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  • Wiley-Blackwell  (45,193)
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  • 2010-2014  (21)
  • 1995-1999  (11,406)
  • 1980-1984  (17,442)
  • 1975-1979  (14,391)
  • 1935-1939
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  • 1
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    Geological and geophysical investigation of Kamil crater, Egypt (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2020-12-21
    Description: We detail the Kamil crater (Egypt) structure and refine the impact scenario, based on the geological and geophysical data collected during our first expedition in February 2010. Kamil Crater is a model for terrestrial small-scale hypervelocity impact craters. It is an exceptionally well-preserved, simple crater with a diameter of 45 m, depth of 10 m, and rayed pattern of bright ejecta. It occurs in a simple geological context: flat, rocky desert surface, and target rocks comprising subhorizontally layered sandstones. The high depth-to-diameter ratio of the transient crater, its concave, yet asymmetric, bottom, and the fact that Kamil Crater is not part of a crater field confirm that it formed by the impact of a single iron mass (or a tight cluster of fragments) that fragmented upon hypervelocity impact with the ground. The circular crater shape and asymmetries in ejecta and shrapnel distributions coherently indicate a direction of incidence from the NW and an impact angle of approximately 30 to 45 . Newly identified asymmetries, including the off-center bottom of the transient crater floor downrange, maximum overturning of target rocks along the impact direction, and lower crater rim elevation downrange, may be diagnostic of oblique impacts in well-preserved craters. Geomagnetic data reveal no buried individual impactor masses 〉100 kg and suggest that the total mass of the buried shrapnel 〉100 g is approximately 1050–1700 kg. Based on this mass value plus that of shrapnel 〉10 g identified earlier on the surface during systematic search, the new estimate of the minimum projectile mass is approximately 5 t.
    Description: Published
    Description: 1842–1868
    Description: 3.8. Geofisica per l'ambiente
    Description: JCR Journal
    Description: restricted
    Keywords: Impact craters ; geophysical survey ; iron meteorite ; impact scenario ; 04. Solid Earth::04.02. Exploration geophysics::04.02.99. General or miscellaneous ; 04. Solid Earth::04.02. Exploration geophysics::04.02.07. Instruments and techniques ; 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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  • 2
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    Revised Chronology of the Sulmona Lacustrine Succession, Central Italy (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2020-12-07
    Description: We present new stratigraphic, palaeomagnetic, 87Sr/86Sr and 40Ar/39Ar data from a lacustrine succession of the Sulmona basin, central Italy, which, according to an early study, included six unconformitybounded lacustrine units (from SUL6, oldest, to SUL1, youngest) spanning the interval 〉600 to 2 ka. The results of the present study, on the one hand confirm some of the previous conclusions, but by contrast reveal that units SUL2 and SUL1, previously attributed to the Holocene, are actually equivalent to the older SUL6 and SUL5 units – here dated to 814–〉530 ka and 530–〈457 ka, respectively – and that the U-series dates previously published for both former SUL2 and SUL1 units yielded abnormally young ages. In light of the present results, a reassessment of the chronology of the Sulmona basin succession and a revision of the tephrostratigraphy of the SUL2/SUL6 and SUL1/SUL5 units is in order.
    Description: Published
    Description: 545–551
    Description: 2.2. Laboratorio di paleomagnetismo
    Description: JCR Journal
    Description: restricted
    Keywords: 40Ar/39Ar dating; central Italy ; Sr isotope composition ; Sulmona lacustrine succession ; Brunhes–Matuyama geomagnetic reversal ; tephrostratigraphy ; U-series dating ; 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::04.05. Geomagnetism::04.05.06. Paleomagnetism
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 3
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    Seismic energy envelopes in volcanic media: in need of boundary conditions (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2020-12-15
    Description: Seismogram envelopes recorded at Campi Flegrei caldera show diffusive characteristics as well as steep amplitude increases in the intermediate and late coda, which can be related to the presence of a non-uniformly scattering medium. In this paper, we first show the results of a simulation with a statistical model considering anisotropic scattering interactions, in order to match coda-envelope duration and shape.We consider as realistic parameters for a volcanic caldera the presence of large square root velocity fluctuations (10 per cent) and two typical correlation lengths for such an heterogeneous crust, a = 0.1 and 1 km. Then, we propose the inclusion of a diffusive boundary condition in the stochastic description of multiple scattering, in order to model intermediate and late coda intensities, and particularly the sharp intensity peaks at some stations in the caldera. Finally, we show that a reliable 2-D synthetic model of the envelopes produced by earthquakes vertically sampling a small region can be obtained including a single drastic change of the scattering properties of the volcano, that is, a caldera rim of radius 3 km, and sections varying between 2 and 3 km. These boundary conditions are diffusive, which signifies that the rim must have more scattering potential than the rest of the medium, with its diffusivity 2–3 orders of magnitude lower than the one of the background medium, so that the secondary sources on its interface(s) could enhance coda intensities. We achieve a good first-order model of high-frequency (18 Hz) envelope broadening adding to the Monte Carlo solution for the incident flux the secondary source effects produced by a closed annular boundary, designed on the caldera rim signature at 1.5 km depth. At lower frequencies (3 Hz) the annular boundary controls the intermediate and late coda envelope behaviour, in a way similar to an extended diffusive source. In our interpretation, the anomalous intensities observed at several stations and predicted by the final Monte Carlo solutions are mainly due to the diffusive transmission reflection from a scattering object of increased scattering power, and are controlled by its varying thickness.
    Description: This work was carried out under the HPC-Europa2 project (project number: 228398) with the support of the European Commission Capacities Area-Research Infrastructures Initiative. We thank the whole staff at EPCC (Edinburgh Parallel Computing Centre) in Edinburgh and particularly Dr. Adam Carter for their help in both developing and parallelizing the code. The challenging comments and suggestions of the editor and two anonymous reviewers helped both in focusing the aim and in overcoming the strong limits of a previous version of the paper.
    Description: Published
    Description: 1102–1119
    Description: 3.1. Fisica dei terremoti
    Description: JCR Journal
    Description: restricted
    Keywords: Numerical solutions; ; Seismic anisotropy; ; Seismic attenuation ; Seismic tomography ; Wave scattering and diffraction ; Calderas ; 04. Solid Earth::04.06. Seismology::04.06.09. Waves and wave analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 4
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    Joint observation of coherent coda waves at surface and underground arrays (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: Local and regional seismicity jointly recorded by two dense small aperture arrays, one installed at surface and one at 1.3 km depth, constitutes an interesting data set useful for coda observations. Applying array techniques to earthquakes recorded at the two arrays we measure slowness, backazimuth and correlation coefficient of the coherent coda wave signals in five frequency bands in the range 1–10 Hz. Slowness distributions show marked differences between surface and underground, with slow signals at surface (slowness greater than 1.0 s km−1) that are not observed underground. We interpret these coherent signals as surface waves produced by the interaction of body waves with the free surface characterized by rough topography. The backazimuth values measured in the frequency bands centred at 1.5 and 3 Hz are almost uniformly distributed between 0 and 360◦, while those measured at higher frequencies show different distributions between surface and underground. On the contrary, the earthquake envelopes show very similar coda shapes between surface and underground recordings, with an almost constant coda-amplitude ratio (between 4 and 8) in a wide frequency range.
    Description: Published
    Description: 367-371
    Description: 1.1. TTC - Monitoraggio sismico del territorio nazionale
    Description: JCR Journal
    Description: restricted
    Keywords: Coda waves ; Wave scattering and diffraction ; Wave propagation ; 04. Solid Earth::04.06. Seismology::04.06.09. Waves and wave analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 5
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    Spatial distribution of intrinsic and scattering seismic attenuation in active volcanic islands – II: Deception Island images (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: In this work, we present regional maps of the inverse intrinsic quality factor (Qi −1), the inverse scattering quality factor (Qs −1) and total inverse quality factor (Qt −1) for the volcanic environment of Deception Island (Antarctica). Our attenuation study is based on diffusion approximation, which permits us to obtain the attenuation coefficients for every single couple source-receiver separately. The data set used in this research is derived from an active seismic experiment using more than 5200 offshore shots (air guns) recorded at 32 onshore seismic stations and four ocean bottom seismometers. To arrive at a regional distribution of these values, we used a new mapping technique based on a Gaussian space probability function. This approach led us to create ‘2-D probabilistic maps’ of values of intrinsic and scattering seismic attenuation. The 2-D tomographic images confirm the existence of a high attenuation body below an inner bay of Deception Island. This structure, previously observed in 2-D and 3-D velocity tomography of the region, is associated with a massive magma reservoir. Magnetotelluric studies reach a similar interpretation of this strong anomaly. Additionally, we observed areas with lower attenuation effects that bear correlation with consolidated structures described in other studies and associated with the crystalline basement of the area. Our calculations of the transport mean-free path and absorption length for intrinsic attenuation gave respective values of ≈950 m and 5 km, which are lower than the values obtained in tectonic regions or volcanic areas such as Tenerife Island. However, as observed in other volcanic regions, our results indicate that scattering effects dominate strongly over the intrinsic attenuation.
    Description: This work has been partially supported by the Spanish project Ephestos, CGL2011–29499-C02–01, by the EU project EC-FP7 MEDiterranean SUpersite Volcanoes (MED-SUV), by the Basque Government researcher training program BFI09.277 and by the Regional project ‘Grupo de Investigaci´on en Geof´ısica y Sismolog´ıa de la Junta de Andaluc´ıa, RNM104.’ Edoardo del Pezzo was partly supported by DPC-INGV projects UNREST SPEED and V2 (Precursori).
    Description: Published
    Description: 1957-1969
    Description: 3.1. Fisica dei terremoti
    Description: 3.6. Fisica del vulcanismo
    Description: JCR Journal
    Description: restricted
    Keywords: Seismic attenuation; ; Seismic tomography ; Volcano seismology ; Wave scattering and diffraction ; Wave propagation ; 04. Solid Earth::04.06. Seismology::04.06.07. Tomography and anisotropy ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.06. Seismology::04.06.09. Waves and wave analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 6
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    The stress field in Europe: optimal orientations with confidence limits (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: This article has been accepted for publication in Geophysical Journal International ©: The Authors 2003. Published by Oxford University Press on behalf of The Royal Astronomical Society. All rights reserved.
    Description: In this study, we modify and extend a data analysis technique to determine the stress orientations between data clusters by adding an additional constraint governing the probability algorithm. We apply this technique to produce a map of the maximum horizontal compressive stress (S_Hmax) orientations in the greater European region (including Europe, Turkey and Mediterranean Africa). Using the World Stress Map dataset release 2008, we obtain analytical probability distributions of the directional differences as a function of the angular distance, θ. We then multiply the probability distributions that are based on pre-averaged data within θ〈3° of the interpolation point and determine the maximum likelihood estimate of the S_Hmax orientation. At a given distance, the probability of obtaining a particular discrepancy decreases exponentially with discrepancy. By exploiting this feature observed in the World Stress Map release 2008 dataset, we increase the robustness of our S_Hmax determinations. For a reliable determination of the most likely S_Hmax orientation, we require that 90% confidence limits be less than ±60° and a minimum of three clusters, which is achieved for 57% of the study area, with small uncertainties of less than ±10° for 7% of the area. When the data density exceeds 0.8×10^-3 data/km2, our method provides a means of reproducing significant local patterns in the stress field. Several mountain ranges in the Mediterranean display 90° changes in the S_Hmax orientation from their crests (which often experience normal faulting) and their foothills (which often experience thrust faulting). This pattern constrains the tectonic stresses to a magnitude similar to that of the topographic stresses.
