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    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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    Effect of concentration on the aggregation of poly(γ-benzyl-L-glutamate) in dioxane: Critical concentration and maximum length for linear head to tail aggregates (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1543-1554 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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    Racemization in the synthesis of sequential polypeptides using N-hydroxysuccinimide esters (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1585-1590 
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    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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    N-methylleucine gramicidin-S and (di-N-methylleucine) gramicidin-S conformations with cisL-Orn-L-N-MeLeu peptide bonds (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1623-1635 
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    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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    Conversion of fibrinogen to fibrin. The correlation between clotting kinetics and morphology of fibrin polymerized in different solvent media (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1979-1990 
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    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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    The X-Pro peptide bond as an nmr probe for conformational studies of flexible linear peptides (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2025-2041 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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.
    Additional Material: 4 Ill.
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    Conformational studies in aqueous solution on random copolymers of L-glutamic acid and ortho-nitrobenzyl-L-glutamate. Circular dichroism and potentiometric titration studies (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2101-2119 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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.
    Additional Material: 9 Ill.
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    Kinetics of γ-benzyl-L-glutamate NCA's polymerizations and molecular-weight distributions on corresponding polymers (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2185-2199 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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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    Electron diffraction of Valonia cellulose. A quantitative interpretation (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1903-1915 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The 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.
    Additional Material: 4 Ill.
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    Relative stability of the α-helix of deuterated poly(γ-benzyl-L-glutamate) (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1939-1950 
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    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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    Electric field-induced conformational change of poly(L-lysine) studied by transient electric birefringence (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1669-1676 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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    Studies of peptide conformation: Backbone folding of tetrapeptide derivatives in methanol and water (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1701-1715 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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    The spatial distribution of moving macromolecules undergoing isomerization (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1717-1739 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 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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    Synthesis of sequential oligopeptides and polypeptide having the sequence of L-alanyl-L-leucylglycine (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1815-1824 
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    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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    Comparison of different theoretical descriptions of helix-coil transitions in DNA (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1841-1844 
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    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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    Time-dependent Hartree calcuations of nucleic acid hypochromism (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1873-1875 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Cooperative disordering of single-stranded polynucleotides through copper crosslinking (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1879-1902 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal transitions of single-stranded polynucleotides are noncooperative. In contrast, Cu(II) cooperatively disorders the single-stranded helical structures of poly(A) and poly(C), as demonstrated by ORD and UV spectral changes as a function of the Cu2+ activity, and by a dramatic chain-length dependence of the spectral changes. Equilibrium dialysis binding studies indicate that the cooperative disordering is paralleled by a somewhat less cooperative binding process.The difference between the thermal- and Cu(II)-induced transition is explained by the following mechanism. (1) Cu(II) initially binds in a noncooperative fashion to phosphate. (2) The Cu(II) so bound forms a second bond to a nonadjacent base site on the same polymer strand or another strand. These intramolecular and intermolecular crosslinks to the bases are responsible for the disordering. (3) The initial crosslinks formed provide nuclei for the cooperative formation of additional crosslinks, producing cooperative spectral changes paralleled by cooperative binding.A comparison of the spectral and binding transitions indicates that there is appreciable noncooperative binding of copper to phosphate, which produces no spectral changes in the presence of added electrolyte. This comparison also indicates that each copper crosslink disorders several bases. The formation of intermolecular crosslinks is demonstrated by a polymer concentration dependence of the disordering. The formation of intramolecular crosslinks can be deduced from the fact that the “cooperative unit” required to explain the differences between the hexamer, which does not readily form intramolecular crosslinks, and the polymer is considerably larger than the cooperative unit determined from the polymer results.The poly(A) disordering transition is less symmetrical than that of poly(C), particularly at low polymer concentrations. These results, together with other phenomena, are explained by a greater flexibility of poly(A), which favors the formation of small intramolecular loops.
    Additional Material: 9 Ill.
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    Influence of ribose 2′-O-methylation on GpC conformation by classical potential energy calculations (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1951-1964 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potential energy calculations were employed to examine the effect of ribose 2′-O-methylation on the conformation of GpC. Minimum energy conformations and allowed conformational regions were calculated for 2′MeGpC and Gp2′MeC. The two lowest energy conformations of 2′MeGpC and Gp2′MeC are similar to those of GpC itself. The helical RNA conformation (sugar pucker-C(3′)-endo, ω′ and ω,g-g-, bases-anti) is the global minimum, and a helix-reversing conformation with ω′, ω in the vicinity of 20°, 80° is next in energy. However, subtle differences between the three molecules are noted. When the substitution is on the 5′ ribose (Gp2′MeC), the energy of the helical conformation is less than that of GpC, due to favorable interactions of the added methyl group. When the substitution is at the 3′ ribose (2′MeGpC) these stabilizing interactions are outweighed by steric restrictions, and the helical conformation is of higher energy than for GpC. Furthermore, the statistical weight of the 2′MeGpC g- g- helical region is substantially less than the corresponding weight for Gp2′MeC. In addition, 2′MeGpC′s methoxy group is conformationally restricted to a narrow range centered at 76°. This group has a broadly allowed region between 50 and 175° in Gp2′MeC. These differences occur because the appended methyl group in 2′MeGpC is located in the interior of the helix cylinder, as it would be in polynucleotide, while it hangs unimpeded in Gp2′MeC. These findings suggest that 2′-O-methylation has both stabilizing and destabilizing influences on the helical conformation of RNA. For 2′MeGpC the destabilizing steric hindrance imposed by the nature of the guanine base dominates.