    Description: This work was supported by the DPC-INGV 2008-2010 S1 project, the EU-FP7 project “Seismic Hazard Harmonization in Europe” (SHARE; Grant agreement no. 226967), and project MIUR-FIRB "Abruzzo" (code: RBAP10ZC8K_003).
    Description: Published
    Description: 3.1. Fisica dei terremoti
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: 4.2. TTC - Modelli per la stima della pericolosità sismica a scala nazionale
    Description: JCR Journal
    Description: partially_open
    Keywords: Neotectonics ; Seismicity and tectonics ; Fractures and faults ; Intra-plate processes ; Plate motions ; Dynamics: gravity and tectonics ; 04. Solid Earth::04.03. Geodesy::04.03.01. Crustal deformations ; 04. Solid Earth::04.04. Geology::04.04.09. Structural geology ; 04. Solid Earth::04.07. Tectonophysics::04.07.05. Stress ; 05. General::05.02. Data dissemination::05.02.99. General or miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 7
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    Location and magnitudes of earthquakes in Central Asia from seismic intensity data: model calibration and validation (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: macroseismic intensity data. A set of 2373 intensity observations from 15 earthquakes is analysed to calibrate non-parametric models for the source and attenuation with distance, the distance being computed from the instrumental epicentres located according to the International Seismological Centre (ISC) catalogue. In a second step, the non-parametric source model is regressed against different magnitude values (e.g. MLH, mb, MS, Mw) as listed in various instrumental catalogues. The reliability of the calibrated model is then assessed by applying the methodology to macroseismic intensity data from 29 validation earthquakes for which bothMLH and mb are available from the Central Asian Seismic Risk Initiative (CASRI) project and the ISC catalogue. An overall agreement is found for both the location and magnitude of these events, with the distribution of the differences between instrumental and intensity-based magnitudes having almost a zero mean, and standard deviations equal to 0.30 and 0.44 for mb and MLH, respectively. The largest discrepancies are observed for the location of the 1985, MLH = 7.0 southern Xinjiang earthquake, whose location is outside the area covered by the intensity assignments, and for the magnitude of the 1974, mb = 6.2 Markansu earthquake, which shows a difference in magnitude greater than one unit in terms of MLH. Finally, the relationships calibrated for the non-parametric source model are applied to assign different magnitude-scale values to earthquakes that lack instrumental information. In particular, an intensity-based moment magnitude is assigned to all of the validation earthquakes.
    Description: Published
    Description: 710-724
    Description: 5.1. TTC - Banche dati e metodi macrosismici
    Description: JCR Journal
    Description: restricted
    Keywords: seismicity and tectonics: seismic attenuarion; Asia ; 04. Solid Earth::04.06. Seismology::04.06.05. Historical seismology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 8
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    Strain rate relaxation of normal and thrust faults in Italy (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: We find that geodetic strain rate (SR) integrated with the knowledge of active faults points out that hazardous seismic areas are those with lower SR, where active faults are possibly approaching the end of seismic cycle. SR values estimated from GPS velocities at epicentral areas of large historical earthquakes in Italy decrease with increasing elapsed time, thus highlighting faults more prone to reactivation. We have modelled an exponential decrease relationship between SR and the time elapsed since the last largest earthquake, differencing historical earthquakes according to their fault rupture style. Then, we have estimated the characteristic times of relaxation by a non-linear inversion, showing that events with thrust mechanism exhibit a characteristic time (∼ 990 yr) about three times larger than those with normal mechanism. Assuming standard rigidity and viscosity values we can infer an average recurrence time of about 600 yr for normal faults and about 2000 yr for thrust faults.
    Description: Published
    Description: 815-820
    Description: 3.2. Tettonica attiva
    Description: JCR Journal
    Description: restricted
    Keywords: Seismic cycle ; Seismicity and tectonics ; Transient deformation ; 04. Solid Earth::04.07. Tectonophysics::04.07.07. Tectonics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 9
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    A comparison among general orthogonal regression methods applied to earthquake magnitude conversions (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: Until a decade ago, regression analyses for conversions between different types of magnitude were using only the ordinary least squares method,which assumes that the independent variable is error free, or the simple orthogonal regression method,which assumes equal uncertainties for the two variables. The recent literature became aware of the inadequacy of such approaches and proposes the use of general orthogonal regression methods that account for different uncertainties of the two regression variables. Under the common assumption that only the variance ratio η between the dependent and independent variables is known, we compared three of such general orthogonal regression methods that have been applied to magnitude conversions: the chi-square regression, the general orthogonal regression, and the weighted total least squares. Although their formulations might appear quite different, we show that, under appropriate conditions, they all compute almost exactly the same regression coefficients and very similar (albeit slightly different) formal uncertainties. The latter are in most cases smaller than those estimated by bootstrap simulation but the amount of the deviation depends on the data set and on the assumed variance ratio.
    Description: European Union project SHARE (Seismic Hazard Harmonization in Europe) within the ambit of Task 3.1‘European Earthquake Database’.
    Description: Published
    Description: 1135-1151
    Description: JCR Journal
    Description: restricted
    Keywords: Earthquake source observations; Statistical seismology ; 04. Solid Earth::04.06. Seismology::04.06.06. Surveys, measurements, and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 10
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    New kinematic constraints of the western Doruneh fault, north-eastern Iran, from interseismic deformation analysis (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: We used the SBAS DInSAR analysis technique to estimate the interseismic deformation along the western part of the Doruneh fault system (DFS), northeastern Iran. We processed 90 ENVISAT images from four different frames from ascending and descending orbits. Three of the ground velocity maps show a significant interseismic signal. Using a simple dislocation approach we model 2-D velocity profiles concerning three InSAR data set relative to the western part of the DFS, obtaining a good fit to the observations. The resulting model indicates that a slip rate of ∼5mmyr−1 accumulates on the fault below 10 km depth, and that in its western sector the Doruneh fault is not purely strike-slip (left-lateral) as in its central part, but shows a significant thrust component. Based on published geological observations, and assuming that all interseismic deformation is recovered with a single event, we can estimate a characteristic recurrence interval between 630 and 1400 yr.
    Description: Published
    Description: 622-628
    Description: 1.10. TTC - Telerilevamento
    Description: 3.2. Tettonica attiva
    Description: JCR Journal
    Description: restricted
    Keywords: Image processing; Satellite geodesy; Seismic cycle; Radar interferometry; Seismicity and tectonics; Continental tectonics: strike-slip and transform. ; 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::04.04. Geology::04.04.09. Structural geology ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.07. Tectonophysics::04.07.02. Geodynamics ; 04. Solid Earth::04.07. Tectonophysics::04.07.07. Tectonics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 11
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    Reassessment of the source of the 1976 Friuli, NE Italy, earthquake sequence from the joint inversion of high-precision levelling and triangulation data (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: In this study, we revisit the mechanism of the 1976 Friuli (NE Italy) earthquake sequence (main shocks M w 6.4, 5.9 and 6.0). We present a new source model that simultaneously fits all the available geodetic measurements of the observed deformation. We integrate triangulation measurements, which have never been previously used in the source modelling of this sequence, with high-precision levelling that covers the epicentral area. We adopt a mixed linear/non-linear optimization scheme, in which we iteratively search for the best-fitting solution by performing several linear slip inversions while varying fault location using a grid search method. Our preferred solution consists of a shallow north-dipping fault plane with assumed azimuth of 282◦ and accommodating a reverse dextral slip of about 1 m. The estimated geodetic moment is 6.6 × 1018 Nm (M w 6.5), in agreement with seismological estimates. Yet, our preferred model shows that the geodetic solution is consistent with the activation of a single fault system during the entire sequence, the surface expression of which could be associated with the Buia blind thrust, supporting the hypothesis that the main activity of the Eastern Alps occurs close to the relief margin, as observed in other mountain belts. The retrieved slip pattern consists of a main coseismic patch located 3–5 km depth, in good agreement with the distribution of the main shocks. Additional slip is required in the shallower portions of the fault to reproduce the local uplift observed in the region characterized by Quaternary active folding. We tentatively interpret this patch as postseismic deformation (afterslip) occurring at the edge of the main coseismic patch. Finally, our rupture plane spatially correlates with the area of the locked fault determined from interseismic measurements, supporting the hypothesis that interseismic slip on the creeping dislocation causes strain to accumulate on the shallow (above ∼10 km depth) locked section. Assuming that all the long-term accommodation between Adria and Eurasia is seismically released, a time span of 500–700 years of strain-accumulating plate motion would result in a 1976-like earthquake.
    Description: Published
    Description: 1279-1294
    Description: 3.1. Fisica dei terremoti
    Description: 3.2. Tettonica attiva
    Description: JCR Journal
    Description: restricted
    Keywords: seismic cycle; earthquake source observations ; 04. Solid Earth::04.03. Geodesy::04.03.01. Crustal deformations
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 12
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    Magnitude scale for LP events: a quantification scheme for volcanic quakes (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: The peculiar source characteristics of long-period seismic events (time persistency of the source, low-frequency peaks in the source spectrum, absence of high-frequency radiation) prevent the formation of a definite high-frequency coda in the seismograms. In contrast, this is well formed in volcano–tectonic quakes. For this reason, the widely used duration magnitude scale that is based on the proportionality between the energy and the coda duration cannot be used for long-period estimation. In observatory practice, the long-period magnitude is sometimes estimated using the same duration magnitude scale, leading to confusing results. In this report, we show a new method to estimate the magnitude of long-period events that generally occur for volcanoes, with some application examples from data for Mt Etna (Italy), Colima Volcano (Mexico) and Campi Flegrei (Italy).
    Description: Published
    Description: 911-919
    Description: 3.1. Fisica dei terremoti
    Description: JCR Journal
    Description: restricted
    Keywords: Earthquake source observations; ; Volcano monitoring ; Volcano seismology ; 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::04.06. Seismology::04.06.09. Waves and wave analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 13
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    Frequency dependent Qα and Qβ in the Umbria-Marche (Italy) region using a quadratic approximation of the coda-normalization method (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: The coda normalization method is one of the most used methods in the inference of attenuation parameters Qα and Qβ . Since, in this method, the geometrical spreading exponent γ is an unknown model parameter, the most part of studies assumes a fixed γ , generally equal to 1. However γ and Q could be also jointly inferred from the non-linear inversion of codanormalized logarithms of amplitudes, but the trade-off between γ and Q could give rise to unreasonable values of these parameters. To minimize the trade-off between γ and Q, an inversion method based on a parabolic expression of the coda-normalization equation has been developed. The method has been applied to the waveforms recorded during the 1997 Umbria-Marche seismic crisis. The Akaike criterion has been used to compare results of the parabolic model with those of the linear model, corresponding to γ = 1. A small deviation from the spherical geometrical spreading has been inferred, but this is accompanied by a significant variation of Qα and Qβ values. For almost all the considered stations, Qα smaller than Qβ has been inferred, confirming that seismic attenuation, in the Umbria-Marche region, is controlled by crustal pore fluids.