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    Nmr studies of the molecular conformations in the linear oligopeptides H-(L-Ala)n-L-Pro-OH (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2043-2057 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular conformations of the linear oligopeptides H-(L-Ala)n-L-Pro-OH, with n = 1,2 and 3, have been investigated. 13C nmr observation of the equilibrium between the cis and trans forms of the Ala-Pro peptide bond indicated the occurrence of nonrandom conformations in solutions of these flexible peptides. The formation of the nonrandom species containing the cis form of the Ala-Pro bond was found to depend on the deprotonation of the carboxylic acid group of proline, the solvent, and the ionic strength in aqueous solution. The influence of intramolecular hydrogen bonding on the relative conformational energies of the species containing the cis and trans Ala-Pro peptide bond was studied by comparison of the peptides H-(Ala)n-Pro-OH with analogous molecules where hydrogen bond formation was excluded by the covalent structure. In earlier work a hydrogen bond between the protonated terminal carboxylic acid group and the carbonyl oxygen of the penultimate amino acid residue had been suggested to stabilize conformations including trans proline. For the systems described here this hypothesis can be ruled out, since the cis:trans ratio is identical for molecules with methyl ester protected and free protonated terminal carboxylic acid groups of proline. Direct evidence for hydrogen bond formation between the deprotonated terminal carboxylic acid group and the amide proton of the penultimate amino acid residue in the molecular species containing cis proline was obtained from 1H nmr studies. However, the cis:trans ratio of the Ala-Pro bond was not affected by N-methylation of the penultimate amino acid residue, which prevents formation of this hydrogen bond. Overall the experimental observations lead to the conclusion that the relative energies of the peptide conformations including cis or trans proline are mainly determined by intramolecular electrostatic interactions, whereas in the molecules considered, intramolecular hydrogen bonding is a consequence of specific peptide backbone conformations rather than a cause for the occurrence of energetically favored species. Independent support for this conclusion was obtained from model consideration which indicated that electrostatic interactions between the terminal carboxylic acid group and the carbonyl oxygen of the penultimate amino acid residue could indeed account for the observed relative conformational energies of the species containing cis and trans proline, respectively.
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    Masthead (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976) 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/bip.1976.360151101
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    Packing analysis of carbohydrates and polysaccharides. IV. A new method for detailed crystal structure refinement of polysaccharides and its application to V-amyloseThe work described in this paper was presented at the “Makromolekulares Kolloquium Freiburg”, in Freiburg, West Germany, March 1975. (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2121-2136 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is described for predicting and solving crystal structures of linear homopolysaccharides. The method is based on the refinement of the structure with respect to either stereochemical constraints or x-ray diffraction intensities. In the refinement process, all conformational and packing features of the molecule, such as bond lengths, bond angles, conformational angles, nonbonded contacts, hydrogen bonds, etc., can be allowed to vary until the structure reaches both a conformation and crystalline packing that are in minimum disagreement with the stereochemical restraints and the diffraction data. In this fashion, both packing and conformational features of the structure can be simultaneously refined, and not separately as has been the custom in the past. The refinement procedure is based on a method of constrained optimization which possesses improved characteristics of reaching a solution and avoiding false minima, in comparison with least squares methods. The procedure is, in addition, capable of easily finding molecules of solvent of crystallization. The method was applied to further refining the previously solved crystal structure of V-amylose. The results indicated that contrary to the previously found six-fold molecular symmetry in the P212121 space group, the V-amylose molecule exhibits only two-fold symmetry with the asymmetric unit consisting of three glucose residues in one-half turn of the helix. The three residues are nonequivalent principally due to unequal rotational positions of the hydroxymethyl groups. The crystal structure of V-amylose predicted from stereochemical refinement was identical in all details with that obtained from refining against X-ray data. The excellent agreement with the diffraction data was indicated by the crystallographic disagreement index R = 0.25.
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    Conformational features of 2′-O-methyl-adenosylyl-adenosine (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2167-2184 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to obtain information about the conformational features of a 2′-O-methylated polyribonucleotide at the nearest neighbor level, a detailed nuclear magnetic resonance study of AmpA was undertaken. AmpA was isolated from alkali hydrolysates of yeast RNA, and proton spectra were recorded at 100 MHz in the Fourier transform mode in D2O solutions, 0.01 M, pH 5.4 and 1.5 at 25°C. 31P spectra were recorded at 40.48 MHz. Complete, accurate sets of nmr parameters derived for each nucleotidyl unit by simulation iteration methods.The nmr data were translated into conformational parameters for all the bonds using procedures developed in earlier studies from these laboratories. It is shown that AmpA exists in aqueous solution with a flexible molecular framework, which shows preferences for certain orientations. The ribose rings exist as a 2E ⇄ 3E equilibrium with the  - pA ribose showing a bias for the 3E pucker. The C(4′) - C(5′) bonds of both nucleotidyl units show significant preference (75-80%) to exist in gg conformation. The dominant conformer (80%) about C(5′) - O(5′) of the 5′-nucleotidyl unit is g′g′. Even though an unambiguous determination of the orientation of the 3′-phosphate group cannot be made, tentative evidence shows that it preferentially occupies g+ domains [O(3′) - P trans to C(3′) - C(2′)] in which the H(3′)  - C(3′) - O(3′) - P(3′) dihedral angle is about 31°. There is reasonable evidence that the 2′-O-methyl preferentially occupies the domain in which the O(2′) - CH3 bond is trans to C(2′) - C(1′).Lowering of pH to 1.5, which results in protonation of both the adenine moieties, causes destacking of AmpA. Such destacking is accompanied by small, but real, perturbations in the conformations about most of the bonds in the backbone.A detailed comparison of the solution conformations of ApA and AmpA clearly shows that 2′-O-methylation strongly influences the conformational preference about the C(3′) - O(3′) bond of the 3′-nucleotidyl unit, in addition to inducing small changes in the overall ribophosphate backbone conformational equilibria. The effect of 2′-O-methylation is such that the C(3′) - O(3′) is forced to occupy preferentially the g+ domain rather than the normally preferred g- domain [O(3′) - P trans to C(3′) - C(4′)] in ApA. The data on ApA and AmpA further reveal that the extent of stacking interaction is less in AmpA compared to ApA.It is suggested that stacked species of AmpA exist as right-handed stacks where the magnitude of ω and ω′ about O(5′) - P and P - O(3′) is about 290°. The reason for the lesser degree of stacking in AmpA compared to ApA is intramolecular interaction between 2′-O-methyl and the flexible O(3′) - P - O(5′) bridge, the interaction causing some perturbation in the magnitudes of ω/ω′, causing destacking. The destacking will lead to an increase in χCN by a few degrees, causing an increase in 2E populations; the latter in turn will shift the 3′ phosphate group from g- to g+ domains. In short, a coupled series of conformational events is envisioned at the onset of destacking, made feasible by the interaction between the 2′-O-methyl group and the swivel O(3′) - P - O(5′) bridge.
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    Interaction of sodium decyl sulfate with poly(L-ornithine) and poly(L-lysine) in aqueous solution (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2263-2275 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The binding isotherms of sodium decyl sulfate to poly(L-ornithine), poly(D,L-ornithine), and poly(L-lysine) at neutral pH were determined potentiometrically. The nature of a highly cooperative binding in all three cases suggests a micelle-like clustering of the surfactant ions onto the polypeptide side groups. The hydrophobic interaction between the nonpolar groups overshadows the coulombic interaction between the charged groups. The titration curves can be interpreted well by the Zimm-Bragg theory. The average cluster size of bound surfactant ions is sufficiently large to promote the β-structure of (L-Lys)n even at a very low binding ratio of surfactant to polypeptide residue, whereas the onset of the helical structure for (L-Orn)n begins after about 7 surfactant ions are bound to two turns of the helix. The CD results are consistent with this explanation.
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    Extrapolation of light-scattering data to determine the molecular weight of T7 DNACommunication presented at the XVII Meeting of the Spanish Society of Physics and Chemistry, Alicante, October 1975 (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2287-2290 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1976.360151115
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    Synthesis of a cross-linked polypentapeptide of tropoelastin (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2337-2351 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of a cross-linked polypentapeptide (an insoluble product) by means of a cross-linking reaction between a lysine-containing (1%) polypentapeptide and a glutamic acid-containing (2%) polypentapeptide is described, following description of the synthesis and polymerization of the corresponding pentapeptide p-nitrophenyl esters. The pentapeptide p-nitrophenylesters - H-Val1-Pro2-Gly3-Val4-Gly5-ONp, H-Val1-Pro2-Gly3-Lys4(ε-Z)-Gly5-ONp, and H-Val1-Pro2-Gly3-Glu4-Gly5-ONp - prior to polymerizing and the polypentapeptides prior to cross-linking were analyzed by proton and carbon-13 magnetic resonance. The cross-linking reaction was achieved in the coacervate state by intermolecular primary amide bond formation. The coupling reagent was a water-soluble carbodiimide (1-cyclohexyl-3-(2-N-methylmorpholinoethyl)-carbodiimide-p-toluenesulfonate).
    Additional Material: 3 Ill.
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    The application of polyelectrolyte limiting laws to the helix-coil transition of DNA. VI. The numerical value of the axial phosphate spacing for the coil form (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2385-2390 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is concluded on the basis of comparison of polyelectrolyte theory with published data that the mean phosphate spacing b along the contour axis of an unfolded polynucleotide single strand is in the range 3-4 Å (polyelectrolyte parameter ξ ≈ 2), regardless of temperature, base composition, or extent of stacking. This result is consistent with the low-angle X-ray scattering measurements of Gulik, Inoue, and Luzzati on poly(C). No conclusion may be drawn from this value of b concerning the structure of the chain skeleton or the spatial arrangement of the bases other than that the chain is far from an all-trans local conformation (for which b would be about 6-7 Å, the length of a nucleotide unit). The structural implications, or lack thereof, are discussed in detail in the following paper.