    Description: Published
    Description: 1726-1731
    Description: 3.1. Fisica dei terremoti
    Description: JCR Journal
    Description: restricted
    Keywords: Seismic attenuation ; coda normalization method ; 04. Solid Earth::04.06. Seismology::04.06.09. Waves and wave analysis
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  • 14
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    Are the source models of the M7.1 1908 Messina Straits earthquake reliable? Insights from a novel inversion and a sensitivity analysis of levelling data (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: For decades, many authors have attempted to define the location, geometry and kinematics of the causative fault for the 1908 December 28, M 7.1 earthquake that struck the Messina Straits between Sicily and Calabria (southern Italy). The coseismic displacement caused a predominant downwarping of the Straits and small land uplift away from it, which were documented by levelling surveys performed 1 yr before and immediately after the earthquake. Most of the source models based on inversion of levelling data suggested that the earthquake was caused by a low angle, east-dipping blind normal fault, whose upper projection intersects the Earth surface on the Sicilian (west) side of the Messina Straits.An alternative interpretation holds that the causative fault is one of the high-angle, west-dipping faults located in southern Calabria, on the eastern side of the Straits, and may in large part coincide with the mapped Armo Fault. Here, we critically review the levelling data with the aim of defining both their usefulness and limits in modelling the seismogenic fault. We demonstrate that the levelling data alone are not capable of discriminating between the two oppositely dipping fault models, and thus their role as a keystone for modellers is untenable. However, new morphotectonic and geodetic data indicate that the Armo Fault has very recent activity and is accumulating strain. The surface observations, together with appraisal ofmacroseismic intensity distribution, available seismic tomography and marine geophysical evidence, lends credit to the hypothesis that the Armo and possibly the S. Eufemia faults are part of a major crustal structure that slipped during the 1908 earthquake.
    Description: Published
    Description: 1025-1041
    Description: JCR Journal
    Description: restricted
    Keywords: Earthquake source ; Messina Straits ; 04. Solid Earth::04.03. Geodesy::04.03.01. Crustal deformations ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics ; 04. Solid Earth::04.07. Tectonophysics::04.07.07. Tectonics ; 05. General::05.01. Computational geophysics::05.01.03. Inverse methods ; 05. General::05.01. Computational geophysics::05.01.04. Statistical analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 15
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    A comparison of moment magnitude estimates for the European–Mediterranean and Italian regions (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: With the goal of constructing a homogeneous data set of moment magnitudes (Mw) to be used for seismic hazard assessment, we compared Mw estimates from moment tensor catalogues available online. We found an apparent scaling disagreement between Mw estimates from the National Earthquake Information Center (NEIC) of the US Geological Survey and from the Global Centroid Moment Tensor (GCMT) project. We suspect that this is the effect of an underestimation ofMw 〉 7.0 (M0 〉 4.0 × 1019 Nm) computed by NEIC owing to the limitations of their computational approach. We also found an apparent scaling disagreement between GCMT and two regional moment tensor catalogues provided by the ‘Eidgen¨ossische Technische Hochschule Z¨urich’ (ETHZ) and by the European–Mediterranean Regional Centroid Moment Tensor (RCMT) project of the Italian ‘Istituto Nazionale di Geofisica e Vulcanologia’ (INGV). This is probably the effect of the overestimation of Mw 〈 5.5 (M0 〈 2.2 × 1017 Nm), up to year 2002, and of Mw 〈 5.0 (M0 〈 4.0 × 1016 Nm), since year 2003, owing to the physical limitations of the standard CMT inversion method used by GCMT for the earthquakes of relatively low magnitude. If the discrepant data are excluded from the comparisons, the scaling disagreements become insignificant in all cases. We observed instead small absolute offsets (≤0.1 units) for NEIC and ETHZ catalogues with respect to GCMT whereas there is an almost perfect correspondence between RCMT and GCMT. Finally, we found a clear underestimation of about 0.2 units of Mw magnitudes computed at the INGV using the time-domain moment tensor (TDMT) method with respect to those reported by GCMT and RCMT. According to our results, we suggest appropriate offset corrections to be applied to Mw estimates from NEIC, ETHZ and TDMT catalogues before merging their data with GCMT and RCMT catalogues. We suggest as well to discard the probably discrepant data from NEIC and GCMT if other Mw estimates from different sources are available for the same earthquakes. We also estimate approximately the average uncertainty of individual Mw estimates to be about 0.07 magnitude units for the GCMT, NEIC, RCMT and ETHZ catalogues and about 0.13 for the TDMT catalogue.
    Description: European Union research project SHARE (Seismic Hazard Harmonization in Europe), within the ambit of Task 3.1 ‘European Earthquake Database’
    Description: Published
    Description: 1733-1745
    Description: JCR Journal
    Description: restricted
    Keywords: Earthquake source observations; Statistical seismology ; 05. General::05.01. Computational geophysics::05.01.04. Statistical analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 16
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    Spatial distribution of intrinsic and scattering seismic attenuation in active volcanic islands – I: model and the case of Tenerife Island (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: The complex volcanic system of Tenerife Island is known to have a highly heterogeneous character, as recently confirmed by velocity tomography.We present new information derived from intrinsic quality factor inverse maps (Qi −1), scattering quality factor inverse maps (Qs −1) and total quality factor inverse maps (Qt −1) obtained for the same region. The data set used in this work is the result of the analysis of an active seismic experiment carried out, using offshore shots (air guns) recorded at over 85 onshore seismic stations. The estimates of the attenuation parameters are based on the assumption that the seismogram energy envelopes are determined by seismic energy diffusion processes occurring inside the island. Diffusion model parameters, proportional to Qi −1 and to Qs −1, are estimated from the inversion of the energy envelopes for any source–receiver couple. They are then weighted with a new graphical approach based on a Gaussian space probability function, which allowed us to create ‘2-D probabilistic maps’ representing the space distribution of the attenuation parameters. The 2-D images obtained reveal the existence of a zone in the centre of the island characterized by the lowest attenuation effects. This effect is interpreted as highly rigid and cooled rocks. This low-attenuation region is bordered by zones of high attenuation, associated with the recent historical volcanic activity. We calculate the transport mean free path obtaining a value of around 4 km for the frequency range 6–12 Hz. This result is two orders of magnitude smaller than values calculated for the crust of the Earth. An absorption length between 10 and 14 km is associated with the average intrinsic attenuation parameter. These values, while small in the context of tectonic regions, are greater than those obtained in volcanic regions such as Vesuvius or Merapi. Such differences may be explained by the magnitude of the region of study, over three times larger than the aforementioned study areas. This also implies deeper sampling of the crust, which is evidenced by a change in the values of seismic attenuation. One important observation is that scattering attenuation dominates over the intrinsic effects, Qi being at least twice the value of Qs.
    Description: This work has been partially supported by the Spanish project Ephestos, CGL2011-29499-C02-01, by the EU project EC-FP7 MEDiterranean SUpersite Volcanoes (MED-SUV), by the Basque Government researcher training program BFI09.277 and by the Regional project ‘Grupo de Investigaci´on en Geof´ısica y Sismolog´ıa de la Junta de Andaluc´ıa, RNM104’. EdP has been partly supported by DPC-INGV projects UNREST SPEED and V2 (Precursori).
    Description: Published
    Description: 1942-1956
    Description: 3.1. Fisica dei terremoti
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: JCR Journal
    Description: restricted
    Keywords: Seismic attenuation ; ; Seismic tomography; ; Volcano seismology ; Wave propagation. ; 04. Solid Earth::04.06. Seismology::04.06.07. Tomography and anisotropy ; 04. Solid Earth::04.06. Seismology::04.06.08. Volcano seismology ; 04. Solid Earth::04.06. Seismology::04.06.09. Waves and wave analysis
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 17
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    Projections of Heavy Rainfall over the Central US based on CMIP5 Models (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: The central United States is a region for which observational studies have indicated an increase in heavy rainfall. This study uses projections of daily rainfall from 20 state-of-the-art global climate models and one scenario (RCP 8.5) to examine projected changes in extreme rainfall. Analyses are performed focusing on trends in the 90th and 99th percentiles of the daily rainfall distributions for two periods (2006-2045 and 2046-2085). The results of this study indicate a large increase in extreme rainfall in particular over the northern part of the study region, with a much less clear signal over the Great Plains and the states along the Gulf of Mexico.
    Description: Published
    Description: 200-205
    Description: 3.7. Dinamica del clima e dell'oceano
    Description: JCR Journal
    Description: embargoed_20160624
    Keywords: precipitation ; extreme events ; cmip5 ; climate change ; 01. Atmosphere::01.01. Atmosphere::01.01.02. Climate
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 18
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    Deformation of Ancient Buildings inferred by Terrestrial Laser Scanning methodology: the Cantalovo church case study (Northern Italy) (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2017-04-04
    Description: The study of the health of a building connects humanistic and scientific research, and a complete characterization can be achieved by integrating all the available historical documentation, architectural and metrological studies, as well as laboratory and in situ analyses of the materials. A contactless, non-invasive surveying technique such as terrestrial laser scanning (TLS) allows the acquisition of dense and accurate geometric and radiometric (electromagnetic measurements such as signal intensity) information about the observed surface of the building, which can be easily integrated with data provided by high-resolution digital imaging. The early Christian Cantalovo church was surveyed for the first time in April 2011, by means of the ILRIS-3D ER very long range scanner. The second and last survey was performed in June 2012, after the main shocks of the Emilia earthquake seismic sequence. A very long range instrument is suitable for fast, simple and independent measurements, due to its technical characteristics and, for this reason, is easily usable for accurate surveying in emergency conditions. The main results are obtained by applying a data analysis strategy based on the creation of TLS-based morphological maps computed as point-to-primitive differences, which allow the creation of a deformation map and its evolution in time.
    Description: Published
    Description: 703-716
    Description: 1IT. Reti di monitoraggio e Osservazioni
    Description: JCR Journal
    Description: restricted
    Keywords: Terrestrial Laser Scanning ; Deformation ; Earthquake ; Ancient Building ; Procedure Standardization ; 04. Solid Earth::04.03. Geodesy::04.03.06. Measurements and monitoring
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 19
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    Measuring the Flow of Energy and Matter in Marine Benthic Animal Populations (2013)
    Wiley-Blackwell
    In:  EPIC3Methods for the study of marine benthos, Methods for the study of marine benthos, West Sussex, Wiley-Blackwell, 78 p., pp. 329-407, ISBN: 978-0-470-67086-6
    Details
    Publication Date: 2014-04-15
    Description: Traditionally, the rationale for energy flow studies was found in the elucidation of energy transfers within ecosystems or within the practical context of the rational management of resources, but it is now widely recognised that its scope embodies almost all biology, including the field of population dynamics and evolutionary studies. Here, we first describe conceptual models of energy and mass budgets at the level of the individual, the population and the community. However, the emphasis is on the next part in which the practicalities of measuring the various components of these budgets in the marine zoobenthic community are described in detail. The measurement of, among other things, ingestion, absorption, defaecation, excretion, growth, reproduction and respiration is discussed. Finally, attention is paid to the estimation of secondary production of benthic populations and to community-level modelling methods.
    Repository Name: EPIC Alfred Wegener Institut
    Type: Inbook , peerRev
    Format: application/pdf
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  • 20
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    Modeling the interseismic deformation of a thrust system: seismogenic potential of the Southern Alps (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2022-05-24
    Description: This article focuses on the Montello thrust system in the Eastern Southern Alps as a potential seismogenic source. This system is of particular interest because of its lack of historical seismicity. Nevertheless, the system is undergoing active deformation. We developed a finite-element model using visco-elasto-plastic rheology. The free parameters of the model (essentially, the locking status of the three thrusts included in the study), were constrained by matching the observed horizontal GPS and vertical levelling data. We show that the amount of interseismic fault locking, and thus the seismic potential, is not necessarily associated with the fastest-slipping faults. More specifically, the locked Bassano thrust has a greater seismic potential than the freely slipping Montello thrust. The findings suggest that faults with subtle evidence of Quaternary activity should be carefully considered when creating seismic hazard maps.
    Description: Published
    Description: 221-227
    Description: 3.2. Tettonica attiva
    Description: 3.3. Geodinamica e struttura dell'interno della Terra
    Description: JCR Journal
    Description: open
    Keywords: interseismic deformation ; Montello thrust ; Southern Alps ; 04. Solid Earth::04.04. Geology::04.04.01. Earthquake geology and paleoseismology ; 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
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 21
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    Anomalous far-field geodetic signature related to the 2009 L’Aquila (central Italy) earthquake (2013)
    Wiley-Blackwell
    Details
    Publication Date: 2022-05-24
    Description: The broad availability of geodetic measurements for the Mw 6.3 April 6th 2009 L’Aquila earthquake allowed an unprecedented description of the co- and post-seismic ground deformations, leading to the definition of the Paganica fault geometry and kinematics. Through DInSAR, we found, in a wide area of 20 kilometres on the Paganica hangingwall, a further displacement up to 7 cm, which might have occurred in the earthquake proximity. In this study, we explore the possibility of the co-, post- and pre-seismic alternative scenarios. Although our data are not sufficient to undoubtedly prove that this signal occurred before the main event, this seems to be the most likely hypothesis based on tectonics constraints and image acquisition times. The nature of this deformation remains unclear, but we speculate that deep fluids played a role. These results can drive ad hoc requirements for future space-based missions and design of the GPS network.
    Description: Published
    Description: 343–351
    Description: 1.10. TTC - Telerilevamento
    Description: JCR Journal
    Description: restricted
    Keywords: InSAR ; L'Aquila earthquake ; GPS ; Anomalous signature ; 04. Solid Earth::04.06. Seismology::04.06.03. Earthquake source and dynamics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 22
    Electronic Resource
    Electronic Resource
    Polycarbonat-ein vielseitiger werkstoff mit zukunft (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 244 (1997), S. 43-66 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The market development of bisphenol-A-polycarbonate has shown higher growth than any other engineering thermoplastic. The reasons can be found in the permanent improvement of the cost/performance-relationship and in the technical use of the variability of the basic structure. Incorporation of specific monomer units leads to tailor-made properties for a wide range of applications, as for example medical devices, electronic parts and glazing.This process has not yet slowed down, rather it is accelerated by new results from research and development. The improvement of flaw behavior and pit replication for new grades of materials for the next generation of compact discs, new grades that can be sterilized by γ-radiation without degradation and the microstructuring by low-energy laser systems are examples for the ongoing expansion of polycarbonate applications. Surface modification by hardcoatings with nanosized particles will allow to enter the fast growing market of glazing.
    Additional Material: 27 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1997.052440103
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  • 23
    Electronic Resource
    Electronic Resource
    Polyamide, polyester und polyoxymethylen. Die klassischen technischen kunststoffe und ihre perspektiven (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 244 (1997), S. 67-92 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polyamide, Polyester und Polyoxymethylen sind mit einem weltweiten Verbrauch von derzeit 2,4 Mio t pro Jahr wichtige technische Kunststoffe. Sie werden aufgrund ihrer besonderen Eigenschaftsprofile überwiegend im Fahrzeugbau und in der Elektroindustrie für hochbelastete Funktionsbauteile eingesetzt. Der vorliegende Beitrag behandelt Polymerisationswege, Eigenschaften und ausgewählte neue Entwicklungen dieser Polymerklassen.Teilaromatische Polyamide stoßen durch ihre Dimensionsstabilität und thermische Belastbarkeit in Anwendungen vor, die bisher Duromeren oder Metallen vorbehalten waren. Glasfaserverstärkte Polyamide mit besonders hoher Dauerwärmebeständigkeit übemehmen wichtige Funktionen im Motorbereich von Fahrzeugen. Polyamid-Blends sind als Karosseriewerkstoffe ein Schlüssel zu leichten Autos mit niedrigem Treibstoffverbrauch. Halogenfrei flammgeschützte Polyamide erhöhen Sicherheit und Umweltverträglichkeit in brandgefährdeten Anwendungsbereichen.Polybutylenterephthalat als technisch wichtigster Polyester eröffnet in Mischung mit amorphen Polymeren neue Perspektiven durch geringerenVerzug und bessere Oberfläche bei glasfaserverstärkten Teilen. Polybutylennaphthalat erweitert den Anwendungsbereich zu höheren Temperaturen. Von Polybutylenterephthalat abgeleitete Copolyester sind biologisch abbaubar und daher vielversprechend für kompostierbare Folien.Polyoxymethylen-Copolymere haben ihre Stärke in der günstigen Kombination aus Steifigkeit, Dimensionsstabilität, Gleit/Reibe-Verhalten und Beständigkeit gegen heißes Wasser und Kraftstoff.Aufgrund ihres hohen und noch weiter steigerungsfähigen Leistungsvermögens werden Polyamide, Polyester und Polyoxymethylen das in den letzten Jahren gezeigte Wachstum in Zukunft weiter ausbauen können.
    Notes: Polyamide, polyester and polyoxymethylene having presently a worldwide sales volume of 2,4 million tons a year are important engineering thermoplastics. Based on their special property profiles they are mainly used in the automotive and electronic industry for high performance functional parts. This contribution presents polymerisation processes, properties, and selected new developments for these polymer classes.Semiaromatic polyamides due to their dimensional stability and thermal resistance lend themselves to applications which were so far reserved for thermosets or metals. Glass fiber reinforce polyamides designed to have the highest possible heat ageing resistance can take important functions under the hood. A polyamide blend used as a material for exterior body parts is key to light weight cars with strongly reduced fuel consumption. Halogene free flame retardant polyamide increases fire safety and environmental safety in flame sensitive applications.Polybutyleneterephthalate as the technically most important polyester offers new perspectives in blends with amorphous polymers leading to lower distortion and better surface quality in glass fiber reinforced parts. Polybutylenenaphthalate is widening the range of application of polyesters towards higher temperatures. Copolyesters derived from polybutyleneterephthalate are biologically degradable and are therefore promising materials for fermentable foils.Polyoxymethylene copolymers show an outstanding combination of stiffness, dimensional stability, friction and wear as well as resistance against hot water and fuel.As a result of their excellent properties and the existing potential for further improvements polyamide, polyester and polyoxymethylene will continue to grow above average in the future.
    Additional Material: 18 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1997.052440104
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  • 24
    Electronic Resource
    Electronic Resource
    Sind polyurethanwerkstoffe ein reifes gebiet? (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 244 (1997), S. 121-133 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The world-wide production of polyurethanes has exceeded 6 mio. metric tons in 1994. Compared with the produced amounts of large-scale thermoplastics such as PE, PVC, PP and PS, polyurethanes keep the 5th place.Polyurethanes (PUR) are segmented polymers, which can be synthesized from preformed building blocks in a modular unit construction system. The chemical modules and the various possibilities of combination will be discussed here.Tailor-made polyurethane materials can be divided into two main-fields of application: foams and compact PUR.The main constituents of polyurethane materials are diisocyanates and polyols. These key- chemicals are well characterised with respect to their technological, economical and ecological properties. Taking into account the availability, the masses of production and the experiences that have been collected with the PUR main constituents, these PUR precursors seem to be very mature already.In contrast to this, the PUR-materials made from these building blocks still offer numerous novel problem-solutions, resulting from the variability of the diisocyanate-poly-addition reaction: PUR materials are most commonly segmented into several phases. The formation of hard- and softsegments can be easily demonstrated by looking at thermoplastic polyurethanes (TPU). A deeper understanding of this phase separation and the molecular organisation within these materials promises to realize prospectic polymeric architectures with new and improved properties. PUR materials will still be able to offer new answers to future requirements in balancing economical and ecological needs. By looking at the life-cycles of soft and hard-foams, polyurethane-coatings and thermoplastic PUR-elastomers, this contribution will adress the question: “Is PUR-chemsitry still a challenging field?”
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1997.052440106
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  • 25
    Electronic Resource
    Electronic Resource
    Fire-retardant action of potassium nitrate in polyamide 6 (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 23-35 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Zugabe von 10-20 Gew.-% Kaliumnitrat (KN03) zu Polyamid 6 (PA 6) vermindert die Brennbarkeit des Polymeren. Das thermische Verhalten der KN03/PA 6-Mischung wurde mittels Thermogravimetrie, Differentialkalorimetrie und Analyse der fluchtigen Anteile untersucht. Feste Zersetzungsprodukte der Mischung wurden mittels Infrarotspektroskopie, Rontgendiffraktometrie und Elektronenresonanzspek-'troskopie analysiert. Es wurde gefunden, daß KNO3 dem Flielßen und Tropfen der Schmelze vorbeugt und die Karbonisierung auf der Oberflache des Polymeren fordert. Das verringert die Brandgefahr und verbessert die Feuerbestandigkeit. Andererseits geht KNO3 mit PA 6 in der kondensierten Phase eine exotherme Reaktion ein und setzt Sauerstoff frei, der wiederum die Brennbarkeit von PA 6 begiinstigt. Der Mechanismus der chemischen Wechselwirkung van KNO3 mit PA 6 wird diskutiert.
    Notes: The addition of 10-20 wt.-% of potassium nitrate (KNO3) to polyamide 6 (PA 6) improves the fire retardance of the polymer. The thermal decomposition behaviour of the PA 6/KN03-mixture was studied using thermogravimetry, differential scanning calorimetry and thermal volatilisation analysis. Solid products of the thermal decomposition of the mixture were analysed by infrared spectroscopy, X-ray diffraction and electron paramagnetic resonance. It was found that KNO, prevents flowing and dripping of the melt and promotes charring on the surface of the polymer which decreases its fire hazard and improves its fire retardance. On the other hand, KNO3 exothermally reacts with PA 6 in the condensed phase and supplies oxygen to the gas phase which increases the combustibility of PA 6. The mechanism of the chemical interaction of KN03 with PA 6 is discussed.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1997.052450103
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  • 26
    Electronic Resource
    Electronic Resource
    Effect of tricalcium phosphate, hydroxyethyl methacrylate, and ethylene glycol dimethacrylate on the mechanical properties of acrylic bone cement (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 49-62 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Einfluß einer Beimischung von Tricalciumphosphat (TCP), Hydroxyethylmethacrylat (HEMA) und Ethylenglycoldimethacrylat (EGDMA) auf die Eigenschaften eines chirurgischen Knochenzements wurde untersucht. Die in Zugversuchen entstandenen Bruchflächen wurden mittels Rasterelektronenmikroskopie charakterisiert. Der Einfluß der Additive auf den Temperaturanstieg während der Polymerisation wurde geprüft. Zug-, Biege- und Druckfestigkeit des ausgehärteten Zements nahmen mit zunehmendem TCP-Gehalt ab, der Elastizitätsmodul stieg dagegen an. Die Zugfestigkeit nahm mit steigendem HEMA-Gehalt geringfügig zu und blieb oberhalb 15 Gew.-% HEMA konstant. Zug-, Biege- und Druckfestigkeit zeigten bei einem EGDMA-Gehalt von 2 Gew.-% (in HEMA) ein Maximum. HEMA und EGDMA beschleunigten die Polymerisation, wogegen TCP retardierend wirkte.