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    URL: http://dx.doi.org/10.1002/bip.1976.360151206
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    Study of thermal denaturation of lysozyme and other globular proteins by light-scattering spectroscopy (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2421-2437 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The technique of intensity correlation light-scattering spectroscopy has been used to accurately determine the extent of physical swelling of lysozyme, ribonuclease, and chymotrypsinogen produced by thermal denaturation. The change in hydrodynamic radius is deduced from direct measurements of the diffusion coefficient, carried out in the temperature range 20° to 70°C at various values of pH in the range 1.0 to 3.0 at ionic strengths of from 0.01 M to 0.2 M. An average radius increase of 18% is observed for lysozyme and ribonuclease, with an estimate of 26% for chymotrypsinogen. Analysis of the pH dependence of the transition temperature leads to the conclusion that the lysozyme charge increases by approximately +2e during unfolding. We have applied this value of the charge increase along with the 18% average radius increase to estimate the electrostatic contribution to the free-energy change for denaturation of lysozyme. The results are consistent with the experimental observation that the transition temperature is nearly independent of ionic strength.
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    Vibrational analysis of peptides, polypeptides, and proteins. II. β-Poly(L-alanine) and β-poly(L-alanylglycine) (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2465-2483 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The normal vibration frequencies of poly(L-alanine) and poly(L-alanylglycine) in the antiparallel chain-pleated sheet structure have been calculated, using the force field for polyglycine I from the previous paper (Biopolymers 15, 2439-2464) plus additional force constants for the methyl group. The agreement with observed ir and Raman bands is very good. This substantiates the excellent transferability of the force field, since polyglycine I was shown to have a rippled-sheet structure. The amide I and amide II mode splittings are very well accounted for by transition dipole coupling, showing that subtle structural differences are sensitively manifested through this mechanism.
    Additional Material: 9 Tab.
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    Conformational energy calculations of enzyme-substrate complexes of lysozyme. I. Energy minimization of monosaccharide and oligosaccharide inhibitors and substrates of lysozyme (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2485-2521 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational energy calculations were performed on monosaccharide and oligosaccharide inhibitors and substrates of lysozyme to examine the preferred conformations of these molecules. A grid-search method was used to locate all of the low-energy conformational regions for N-acetyl-β-D-glycosamine (NAG), and energy minimization was then carried out in each of these regions. Three stable positions for the N-acetyl group have ben located, in two of which the plane of the amide unit is normal to the mean plane of the pyranosyl ring. Nine local energy minima were located for the  - CH2OH group. The positions of the two vicinal cis  - OH groups are determined predominantly by interactions with either the  - CH2OH or the N-acetyl group. The most stable conformations of β-N-acetylmuramic acid (NAM) were determined from the study of the low-energy conformations of NAG. In the two stable orientations for the D-lactic acid side chain, the O - C - C′ plane (C′ being the carbon atom of the terminal carboxyl group) was found to be normal to the mean plane of the pyranosyl ring. The low-energy positions for the COOH group of NAM are determined mainly by interactions with neighboring groups.The conformational preferences of the α-anomers of NAG and NAM were also explored. The calculated conformation of the N-acetyl group for α-NAG was quite close to that determined by X-ray analysis. Two of the three lowest energy conformations of α-NAM are similar to the corresponding conformations of the β-anomer. A third low-energy structure, which has a hydrogen bond from the NH of the N-acetyl group to the C=O of the lactic acid group, corresponds very closely to the X-ray structure of this molecule.The preferred conformations of the disaccharides NAG-NAG, NAM-NAG and NAG-NAM were also investigated. Two preferred orientations of the reducing pyranosyl ring relative to the nonreducing ring were found for all of these disaccharides, both of which are close to the extended conformation. In one of these conformations, a hydrogen bond can form between the OH group attached to C3 of the reducing sugar and the ring oxygen of the preceding residue. Each conformation can be stabilized further by a hydrogen bond between the CH2OH (donor) of residue i + 1 and the C=O of residue i (acceptor). The interactions that determine conformations for all oligosaccharides containing both NAG and NAM are shown to be exclusively intraresidue and nearest neighbor interactions, so that it is possible to predict all stable conformations of oligosaccharides containing NAG and NAM in any sequence.
    Additional Material: 11 Ill.
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    An electrostatic model for collagen fibrils. The interaction of reconstituted collagen with Ca++, Na+, and Cl- (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1439-1460 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A model for the electrostatic properties of hydrated collagen fibrils, based on the concept of a “penetrable” protein, has been evaluated through studies of collagen fibrils that had been chemically modified to change their electrostatic properties,. A value of 0.28 ± 0.07 ml/g was found for the intrafibrillar space sterically inaccessible to a molecule that had an equivalent spherical radius of 4.5 Å.The net intrinsic charge on reconstituted collagen is +14 mol/mol under physiological conditions, but decreases, at constant pH, with ionic strength. A value of 7.1 for the pK of the histidine and α-amino groups in reconstituted collagen was obtained through the application of the electrostatic model to this effect.The values obtained for calcium binding parameters for collagen fibrils, under solution conditions in which the nonspecific electrostatic properties of collagen fibrils were eliminated (3-5 M tetramethyl ammonium chloride), were in agreement with values obtained in 0.16 M NaCl solutions calculated through the use of the electrostatic theory. These are 0.73 ± 0.23 and 56.2 ± 12.3 sites per molecule with intrinsic association constants of 1101 ± 386 and 21.4 ± 5.2 M-1, respectively.The model also predicts that an average 4-mV potential difference exists between the reconstituted collagen fibrils and physiological solutions, and that collagen fibrils under such conditions have piezoelectriclike properties.The pattern of interaction of ions with collagen fibrils is such that an allosteric mechanism for the catalytic step in the mineralization of collagen is a possibility.