    Notes: The effects of the addition of tricalcium phosphate (TCP), hydroxyethyl methacrylate (HEMA), and ethylene glycol dimethacrylate (EGDMA) on the properties of standard surgical Simplex-P radiopaque bone cement have been investigated. The fracture surface after tensile test was studied by scanning electron microscopy. The influence of these components on the temperature rise during polymerization was investigated. It was found that the tensile strength, the bending strength, and the compressive strength decreased with increasing TCP content, whereas the inverse was observed for the Young's modulus. The tensile strength slightly increased with increasing HEMA content and then it levelled off when the HEMA content was higher than 15 wt.-%. It seemed that there were maximum tensile, bending and compressive strengths when 2 wt.-% EGDMA (in HEMA) was added. Polymerization occurred more rapidly when HEMA and EGDMA were added, whereas the inverse result was found with TCP.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1997.052450105
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  • 27
    Electronic Resource
    Electronic Resource
    The relative physical and thermal properties of polyurethane elastomers. Effect of chain extenders derived from dihydroxynaphthalene (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 89-104 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polyurethanelastomere wurden in Gegenwart von zwei Dihydroxynaphthalin(DHN)-Verbindungen und deren bromierter Derivate als Kettenverlängerer hergestellt. Als Polyole wurden Polycaprolactondiol und Polytetramethylenglykol und als Diisocyanat-Komponenten Diphenylmethandiisocyanat (MDI) und Dicyclohexylmethan-4,4′-diisocyanat (HMDI) eingesetzt. Der Einfluß der Struktur der Kettenverlängerer auf die physikalischen und thermischen Eigenschaften der Polyurethane wurde untersucht. Wegen der besseren Phasenmischungswirkung der 1,5-DHN-Segmente haben die damit hergestellten Polyurethane höhere Glasübergangstemperaturen und bessere dynamische Eigenschaften als die Polyurethane auf 2,7-DHN-Basis. Der Einbau von bromierten DHN-Einheiten erschwert die Entflammbarkeit. Durch das große freie Volumen der Bromatome wird jedoch die Rotation der DHN-Einheiten eingeschränkt, was zu Polyurethanen mit verringerten Phasenmischungs- und Kristallisationsgraden führt. Die bromhaltigen Polyurethane zeigen zudem eine Verschlechterung der mechanischen und physikalischen Eigenschaften und eine erhöhte Löslichkeit.
    Notes: Polyurethane elastomers were synthesized based on polyols such as poly(caprolactonediol) and poly(tetramethylene glycol), diisocyanates such as diphenylmethane-4,4′-diisocyanate (MDI) and dicyclohexylmethane-4,4′-diisocyanate (HMDI), and two dihydroxynaphthalenes (DHNs) and their brominated derivatives used as chain extenders. The effects of the chemical structures of the chain extenders on the physical and thermal properties of the polyurethanes were investigated. Because of the higher degree of phase mixing of the 1,5-DHN unit, the 1,5-DHN-based polyurethanes have higher Tg values and higher dynamic properties than 2,7-DHN-based polyurethanes. Introduction of bromine atoms increased the flame retardance. However, the large free volume of bromine atoms restricted the rotation of DHNs, thus, directly decreasing the degree of phase-mixing and crystallinity of the polyurethanes. Introducing bromine atoms also decreased the mechanical and dynamic properties and increased the solubility of the polyurethanes.
    Additional Material: 1 Ill.
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    Synthesis and characterization of polypyrrolepolyurethane cationomer composites (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 139-147 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Aus Poly(oxytetramethylen), 4,4′-Bibenzyldiisocyanat, N-Methyldiethanolamin als Kettenverlängerer und Acrylsäure/Polyacrylsäure als Quaternisierungsagens wurden Poly(etherurethan)-Kationomere hergestellt. In aus diesen Kationomeren hergestellten Filmen wurde Pyrrol (15 Gew.-%) in Gegenwart von CuCl2 polymerisiert. Die Filme wurden mittels dynamisch-mechanischer Analyse, Thermogravimetrie und Differentialthermoanalyse charakterisiert. Die elektrische Leitfähigkeit beträgt für den Film ohne Polypyrrol 7.5 · 10-12 Ω-1 cm-1 und mit Polypyrrol 4.5 · 10-6 Ω-1 cm-1.
    Notes: Poly(ether urethane) cationomers based on poly(oxytetramethylene), 4,4′-bibenzyldiisocyanate, N-methyldiethanolamine as chain extender, and acrylic acid/poly(acrylic acid) as quaternization agent were synthesized. Pyrrole (15 wt.%%) was polymerized in films of the ionomer containing CuCl2. The films were characterized by dynamic mechanical analysis, thermogravimetry and differential scanning calorimetry. The electric conductivity of the film without polypyrrole is 7.5 · 10-12 Ω-1 cm-1, while incorporation of polypyrrole increases the conductivity to 4.5 · 10-6 Ω-1 cm-1.
    Additional Material: 2 Ill.
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    Synthesis, characterization and polymerization of waxy monomers (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 155-164 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Wachsartige Monomere und Vernetzer wurden aus kommerziellen Wachsen durch Veresterung mit 2-Hydroxyethylmethacrylat, Glycerindimethacrylat oder Glycidylmethacrylat oder durch Funktionalisierung mit 2-Isocyanatoethylmethacrylat synthetisiert. Die erhaltenen opaken Methacrylate mit Schmelzpunkten zwischen 45 und 80°C wurden in Substanz bzw. Toluollösung in Gegenwart von Radikalinitiatoren polymerisiert. Die Polymeren zeichnen sich durch eine breite Molmassenverteilung aus. Im Gegensatz zur Substanzpolymerisation ist der Doppelbindungsumsatz nach der Lösungspolymerisation nahezu vollständig. Aufgrund der hohen Molmasse der Monomeren ist der beobachtete Polymerisationsschrumpf sehr gering. Polymerisate mit Vernetzermonomeren zeigen eine verbesserte mechanische Stabilität.
    Notes: Waxy monomers and crosslinkers, respectively, were synthesized from commercially available waxes by esterification with 2-hydroxyethyl methacrylate, glycerol dimethacrylate, or glycidyl methacrylate or by functionalization with 2-isocyanatoethyl methacrylate. The resulting opaque methacrylates with melting points between 45 and 80°C were polymerized in bulk and in toluene solution in presence of free radical initiators. The obtained polymers were characterized by a broad molecular weight distribution. Opposite to the bulk polymerization, the double bond conversion in solution polymerization is nearly quantitative. The observed volume shrinkage during polymerization is very low due to the high molecular weight of the monomers. Polymerizates containing crosslinking comonomers exhibit improved mechanical stability.
    Additional Material: 5 Tab.
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    Zur Kinetik der stabilisierten Fällungs-polymerisation eines Kationischen Monomeren in wäßrigen Natriumchlorid-Lösungen (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 245 (1997), S. 165-181 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The stabilized free-radical precipitation polymerization of the cationic monomer N-(2-methacryloyloxyethyl)-N,N-dimethylbenzylammonium chloride (MADAMBQ) in aqueous solutions of sodium chloride was studied by reaction calorimetry. Poly(ethylene oxide) was used as stabilizer. The rate of polymerization reaches its maximum immediately after initiation and remains nearly constant up to 50 % conversion followed by a decrease that could be described by a first order kinetics. The particles formed are approximately 1 to 30 μm in diameter and are stable over a period of several months.A model based on the theory of homogeneous particle nucleation is suggested to describe the kinetic course of polymerization, taking into account the rate of polymerization in both phases. With the assumption that the concentration of monomer in the phases is determined by a Nernst distribution law, the kinetics of the early stage of polymerization can be modelled reasonably well.The solution polymerization and the unstabilized precipitation polymerization of MADAMBQ was also studied.
    Notes: Die Kinetik der stabilisierten Fällungspolymerisation des kationischen Monomeren N-(2-Methacryloyloxyethyl)-N,N-dimethylbenzylammoniumchlorid (MADAMBQ) in wäßrigen Natriumchlorid-Lösungen wurde mittels Reaktionskalorimetrie untersucht. Polyethylenoxid höherer Molmasse wurde als Stabilisator eingesetzt. Die Reaktionsgeschwindigkeit ist über einen größeren Umsatzbereich nahezu konstant und fällt anschließend mit dem Umsatz annähernd linear ab. Die Teilchengrößenverteilung der gebildeten Dispersion ist bimodal mit Teilchen von etwa 1 bis 30 μm Durchmesser.Zur Beschreibung des Geschwindigkeitsverlaufs der Fällungspolymerisation wird ein Modell vorgeschlagen, das die Polymerisation in der Wasser- sowie in der Polymerphase berücksichtigt. Die Teilchenbildung soll durch homogene Nukleierung erfolgen. Es wird angenommen, daß die Konzentration des Monomeren in den Phasen durch ein Nernstsches Verteilungsgleichgewicht bestimmt wird. Zu Vergleichszwecken wurde auch die Polymerisation von MADAMBQ in Lösung und als nicht stabilisierte Fällungspolymerisation durchgeführt.
    Additional Material: 8 Ill.
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    An investigation of the grafting of cellulose powder with acrylamide under a magnetic field (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 246 (1997), S. 1-9 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Cellulosepulver, hergestellt durch Nitrierung von Eichen-Furfural-Lignocellulose, wurde mit Acrylamid radikalisch gepfropft. Die Pfropfreaktion wurde sowohl in Gegenwart eines äußeren Magnetfeldes (0,15-0,35 T) als auch ohne Magnetfeld durchgeführt. Der Einfluß von Monomerkonzentration, Initiatorkonzentration, Polymerisationszeit und temperatur sowie der magnetischen Feldstärke auf den Polymerisationsverlauf wurde untersucht. Es wurde festgestellt, daß der Pfropfumsatz mit zunehmender Feldstärke signifikant ansteigt.
    Notes: Cellulose powder obtained from oak furfural lignocellulose by nitration reaction was grafted with acrylamide using a radical initiation. The grafting reactions were carried out and compared both in presence and in absence of a continuous external magnetic field with the intensity extended between 0.15-0.35 T. The effect of monomer and initiator concentration, time and temperature of reaction and magnetic field intensity onto the grafting process were examined. It was observed that the presence of a magnetic field leads to a significant increase of the graft conversion.
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    Radical polymerization of poly(butyl acrylate) in the presence of poly(L-lactic acid), 1. Synthesis, characterization and properties of blends (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 246 (1997), S. 49-63 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Poly(L-milchsäure) ist ein biokompatibler, semikristalliner, thermoplastischer Polyester mit ungünstigen mechanischen Eigenschaften. Daher wurde in einem “reactive blending”-Prozeß ein Acrylkautschuk, n-Butylacrylat, mittels einer Suspensionspolymerisation in Wasser auf in einem organischen Lösungsmittel gelöste Poly(L-milchsäure) gepfropft. Die gebildeten Copolymeren konnten isoliert und durch NMR-Spektroskopie und DSC-Messungen charakterisiert werden. Die Untersuchung der mechanischen Eigenschaften ergab keine befriedigenden Ergebnisse, weil die Kautschukphase wahrscheinlich aus viskosen linearen Makromolekülen besteht und daher keine elastischen Eigenschaften besitzt. In weiteren Arbeiten soll der Syntheseweg so modifiziert werden, daß durch den Einbau von Diacrylaten eine zumindest partielle Vernetzung der Kautschukphase erreicht wird.
    Notes: Poly(L-lactic acid) is a biocompatible polyester, semicrystalline, thermoplastic, with low versatility in mechanical properties. To overcome this problem, a reactive blending procedure was performed by grafting an acrylic rubber, n-butyl acrylate, via water suspension polymerization onto poly(L-lactic acid) dissolved in an organic solvent. It was possible to isolate the copolymeric phase formed from the two polymers and characterize it by using NMR and DSC techniques. Mechanical tests on blends gave no satisfactory response, probably because the rubbery phase is composed essentially of viscous linear macromolecules, not able to perform elastic properties. Work is in progress to modify the synthetic pathway to incorporate diacrylates in order to realize a rubbery phase at least partially cross-linked.
    Additional Material: 7 Ill.