    Additional Material: 7 Ill.
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    Vibrational spectrum of the unordered polypeptide chain: A Raman study of feather keratin (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1513-1528 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Raman spectra of native and solubilized feather keratin have been obtained, and the amide I and amide III regions have been analyzed by band resolution techniques. The amide I region of the native form indicates that at least 64% of the protein has an antiparallel chain pleated sheet structure, the remainder being unordered. For the solubilized keratin all of the protein is in an unordered state. The amide III region is not as easily analyzed into component contributions. Normal vibration analyses on N-acetyl-L-alanine-N-methylamide support the conclusion that the amide III region is not as satisfactory as the amide I region in characterizing unordered structures. Even in the latter case caution must be used, since the observed amide I band is an average over the conformational distribution in the particular unordered system.
    Additional Material: 11 Ill.
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    The optical birefringence of DNA solutions induced by oscillatory electric and hydrodynamic fields (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1555-1572 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optical birefringence induced in DNA solutions by both oscillating hydrodynamic fields (flow birefringence) and oscillating electric fields (Kerr effect) is measured over a wide frequency range. The observed frequency response of the birefrigence is compared with theories for rigid ellipsoidal particles and for Gaussian chains. DNA at 6 × 105 molecular weight is found to exhibit rigid particle hydrodynamic behavior, while DNA at 5 × 106 molecular weight behaves like a flexible chain. Characterization of the hydrodynamic relaxation spectra for the DNA's by oscillatory flow birefringence allows precise comparison between theory and the experimental Kerr effect response. The dielectric model for DNA contains both permanent and dispersionless induced dipole moments. The dielectric behavior of DNA has the character of a permanent dipole but with anomalous low-frequency dispersion in the Kerr effect. The existing theories do not adequately describe this dispersion. A fluctuation dipole mechanism with relaxation times comparable to those associated with the hydrodynamic motion could possibly demonstrate the observed polar behavior.
    Additional Material: 8 Ill.
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    The effects of isolated N-methylated residues on the conformational characteristics of polypeptides (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1615-1622 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Conformational energies have been estimated for the tripeptide fragments L-Ala-N-methyl-L-Ala-L-Ala, L-Ala-L-Ala-N-methyl-L-Ala, L-Ala-Sar-L-Ala, and L-Ala-Gly-N-methyl-L-Ala. The peptide bonds connecting L-Ala and Gly with N-methyl-L-Ala and L-Ala with Sar were permitted to adopt the planar cis as well as the usual trans conformation. Contour maps of the conformational energies of the central residue in these tripeptide fragments are presented and compared to the conformational energy maps previously calculated for unmethylated L-Ala and Gly surrounded by residues which are also unmethylated. In generl it is observed that L-Ala and Gly residues that are either N-methylated in their conformational freedom relative to the same residues in an unmethylated polypeptide chain.
    Additional Material: 10 Ill.
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    Circular dichroism and structure of the complex of acridine orange with poly(L-glutamic acid) (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1655-1667 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Circular dichroism and absorption spectra have been measured on solutions of acridine orange and poly(L-glutamic acid) mixed at two molar ratios of carboxyl group-to-dye, P/D 25 and 0.8, and at different pH's. Characteristic circular dichroism is induced at the absorption bands of acridine orange when the P/D is 25 and the solution is acidic. Another type of circular dichroism is manifest at neutral and alkaline pH when P/D is 0.8. For the induction of the former type of circular dichroism, a helical array of acridine-orange dimers bound to the α-helix is postulated, in which the dye molecular planes are almost perpendicular to the helical axis. Assuming the helical geometry and optical parameters, combined with the observed magnitude of transition electric moment, the rotatory strength of the complex is calculated to the zeroth order approximation, and the observed circular dichroism spectra have been reproduced.
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    Nmr studies of aqueous solutions of tetra and branched peptides. I. Sequence determination of amino-acid residues and the assignment of peptide hydrogen signals (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1643-1653 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sequential determination of glycyl residues (and in several cases different amino-acid residues) in tetra and branched peptides using the nmr technique is reported. The method is based on changes in the nmr spectra of (1) the peptide hydrogens of the different residues and (2) the methylene groups of the glycyl residues, as a result of increasing the rate of the base-catalyzed exchange reaction of the peptide hydrogens. Hence, the spectral changes are pH dependent. However, the exact pH dependence is a function of the location of the residue in the peptide molecule. Thus, it is possible to determine the sequence of the amino-acid residues by studying the changes in the spectra with pH.For peptide molecules of known sequences, the above method can be used for unequivocal assignment of the peptide hydrogen signals.
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    Induced circular dichroism of acridine orange bound to double-stranded RNA and transfer RNA (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1693-1699 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The induced circular dichroism (CD) in the visible region of acridine orange bound to the double-stranded RNA from cytoplasmic polyhedrosis virus and to yeast tRNA has been measured as a function of RNA phosphate-to-dye ratio (P/D), under the conditions of 0.01 M Na+ at pH 7.0. The shape of the CD spectrum of acridine orange bound to the double-stranded RNA was quite different from the spectrum of the dye bound to DNA. The CD spectral features of acridine orange bound to the double-stranded regions in tRNA closely resembled those of the double-stranded RNA-dye complex, suggesting that the dyes bind similarly to the two RNA's. It was further found that the CD spectrum of the tRNA-dye complex at sufficiently high P/D ratios, which is assignable to monomeric, intercalated dye to the base-paired parts in tRNA, is also distinct from the corresponding spectrum of the DNA-dye complex.
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    Dinucleoside monophosphates. I. Optical properties and conformation in solution with one base charged (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1755-1773 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A least squares analysis of the titration properties of several dinucleoside monophosphates enables calculation of the pK's for protonation. These pK's are used to resolve the spectral properties of dinucleoside monophosphates with one base charged from the apparent spectral properties of a dinucleoside monophosphate in aqueous solution. This method is applied to dinucleoside monophosphates containing adenosine and/or cytidine. Results of CD, nmr, and CD-temperature dependence measurements are presented. The results indicate that singly protonated dimers of these nucleosides stack as do their unprotonated analogs. It is suggested that this is true for all dimers with one base charged.
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    An easy method for retrieving atomic coordinates from CPK space-filling molecular models (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1825-1833 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Connectors for CPK space-filling molecular models have been supplemented with pointed steel wires (φ = 1.59 mm) of appropriate lengths and positions to represent atomic bonds. For illustration purposes, the polypeptide backbone of glucagon was equipped with such wire-core connectors and given a possible conformation. The molecular model was packed into a cubic box and, using a clinical instrument, X-ray films were taken from three orthogonal directions. Atomic coordinates on the films were then corrected to real-space coordinates.This method for retrieving atomic coordinates from space-filling models of modium-sized polypeptides is easy and can be done wih equipement available everywhere. Coordinates obtained in this way should be useful as starting points for energy minimization, for the calculation of frictional coefficients, and in attempts to solve crystal structures by X-ray diffraction, using molecular replacement methodology.
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    Viscosity/molecular-weight relationship of poly(α-L-glutamic acid) in water and in water/dioxane mixtures (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1857-1862 
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    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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    URL: http://dx.doi.org/10.1002/bip.1976.360150920
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    The dependence of the swelling of elastin on elongation, and its importance in fluorescence probe analysis (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1853-1856 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1976.360150919
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    Polypeptide modeles of collagen. Solution properties of (Gly-Pro-Sar)n and (Gly-Sar-Pro)n (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1877-1877 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    URL: http://dx.doi.org/10.1002/bip.1976.360150924
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    Threshold effects observed in conformation changes induced by electric fields (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1917-1928 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Single-stranded polynucleotides are used as model systems for the investigation of conformational changes induced by electric fields. It is demonstrated that the single-strand helix-coil transition in poly(A), poly(dA), and poly(C) can be induced by application of high electric fields. The transition is measured by UV absorbance using polarized light at an angle of 54.8° with respect to the vector of the electric field and by electrodichroism. A linear increase of the absorbance, reflecting the helix-to-coil transition, is observed at increasing field strength. When ions are added to the polymer, electric fields do not induce conformation changes, unless a threshold value of the electric field strength E0 is exceeded. At field strengths above this threshold, the degree of transition is a linear function of the increase in field strength. The threshold values E0 show a linear increase with the logarithm of the ion concentration. Bivalent ions cause thresholds at much lower ion concentrations than mo-novalent ions. The shielding efficiency of ions is correlated to the binding affinity of these ions to the polymer.The conformation changes induced by the field and the existence of thresholds can be explained on the basis of dissociation field effects. Similar threshold effects may be expected for other macromolecules as well as for membrane structures and may be important in the regulation of bioelectricity.
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    The effect of changes in salt concentration and pH on the interaction between glycosaminoglycans and cationic polypeptides (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 1965-1977 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Circular dichroism (CD) spectroscopy has been used to investigate the effects of changes in salt concentration and pH on the interactions between basic polypeptides and connective tissue glycosaminoglycans in dilute aqueous solution. The polypeptides undergo conformation-directing interactions in the presence of glycosaminoglycans, which are subject to transitions as the ionic strength and pH are varied. For poly(L-lysine), the conformational change due to interaction breaks down as the ionic strength (monovalent ions) is increased. Based on the ionic strength at which disruption occurs, the glycosaminoglycans can be placed in order of increasing strength of interaction: chondroitin 6-sulfate, hyaluronic acid, chondroitin 4-sulfate, heparin, and dermatan sulfate. Prior to the conformational transition, scattering effects are observed, indicating the development of larger aggregates. Each glycosaminoglycan induces α-helicity for poly(L-arginine), which does not break down as the ionic strength is increased, indicating a stronger interaction for this polypeptide. The pH-induced transitions are in the pH range 2.5-3.8 and are probably related to deionization of carboxyl groups. For poly(L-lysine) the conformational effect is disrupted at low pH. For poly(L-arginine), the transitions are not complete, but appear to correspond to an increase in scattering.