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    Tin-coupled styrene-butadiene rubbers (SBRs). Relationship between coupling type and propertiesBased on a paper presented at the 148th Meeting of the Rubber Division, American Chemical Society, Cleveland, Ohio, 17-20 October 1995. (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 246 (1997), S. 85-96 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Zur Entwicklung von neuen Styrol-Butadien-Kautschuken (SBRs) für Reifenanwendungen sind mehrere Arten von Zinn-Polymer-Bindungen (Styryl-, Butadienyl-, Isoprenyl- and α-Methylstyryl-Zinn) sowohl in linearen als auch in verzweigten Ketten untersucht worden. Die dynamisch-mechanischen Eigenschaften von Vulkanisaten mit Ruß wurden analysiert, um eine Beziehung zwischen den Strukturparametern der Polymeren und den Materialeigenschaften herzustellen. Der Polymer-Füll-stoff-Wechselwirkungsparameter, der durch das Verhältnis von mechanischen und dynamischen Termen definiert ist, wurde zur Charakterisierung der Verbindungen herangezogen. Der Einbau von verschiedenen Zinn-Polymer-Bindungen in lineare und in verzweigte SBR-Ketten bewirkte eine Verbesserung der Hystereseeigenschaf-ten der Vulkanisate und eine Veranderung des Wechselwirkungsparameters.
    Notes: Following the development of new SBRs for tyre applications, several kinds of tin-polymer bonds (styryl-, butadienyl-, isoprenyl- and α-methylstyryltin) have been studied, in both branched and linear chains.Dynamic-mechanical properties of the carbon black vulcanizates have been analyzed to establish a relationship between structural parameters of polymers and compound properties. The filler-polymer interaction parameter, defined by a ratio of mechanical and dynamic terms, has been used for the evaluation of the compounds. The introduction of different types of tin-polymer bonds, in branched and linear chains of the SBRs, implies an improvement in the hysteresis properties of the vulcanizates as well as a modification of the interaction parameter.
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    A novel spin-finishing method for antistatic modification of polyester fiber. Surface reaction onto amine-containing copoly(amide-ethers) blended with polyester fiber (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 246 (1997), S. 109-123 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Copoly (amid-ether) rnit zwei unteschiedlichen Aminfunktionalitäten wurden als antistatische Modifikatoren für Polyethylenterephthalatfasern (PET) eingesetzt. Die tertiären Aminogruppen schmelzegesponnener Copolymerfilamente wurden rnit drei Alkylierungsmitteln umgesetzt, wobei ein Sulfobetain, ein Carbobetain bzw. Ammoniumionen gebildet wurden. Dadurch wurde der scheinbare spezifische Widerstand der Filamente auf größfienordnungsmäßfiig 106 bis 108 Ω/cm verringert. Da sich die quaternisierten Copolymeren beim Blend-Spinnen rnit PET zersetzen, wurden Blendfasern von PET mit einem Copolymeren nach dem Schmelzespinnen einer Quaternisierung oder Vernetzung rnit Alkylierungsmitteln bzw. Epoxyvernetzern unterzogen, was die antistatischen Eigenschaften der Fasern im Vergleich rnit der unbehandelten Faser verbesserte. Insbesondere die mit Epoxiden vernetzten Fasern wiesen antistatische Eigenschaften auf, wie sie mit dieser Modifizierungsmethode bislang nicht erreicht wurden. Die antistatischen Eigenschaften blieben nach dem Fkben erhalten, da sowohl die hydrophilen als auch die ionischen Gruppen auf der Faseroberflache immobilisiert waren. Da Quaternisierung bzw. Vernetzung in einem Arbeitsgang rnit dem Verspinnen und Verstrecken der Fasern innerhalb einer kurzen Reaktionszeit erfolgen, sollte diese “spin-finishing„ genannte Methode konventio- nellen Verfahren bezuglich Kosten und Produktivitat uberlegen sein.
    Notes: Copoly(amide-ethers) containing two types of tertiary amine units were made as antistatic modifiers for poly(ethylene terephthalate) (PET) fibers. The filaments of the copolymers were melt-spun and reacted with three alkylating agents in order to quaternize the tertiary amine into a sulfo-betaine, a carbobetaine, and an ammonium ion. The apparent electric resistivity of the filaments was greatly reduced by this reaction, being in the range of 106 to 108 Ω/cm. However, because these quaternized copolymers incurred decomposition during blend spinning with PET, a blend PET fiber containing one type of copoly(amide-ether) was melt-spun and subjected to quaternization of the amino groups as well as to surface crosslinking with various alkylating and epoxy agents. The quaternized blend fibers obtained showed improved antistatic properties compared with the original blend fiber. Particularly, the fibers crosslinked with epoxy compounds were found to have the best antistatic properties that had ever been attained with this type of modification. The antistatic properties were retained even after dyeing, because both hydrophilic and ionic groups had been effectively immobilized on the surface. Since this quaternization and crosslinking could be conducted on-line with spinning and drawing within a short reaction time, this modification technique is called “spin-finishing method”, which should be superior to the conventional methods in terms of cost performance and productivity.
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    Etching of a low-density polyethylene film by fuming nitric acid (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 249 (1997), S. 33-46 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Filme aus Polyethylen niedriger Dichte (LDPE) wurden mit rauchender Salpetersäure behandelt. Die Oberflächeneigenschaften sowie die Bildung polarer Gruppen wie auf der geätzten Filmoberfläche wurden mit SEM-, IR- und XPS-Methoden analysiert. Die mechanische Festigkeit eines aus dem geätzten LDPE-Film und einem Epoxidharz hergestellten Laminats sowie die Bedruckbarkeit der geätzten Oberflächen wurden untersucht und mit einer unbehandelten Probe verglichen. Die Oberflächenrauhigkeit und die Gegenwart polarer Gruppen erhöhen die mechanische Festigkeit des Laminats aus dem geätzten Film durch mechanische Verankerung und chemischer Wechselwirkungen. Die Oberfläche des behandelten LDPE-Films ist besser bedruckbar als die des unbehandelten Films.
    Notes: Low-density polyethylene (LDPE) films were treated with fuming nitric acid (FNA). The surface characteristics and also the insertion of polar groups like on the etched LDPE film surface were measured by SEM, IR and XPS analyses, respectively. The mechanical performance of a laminate of the etched film with epoxy resin and also the printability of the etched film surface were tested and compared with the unetched sample. The surface roughening and the presence of polar groups enhance the mechanical strength of the laminate of FNA-treated film due to mechanical interlocking and chemical interaction. The printability of the treated film surface is also superior to that of the untreated LDPE film surface.
    Additional Material: 10 Ill.
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    Celluloseether als Trennschichten hydrophiler Polymermembranen (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 249 (1997), S. 11-32 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: This paper reports on polymer membranes characterized by a surface layer of hydroxyalkyl derivatives of cellulose. Water compatible polymers like hydroxyalkyl derivatives of cellulose are preferably those exhibiting good chemical stability and desired membrane characteristics. Normally, water-compatible polymers used in the coating solutions must be rendered water-insoluble after coating. By adapting crosslinking conditions on separation problems, the membranes are useful for many processes in the fields of biotechnology, food and chemical industry.The membranes presented here possess the advantage of being highly resistant to chemical and biological degradation and, hence, have long lifetimes under many process conditions.
    Notes: Es wird die Entwicklung hydrophiler Polymermembranen diskutiert, die nach Beschichtung mit Celluloseethern und anschließender Vernetzung auf den asymmetrischen Trägermembranen interessante Permeations- und Trenneigenschaften bei hervorragenden chemischen Stabilitäten, vor allem beim Membrantrennverfahren der Nanofiltration, aufzeigen. Weiterhin werden Aussagen zu den Gastrenneigenschaften der Celluloseetherkompositmembranen getroffen.Erläutert werden die Permeations- und Trenndaten der Kompositmembranen in Korrelation zur Vernetzung der Celluloseether anhand verschiedener Einflußgrößen, was qualitative und gegebenenfalls quantitative Aussagen zum Vernetzungsmechanismus der Celluloseetherderivate erlaubt. Dabei stehen die Vernetzungstemperatur, der Einfluß der katalysierenden Wasserstoffionen und bedingt die Vernetzungszeit im Vordergrund. Abgerundet werden die Arbeiten durch Ermittlungen rheologischer Daten, die in Zusammenhang zu den Vernetzungsreaktionen und damit zu membranspezifischen Größen stehen.Infolge der hervorragenden chemischen Stabilität der Celluloseether werden Einsatzmöglichkeiten der Kompositmembranen zur Nanofiltration niedermolekularer Verbindungen aus organisch hochbelasteten Systemen beschrieben.
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    Products of polycondensation of 4,4′-biphenyldithiol with some hydrocarbon dihalides (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 13-21 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polysulfide wurden mit hoher Ausbeute durch Hochtemperatur-Lösungspolykondensation von 4,4′-Dimercaptobiphenyl mit ausgewählten aliphatischen und aromatisch-aliphatischen Dihalogenkohlenwasserstoffen hergestellt. Um die optimalen Polykondensationsbedingungen zu bestimmen, wurde der Einfluß folgender Faktoren auf die reduzierte Viskosität und die Ausbeute der Polysulfide ermittelt: Art des organischen Lösungsmittels, Art des Halogenwasserstoff-Akzeptors, Konzentration der organischen Reagenzien, Reaktionstemperatur und -zeit. Die Polykondensation des Dithiols mit Bis(4-chlormethylphenyl)methan wurde als Modellsystem eingehender untersucht. Die Polysulfidstrukturen wurden mittels Elementaranalyse, IR-Spektroskopie und Röntgenstrukturanalyse bestätigt. Aus der thermogravimetrischen Analyse wurden die Zersetzungstemperatur, der Gewichtsverlust bei dieser Temperatur und das Maximum der Zersetzungsgeschwindigkeit erhalten. Weiterhin wurden einige physikalisch-chemische, mechanische und dielektrische Eigenschaften ermittelt. Die beste thermische und chemische Bestandigkeit zeigt das aus dem Dithiol und 4,4′-Bis(chlormethyl)biphenyl hergestellte Polysulfid, was auf dessen vorwiegend aromatische Struktur zuriickgefuhrt werden kann.
    Notes: Polysulfides were synthesized with high yield by high-temperature solution polycondensation of 4,4′-biphenyldithiol with selected aliphatic and aromatic-aliphatic hydrocarbon dihalides. To determine the optimum polycondensation conditions, the influence of the following factors on reduced viscosity and yield was studied: type of organic solvent, type of hydrogen halide acceptor, concentration of reagents, reaction temperature, and reaction time. A thorough examination was carried out only for the polycondensation of dithiol with bis(4-chloromethylphenyl)methane chosen as model system. The structures of the polysulfides were confirmed by elemental analysis, X-ray analysis, and infrared spectroscopy. The temperature of initial decomposition, the percentage of mass loss, and the temperature of the fastest decomposition, process were determined from curves of differential thermal and thermogravimetric analysis. Some physicochemical, mechanical and electrical properties were determined. The highest thermal and chemical resistance has been found for the polysulfide obtained from 4,4′-biphenyldithiol and 4,4′-bis(chloromethyl)biphenyl, probably because of the predominantly aromatic structure.
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    Organic-inorganic hybrid sol-gel materials, 2. Application for dental composites (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 61-72 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Drie organisch-anorganische Hybridmaterialien wurden nach dem Sol-Gel-Verfahren durch kovalenten Einbau von Poly(styrol-co-methylmethacrylat)(Poly(St-co-MMA))-, Polymethylmethacrylat(PMMA)- und Polystyrol(PS)-Struktureinheiten in ein SiO2-Netzwerk hergestellt und als Füllstoffe (bis zu 60 Gew.-%) in Dentalharzen verwendet. Der Einfluß der Füllstoffe auf einige mechanische Eigenschaften der Harze wurde untersucht. Die Härte der gefüllten Dentalharze nahm mit steigendem Füllstoffgehalt zu, wogegen die Biegefestigkeit abnahm. Die Druckfestigkeit der gefüllten Harze war besser als die des ungefüllten Harzes, nahm jedoch mit steigendem Füllstoffgehalt ab.
    Notes: By incorporating poly(methyl methacrylate) (PMMA), polystyrene (PS), and poly(styrene-co-methyl methacrylate) (poly(St-co-MMA)) structure units covalently into the SiO2 glass network via a sol-gel approach, three organic-inorganic hybrid materials (PMMA-SiO2, PS - SiO2, and poly(St-co-MMA) - SiO2) have been prepared. The three hybrid sol-gel materials were used as filler (up to 60 wt.-%) for dental composite resins. The effect of the three filler materials on several mechanical properties of the dental composite resins was investigated. The hardness of the filled dental composites increased with increasing filler content, whereas the bending strength decreased. The compressive strength of the composites was improved, compared with the unfilled resin, but decreased with inreasing filler content.
    Additional Material: 6 Ill.
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    Adsorption of BTX compounds from aqueous solutions by water-insoluble starch (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 107-116 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Adsorption von Benzol, Toluol und p-Xylol (BTX) aus wäßrigen Lösungen mittels hochvernetzter kationischer Stärke mit tertiären Amingruppen wurde untersucht. Der endotherme Adsorptionsvorgang ist vom Anfangs-pH-Wert und der Anfangskonzentration abhängig und kann mit einer Langmuir-Isotherme beschrieben werden.Die Adsorptionswärme (Δ) bei pH 4 beträgt für Benzol, Toluol und Xylol 29,45 kJ mol-1, 34,41 kJ mol-1 bzw. 35,58 kJ mol-1, bei pH 10 30,17 kJ mol-1, 35.56 kJ mol-1 bzw. 39,39 kJ mol-1. Die adsorbierte Menge nimmt in der Reihenfolge Benzol 〉 Toluol 〉 Xylol ab.
    Notes: The removal of benzene, toluene and p-xylene (BTX) compounds from aqueous solutions with highly crosslinked cationic starch containing tertiary amine groups was investigated. The adsorption process has found to be initial pH- and initial concentration-dependent, endothermic, and follows the Langmuir isothermal adsorption.The heats of adsorption (ΔH) at initial pH = 4 of benzene, toluene and p-xylene compounds are 29.45 kJ mol-1, 34.41 kJ mol-1, and 35.58 kJ mol-1, respectively, those at initial pH = 10 are 30.17 kJ mol-1, 35.56 kJ mol-1, and 39.39 kJ mol-1, respectively. The order of the amount of adsorbed BTX compounds on the adsorbent is benzene 〉 toluene 〉 p-xylene.
    Additional Material: 3 Ill.
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    Thermogravimetric and ESR studies of polymer/metal precursors for high-temperature superconductors (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 157-170 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Bi-Sr-Ca-Cu-Komplexverbindungen von Polymethacrylsäure (PMAA) und Kresolnovolaken, die als Precursoren für Hochtemperatursupraleiter (HTSL) eingesetzt werden, sowie deren Cu-Komplexsalze wurden ESR-spektroskopisch und thermogravimetrisch untersucht. In den PMAA-Proben wurden drei verschiedene Cu2+-Spezies nachgewiesen: i) Cu2+-Paare, ii) isolierte Cu2+-Ionen und iii) Cu2+-Cluster. Bei niedrigem Cu-Gehalt der Proben bilden die Cu2+-Paar-Bindungen den Hauptanteil, bei hohem Cu-Gehalt überwiegen die Clusterbindungen. In den Novolakproben wurden nur isolierte Cu2+-Ionen und Cu2+-Cluster nachgewiesen. Die Einführung der Cu-Ionen erniedrigt die thermische Stabilität der Polymeren, der thermische Abbau erfolgt stufenweise. In den PMAA-Proben wird die erste Abbaustufe bei ≈ 220°C durch die Cu2+-Paar-Komplexe verursacht.
    Notes: Bi-Sr-Ca-Cu complexes of poly(methacrylic acid) (PMAA) and cresol novolac, which are precursors for high-temperature superconductors (HTSC) and Cu complexes of those polymers were investigated by ESR spectroscopy and thermogravimetry. In the PMAA samples three different kinds of Cu2+ species were detected: i) Cu2+ pairs, ii) isolated Cu2+ ions and iii) Cu2+ clusters. While Cu2+ pairs are the main species at low Cu concentrations, clusters become dominant at high Cu contents. In the novolac samples Cu2+ was only detected in isolated sites and clusters. The introduction of Cu ions lowered the thermal stability of the polymers and led to a stepwise decomposition. In the PMAA samples the first decomposition step at ≈ 220°C is caused by the Cu2+ pair complexes.
    Additional Material: 6 Ill.
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    Polymerization of 1,3-butadiene with neodymium chloride/2-ethylhexanolate/triethylaluminium catalyst systemIPCL communication No. 325. (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 193-205 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Neodymchlorid-2-ethylhexanolate mit der allgemeinen Formel NdCl3 · nL wurden durch eine Liganden-Austauschreaktion zwischen Neodymchloridisopropanolat (I) und 2-Ethylhexanol (EH) hergestellt. Die Hexanolate NdCl3 · 1,5 EH (II) und NdCl3 · 2,5 EH (III) wurden durch Elementaranalyse und Gravimetrie charakterisiert. Die katalytische Aktivität der Hexanolate bei der Homopolymerisation von 1,3-Butadien in Gegenwart von Triethylaluminium wurde untersucht. Die Verbindung III zeigte eine höhere Aktivität als die Verbindung II. Höhere Katalysator- und Cokatalysatorkonzentrationen sowie eine höhere Temperatur steigerten den Umsatz, wogegen die Viskosität der Produkte abnahm. Mit zunehmender Reaktionszeit erhöhten sich sowohl der Umsatz als auch die Viskosität. Die cis-1,4-Konformation wurde durch die Variation von Temperatur und Cokatalysatorkonzentration beeinflußt. Der gesamte Anteil der cis-1,4-Stuktur lag jedoch in allen Fällen über 99%, während die Produkte nur einen sehr geringen Vinyl-Anteil von 〈1% enthielten. Die Zugabe einer elektronenspendenden Verbindung verringerte den cis- 1,4-Gehalt aber auf 87%.
    Notes: Neodymium chloride 2-ethylhexanolates of the general formula NdCl3 · nL were prepared by ligand exchange reaction between neodymium chloride ispropanolate (I) and 2-ethylhexanol (EH). These hexanolates, NdCl3 · 1.5 EH (II) and NdCl3 · 2.5 EH (III), were characterized by elemental analysis and gravimetry. The catalytic activity of these hexanolates in combination with triethyl aluminium in the homopolymerization of 1,3-butadiene was studied, and the activity was found to be higher with III than II. The conversions increased with increasing the catalyst and co-catalyst concentrations and the temperature, whereas the intrinsic viscosity decreased. The conversions and the intrinsic viscosity decreased. The conversions and the intrinsic viscosity increased with reaction time. The cis-1,4 structure was influenced by variation in temperature and co-catalyst concentration, however, the total cis-1,4 structure was always more than 99% with very low vinyl content (〉1%). Addition of an external electron donor decreased the cis-1,4 content to 87%.
    Additional Material: 8 Ill.
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    The effects of desolvation methods of the recrystallized MgCl2-alcohol adduct on catalyst characteristics and the bulk density of polyethylene (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 253 (1997), S. 17-25 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: MgCl2-Träger für einen Ethylenpolymerisationskatalysator wurden mit Hilfe der Rekristallationsmethode hergestellt, wobei Methanol als Lösungsmittel diente. Der Einfluß verschiedener Lösungsmethoden des rekristallisierten MgCl2-Alkohol-Adduktes auf die morphologischen Charakteristika der Katalysatoren wurde untersucht. Die Lösungsmethode beeinflußt die Eigenschaften der Katalysatoren beträchtlich. Die dargestellten Katalysatoren wiesen unterschiedliche Ti/Mg-Verhältnisse auf, sowohl was die Oberfläche als auch die gesamten Katalysator-Partikel betrifft. Betrachtet man die Ti-Verteilung und Aktivitätsprofile, dann erweisen sich nicht nur die Polymerisationsbedingungen, sondern auch die Ti-Verteilung auf dem Katalysator als wichtige Faktoren, welche die Dichte der Polymeren beeinflussen.
    Notes: The MgCl2 supports for an ethylene polymerization catalyst were prepared by the recrystallization method using methanol as a solvent. The effects of different desolvation methods of the recrystallized MgCl2-alcohol adduct on the morphological characteristics of the catalysts were examined. The desolvation method greatly affects the characteristics of the catalyst. The prepared catalysts had different Ti/Mg ratios with respect to both surface content and entire catalyst particles. Considering Ti distribution and activity profiles, not only the polymerization conditions but also the Ti distribution on the catalyst appear to be an important factor which affects the bulk density of the polymers.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/apmc.1997.052530102
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    Synthesis of aromatic poly(ether ketone)s with ferrocene units in the main chain (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 253 (1997), S. 89-97 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Aromatische Poly(etherketon)e mit Ferrocen-Einheiten in der Hauptkette wurden durch direkte Polykondensation von 1,1′-Ferrocendicarbonsäure mit Diphenylether oder 1,4-Diphenoxybenzol hergestellt. Als Katalysatoren wurden Trifluormethansulfonsäure, Methansulfonsäure/P2O5 (Eatons Reagens) oder Trifluormethansulfonsäure/P2O5 verwendet. Polykondensationen bei Raumtemperatur für 24 h ergaben Poly(arylenetherketon)e mit Grenzviskositäten bis zu 40 mL g-1. Die Monoacylierung von Diphenylether mit Ferrocencarbonsäure wurde im Hinblick auf die Effektivität von Eatons Reagens als Katalysator und Lösungsmittel eingehender untersucht.
    Notes: Aromatic poly(ether ketone)s with ferrocene units in the main chain were prepared by direct polycondensation of 1,1′-ferrocenedicarboxylic acid with diphenyl ether or 1,4-diphenoxybenzene using various catalysts such as trifluoromethanesulfonic acid (triflic acid), a combination of methanesulfonic acid/P2O5 (Eaton's reagent) or a combination of triflic acid/P2O5. Polycondensations at room temperature for 24 h gave poly(arylene ether ketone)s with inherent viscosities up to 40 mL g-1. Monoacylation of diphenyl ether with ferrocenecarboxylic acid was studied in detail in order to show the efficiency of polymer formation employing Eaton's reagent as catalyst and solvent.
    Additional Material: 6 Ill.
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    Mechanical and structural characteristics of phenolphthalein poly(ether sulfone)/ultra-high molecular weight polyethylene blends (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 73-80 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die mechanischen und strukturellen Eigenschaften von Blends aus Phenolphthalein-Polyethersulfon und ultrahochmolekularem Polyethylen (UHMWPE) wurden anhand von Zug- und Biegeversuchen, Raster- und Transmissionselektronenmikroskopie untersucht. Die Zugabe einer geringen Menge UHMWPE (2 Gew.-%) führt zu einer Verstärkung der PES-C-Matrix. Höhere UHMWPE-Konzentrationen verschlechtern die mechanischen Eigenschaften. Die Strukturuntersuchungen zeigen, daß die Blends im gesamten Zusammensetzungsbereich mehrphasig sind. Bei geringen UHMWPE-Konzentrationen ist die UHMWPE-Phase gleichmäßig verteilt und entlang der Fließrichtung orientiert, was mit der starken Grenzflächenadhäsion zur Verbesserung des mechanischen Verhaltens beiträgt. Mit steigender UHMWPE-Konzentration nimmt die Domänengröß der UHMWPE-Phase zu.