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    Synthesis and characterization of an ionizable polyhexapeptide collagen model (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2005-2024 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(Lys(HBr)-Gly-Pro-Pro-Gly-Pro) has been synthesized and studied by circular dichroism (CD) spectroscopy. It is apparently the first polyhexapeptide collagen model reported with an ionizable side chain. The monomer (ε-(p-nitrobenzyloxycarbonyl)-Lys-Gly-Pro-Pro-Gly-Pro-p-nitrophenyl-ester) was prepared by a stepwise strategy employing active esters. Polymerization in N,N-dimethyl formamide, followed by removal of the Lys side chain protection with HBr/acetic acid, gave a polydisperse product. Fractionation was accomplished by gel filtration chromatography. The polydisperse material had a molecular weight (Mr = 5-17,000). High molecular weight fractions from triple helices under concentrated conditions at 2°C. The triple helical structure gives a CD pattern very similar to that of collagen and its triple helical analogs. However, unlike collagen, the polyhexapeptide undergoes spontaneous dissociation at temperatures substantially below the melting temperature from a triple helical form to single chains. This process is promoted at low concentrations, high temperature, neutral pH, and low molecular weight, and is apparently due, in large part, to unfavorable ionic side-chain interactions. In addition to this relatively slow “ionic” dissociation the triple helical polypeptide may be thermally dissociated in a manner similar to collagen. The thermal denaturation is a relatively fast process compared with ionic dissociation.A high molecular weight fraction (3 × Mr = 48,000) was found to melt at 42°C at neutral pH but increased to 54°C at pH 12 where the lysyl side chains are predominantly deprotonated. Furthermore, reconstitution of triple helices appeared to be more readily achieved at high pH. Thus it is concluded that ionic repulsion between side chains causes destabilization of the triple helix and hinders reconstitution.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1976.360151011
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    Étude thermodynamique de la transition hélice-pelote statistique en solvants mixtes de différents esters de l'acide poly(L-glutamique) (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 2059-2079 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Helix-coil transition of poly(γ-methyl-L-glutamate), poly(γ-ethyl-L-glutamate), and poly(γ-benzyl-L-glutamate) has been studied in mixed solvents by calorimetry, polarimetry, and viscometry. The experimental data have allowed the evaluation of solvation enthalpy Δhb, equilibrium constant K for hydrogen bond formation between the active solvent component and CO and NH groups, and the cooperativity parameter σ. The conformational transition of polypeptides in solution in a mixed solvent containing enough active solvent to maintain the coiled conformation has been produced by dilution with the helix-supporting solvent for the measurements of enthalpy of transition Δhs. The average value for Δhs is 3550 ± 300 J/mol and is practically independent of the nature of the side chain for the dichloroacetic acid-ethylene dichloride solvent pair at 25°C. A noticeable concentration effect exists in the case of poly(γ-benzyl-L-glutamate). The helical conformation is less stable for poly(γ-ethyl-L-glutamate), and this is explained by a steric effect hindering the access of dichloroacetic acid to side chains. Constant K has been calculated using polarimetric data and also from values of Δhs obtained at different temperatures using the Bixon and Lifson theory on the one hand and that of Sayama and coworkers on the other hand. Values of σ for poly(γ-ethyl-L-glutamate) have been calculated according to both theories mentioned, and the results show that the two sets of values are quite similar. The constant σ depends on the nature of the active solvent, on temperature, and on the binary-solvent composition. These conclusions are confirmed by viscometric results. Values of Δhb calculated from constant K are 5230 J/mol when Bixon and Lifson theory is used and 5569 J/mol when the theory at Sayama and coworkers is used. In both cases the value for Δhb is much lower than that of an intramolecular hydrogen bond. Experimental results suggest that the solvation mechanism would proceed in a manner so that mechanisms described in both theories are involved.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1976.360151014
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    Irreversible thermodynamic analysis of electrophoretic light scattering experiments (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 21-28 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A fluctuation theory for electrolyte solutions is developed based on the coupling between the equations of nonequilibrium thermodynamics and the Poisson equation. The resulting fluctuation theory is applied to the analysis of electrophoretic light scattering. It is shown that in a binary electrolyte solution (two ionic species), the Doppler shift is not determined by the electrical mobility of either ion, but depends instead on the rate of change of transference number with salt concentration. In addition the ionic relaxation time is shown to be proportional to the conductivity of the solution.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1976.360150104
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  • 95
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    Binding of proflavin to T2L bacteriophage and its DNA (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 97-111 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have measured the binding equilibria of proflavin to T2L bacteriophage, in both “slow” and “fast” sedimenting forms, and to free T2L DNA. Measurements were carried out by difference spectroscopy at 430 nm at temperatures from 13 to 43°C and at pH 5.6 and 7.6. We found no significant difference in the binding parameters of the two phage forms. Also, the fraction of nucleotides available as binding sites for proflavin was the same for both free and intraphage DNA. However, the binding constant is about an order of magnitude lower for encapsulated than for free T2L DNA, due to the decreased exothermicity of the binding reaction within the phage head.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1976.360150108
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    Application of the nearest-neighbor ising model to the helix-coil transition of polypeptides in mixed organic solvents (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 113-129 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the formalism of nearest-neighbor Ising model and assuming that the allowed states for a monomeric unity of a polypeptide chain in solutions containing strong acids are E (helix), C (coil), and CS (solvent-bonded coil), the partition function of the system was deduced analytically. Equations were obtained which permitted the prediction of the characteristic thermodynamic behavior of the helix-coil transition under these conditions. These equations were used to examine critically the possible correlations between experimental data obtained using different techniques. Particular attention was devoted to quantities called “transition enthalpies,” obtained from the slope of the transition curves at the point where the helix fraction is one-half (ΔHoptexp), or for measurements of the heat of solution of the polymer over the total range of solvent composition (ΔHsolexp), or from heat capacity measurements taken at various temperatures (ΔHcalexp). Literature data of ΔHjexp(j = opt, sol, cal) for the system poly-γ-benzyl-L-glutamate in mixtures of dichloroacetic acid and 1,2-dichloroethane were carefully analyzed.
    Additional Material: 11 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1976.360150109
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    Kinetic study of cooperative binding reaction of toluidine blue to poly(α,L-glutamic acid) by means of the electric-field pulse method (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 187-201 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Interaction of toluidine blue with helical and randomly coiled poly(α,L-glutamic acid) was studied with absorption spectra, titration, and electric-field pulse measurements. The obtained values of various parameters for the helical form of poly(α,L-glutamic acid)differed from those for its coiled form. The difference of parameters in these two forms of poly(α,L-glutamic acid) was attributed to differences of the binding mechanism in both forms. Furthermore, the binding of toluidine blue to poly(α,L-glutamic acid) was considered to be due to hydrogen binding in the helical conformation and ionic interaction in the coiled conformation of the polymer.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1976.360150113
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    Cu(II) ions-DNA interaction: A dilatometric study (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 227-228 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1976.360150116
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    Analysis of derivative binding isotherms. Theoretical considerationsPreliminary reports of this paper were presented at the Annual Meeting of the French Chemical Society, May, 1973, and the 26th Annual American Calorimetry Conference, Worcester, Mass, June, 1973. (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 337-354 
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    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The basic theoretical groundwork for the use of derivative binding isotherms in the analysis of ligand binding is presented. The derivative binding isotherm is defined as Γ (Y) = df/dy where f = fractional degree of saturation and y = natural logarithm of the free ligand concentration. Since Γ (y) is a positive function, which goes to zero as y → ±∞, the mean value of y, 〈y〉, and the second and third moments, μ2 and μ3 about 〈y〉 are well defined.For a macromolecular system consisting of N equivalent and independent binding sites, Γ (y) is a symmetrical bell-shaped function with one maximum. The maximum occurs when y = -ln Kassoc; μ2 = π2/3, and μ3 = 0. For multiple sets of independent binding sites, Γ (y) is a superposition of Γ-type functions. If the sets are sufficiently well separated in binding free energy, multiple extrema may be seen at positions corresponding to the logarithms of the dissociation constants for the individual sets. In any case, 〈y〉 is equal to the mean value of the logarithms of the dissociation constants for the sets; μ2 〉 π2/3 and equal to π2/3 plus the variance of the logarithms of the dissociation constants about their mean value; and μ3 is, except by coincidence, not equal to zero and equals the third moment of the distribution of logarithms of the dissociation constants about their mean value.Analysis of Γ(y) for the case of cooperative interactions within a set of binding sites was investigated by examining (1) the Hill model (whose mathematical representation is equivalent to that used to describe antibody heterogeneity except that in the latter case the parameter a, the Sips, constant, is constrained (0 〈 a ≤1);(2) a common model for cooperativity in which the cooperative free energy is a linear function of the fraction bound; and (3) a general representation of cooperative interactions within a set of sites in terms of φ(f), a smooth function that gives the interaction free energy in units of RT.For the Hill model (or Sips model) Γ(y) is a symmetrical function with one maximum at y = (-1)/a)lnK, μ2 = π2/3a2; and μ3 = 0. For the case in which the cooperative free energy is a linear function of f [φ(f) = cf], 〈y〉 = -ln K0 + (c/2); μ2 = (π2/3) + c[(c/12) + 1] where c 〉 -4; and μ3 = 0. General expressions for the moments in terms of φ(f) are derived. In general, μ2 〈 (π2/3) for positive cooperativity and μ2 〉 (π2/3) for negative for negative cooperativity. Γ(y) will be symmetrical if and only if the cooperative free energy is introduced symmetrically about f = 0.5.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1976.360150211
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    Specific heat thermal variations of L-valine and poly(L-valine) (1976)
    New York : Wiley-Blackwell
    Biopolymers 15 (1976), S. 415-418 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1976.360150217
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