    Notes: Mechanical and structural properties of blends of phenolphthalein poly(ether sulfone) (PES-C) with ultra-high molecular weight polyethylene (UHMWPE) were investigated using tensile and bending testing, scanning electron microscopy and transition electron microscopy. The incorporation of minor amounts of UHMWPE (2 wt.-%) into PES-C has a reinforcement effect. With higher concentrations of UHMWPE, the mechanical properties decrease gradually. Structural studies demonstrated that the blends are multiphasic in the whole composition range. The minor UHMWPE, dispersed uniformly and oriented along the flow direction, as well as the strong interfacial adhesion contribute to the increase of the mechanical performance of the blends. The domain size of the UHMWPE phase was found to increase with the increase of its concentration.
    Additional Material: 6 Ill.
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    Redox copolymer with N-bromosulfonamide groups for the decomposition of cyanide ions in dilute aqueous solutions (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 117-130 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Ein Redoxcopolymeres, ein makroporöses Poly(Styrol-co-Divinylbenzol) (S/DVB)-Harz mit N-Bromsulfonamidgruppen, wurde angewandt, um Cyanide aus wäßrigen Lösungen zu entfernen. Dieses Harz enthält aktives Brom in den funktionellen Gruppen (1.86 mmol g-1, 3.72 meq g-1) und weist Oxidationseigenschaften auf. Es wurde sowohl in statischen als auch in dynamischen Systemen für die Oxidation von Cyanidionen zu nichttoxischen Verbindungen angewandt. Die Reaktionen wurden in wäßrigen Lösungen mit 26-2600 mg L-1 CN- bei unterschiedlichen pH-Werten durchgeführt. Die Ergebnisse zeigten, daß dieses Harz die Cyanide leicht zu Cyanaten oxidiert, die ca. 1000 mal weniger toxisch sind. Bei Kontakt mit dem Harz fiel die Cyanidkonzentration in den Lösungen unter 0.05 mg L-1 CN-. Die —SO2NBrNa-Gruppen gingen dabei in —SO2NH2-Gruppen über. Diese konnten wiederum mit Natriumhypochlorit- und Natriumbromid-Lösungen reaktiviert werden. Es wurde auch eine Alternative zu der Cyanidionenoxidation mit N-Bromsulfonamid-Harz untersucht, indem ein analoges N-Chlorsulfonamid-Harz in Gengenwart von katalytischen Mengen von Bromiden angewandt wurde.
    Notes: A redox copolymer, macroporous poly(styrene-co-divinylbenzene) (S/DVB) resin having N-bromosulfonamide groups, was used for removal of cyanide ions from aqueous solutions. This resin contains active bromine in functional groups (1.86 mmol g-1, i. e. 3.72 meq g-1) and shows oxidative properties. It was employed in static and flow system for oxidation of cyanide ions to non-toxic compounds. The reactions were carried out in aqueous media containing 26-2600 mg L-1 CN- at different pH values. The data showed that the resin having active bromine easily oxidized cyanides, forming cyanates being 1000-times less toxic than cyanides. In contact with the resin the concentration of cyanides in tested solutions dropped below 0.05 mg L-1 CN-. During the oxidation processes the —SO2NBrNa groups transform to —SO2NH2 groups. They can be reactivated by use of sodium hypochlorite and bromide solutions. As an alternative to oxidation of cyanides by N-bromosulfonamide resin, the oxidation of these ions by N-chlorosulfonamide resin with addition of a small amount of bromides was examined.
    Additional Material: 3 Ill.
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    Mitteilungen/Announcements (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 251 (1997), S. 207-208 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: No Abstract
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    URL: http://dx.doi.org/10.1002/apmc.1997.052510118
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    Hydrolytic and thermal stability of novel polyurethane elastomers (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 252 (1997), S. 33-43 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Novel Polyester glycols with alkyl side groups were used for the improvement of thermal stability and hydrolytic stability of polyester urethane elastomers. The novel polyester glycols used are poly( β -methyl- δ -valerolactone)glycol (PMVL), poly(3-methyl pentamethylene adipate) glycol (PMPA), poly(nonamethylene-co-2-methyl octamcthylene carbonate) gycol (PNCO). A mixture of PNCO and poly(dimethyl siloxane)gycol (PNCO/PDMS) was also used. Polyurethane network elastomers were prepared from 4,4′-diphenylmethane diisocyanate (or 2,4-tolylene diisocyanate), and a mixture of 1,4-butane diol and trimethylol propane by a prepolymer method. Mechanical properties, Tg, thermal stability, and hydrolytic stability were measured. Morphology were also measured by means of polarizing microscopy, dynamic viscoelastometer, and ESR. The properties of novel polyurethane elastomers have good mechanical properties comparable to those of the general purpose polyester urethanes, and better thermal and hydrolytic stability than PTMG-based polyurethane. These polyurethane elastomers were exposed in out door during 2 year in Nagasaki, JAPAN. The novel polyurethane clastomers held alomost constant values for gel fraction, swelling ratio, relative modulus during 12 months, while poly(oxytetramethylene oxide)-based polyurethane as a control decreased the these values. Relationship of degradation behaviors with chemical structure and morphology were discussed.
    Additional Material: 9 Ill.
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    Oxidizability of lactams and lactam-based polyamidesDedicated to Dr Jan Šebenda on the occasion of his 70th birthday (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 252 (1997), S. 139-151 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the chain oxidation of N-alkylamides with molecular oxygen, propagation is the ratedetermining step under conditions when the oxidation rate is independent of oxygen pressure. The oxidizability of lactams and lactam-based polyamides correlates with the energy of the formation of N-alkylamide radical by abstraction of hydrogen from the methylene group adjacent to nitrogen. While for lactams this energy depends on the number of carbons in the lactam ring, for N-alkylamides and polylactams such dependence is not observed.
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    Use of EPR to image nitroxyl radicals in hals stabilized polymers (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 252 (1997), S. 179-193 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: An X-band EPR-Imaging apparatus which allowed us to determine the distribution of nitroxyl radicals within solid samples of polymeric materials containing hindered amine stabilizers, is described. It is shown that EPR Imaging represents a powerful tool for investigating the growth and decay of nitroxyls formed in polymers irradiated under air for long periods. Since the variations of the radical concentration can be monitored both in time and in the space, this technique provides valuable information not easily attainable by means of other methods.
    Additional Material: 7 Ill.
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    Photo-oxidation mechanisms of poly(2,6-dimethyl-1,4-phenylene oxide). (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 252 (1997), S. 237-256 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A re-examination of the photo-oxidation mechanism of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) at both long and short irradiation wavelengths under accelerated conditions is reported. The formation rate of poly-2,6-dimethylphenoxy (PDMP) radicals, have been observed by esr spectroscopy, while benzylic-type radicals have been detected by spin trapping experiments using nitrosodurene under UV irradiation conditions. The changes of FTIR spectra obtained under accelerated photo-oxidative conditions show the formation of primary oxidation products such as aromatic aldehydes and quinones. The direct formation of radical cations and superoxide anions by a photo-induced electron-transfer reaction is suggested under our conditions. In addition, some results on the of photo-oxidation PPO/PS blends as a function of polystyrene tacticity are also reported. In the case of syndiotactic polystyrene the blend photostability shows some differences in comparison with the blend containing atactic polystyrene. This effect has been ascribed to the absence of excimers in syndiotactic polystyrene which are not revealed by fluorescence measurements. Finally, the chemical modification of PPO with bromine gave a bromomethylated PPO with different amounts of CH2 Br groups, which has been used for further substitution reactions with alkoxy sodium salts of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and 4-hydroxy-1,2,2,6,6-pentamethylpiperidine (PMPP). The accelerated photo-oxidation of a modified copolymer PPO-PMPP containing a 60% PMPP moieties as side groups and its blends with pure PPO has been followed by FTIR and esr spectroscopies. Some comparisons with a commercially available hindered amine light stabilizers (HALS) and a modified copolymer PPO-PMPP are also reported under the same photo-oxidative conditions.
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    Zähigkeit und Relaxationsverhalten von Polymethylmethacrylat, Polystyrol und Polycarbonat (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 253 (1997), S. 27-49 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: For innovative applications of plastics, which take advantage of special properties of polymeric materials, comprehensive understanding on strengthening and toughening mechanisms is required. The temperature-dependent mechanical behaviour of PMMA, PS and PC under dynamic loading conditions were investigated by means of an instrumented Charpy impact tester. The elastic-plastic fracture mechanics parameters, the energy-determined J-integral, and the deformation-determined crack opening displacement, δ, enable to do structure-related quantification of micromechanical processes. The J-integral values showed a maximum, resulting from an energy-dissipative process. The maximum values for PMMA occurred at 50°C and for PC at 40°C , which is related to the secondary(β) relaxation as evaluated from the frequency dependence of the mechanical loss factor. The 0-relaxation initiated shear deformation mechanisms, which led to a local increase of toughness. In polycarbonate, toughness is strongly increased due to a stress-induced shear flow process at temperatures higher than -25°C. Correlations between morphology and toughness can be derived with the help of optical investigations of stable crack propagation on fracture surfaces.
    Notes: Innovative Kunststoffanwendungen, die die speziellen Eigenschaften polymerer Werkstoffe gezielt ausnutzen, erfordern vertiefte Kenntnisse über festigkeits- und zähigkeitsbestimmende Mechanismen. Das sich in Abhängigkeit von der Temperatur ändernde Werkstoffverhalten von PMMA, PS und PC wurde bei dynamischer Beanspruchung mittels instrumentierter Kerbschlagbiegeprüfung bestimmt. Mit der verformungsbestimmten Rißöffnungsverschiebung δ und dem energiebestimmten J-Integral stehen Kenngrößen der Fließbruchmechanik zur Verfügung, die eine strukturbezogene Quantifizierung der temperaturabhängigen mikromechanischen Prozesse erlauben. Die J-Integralwerte zeigen für PMMA bei 50°C und für PC bei -60°C ein durch einen energiedissipativen Prozeß verursachtes Maximum. Dieses Maximum steht, wie sich aus der Interpretation der Frequenzabhängigkeit des mechanischen Verlustfaktors ergibt, mit der Neben(β)-Relaxation in Beziehung. Dabei initiiert die β-Relaxation Scherdeformationsmechanismen, die ihrerseits die lokale Zähigkeitserhöhung bewirken. Ab -25°C führt für PC ein spannungsinduzierter Scherfließprozeß zu einer erheblichen Zähigkeitssteigerung. Durch die Einbeziehung lichtmikroskopischer Untersuchungen des stabilen Rißfortschritts auf der Bruchfläche können Morphologie-Zähigkeits-Korrelationen abgeleitet werden.
    Additional Material: 16 Ill.
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    Thermostable block copolymers, 2Part 1 cf. 16.. Preparation and characterization of soluble blockcopolyimides (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 253 (1997), S. 71-88 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Eine Reihe von Polyamidimid-Polyimid-Blockcopolymeren (PAI-PI-BCPs) wurde durch Polykondensation von PAI-Blöcken mit Amino-Endgruppen und PI-Blöcken mit Anhydrid-Endgruppen hergestellt. Zur Synthese der Blöcke mit Molekulargewichten im Bereich von ca. 2000 bis 15000 wurden nur technisch leicht zugängliche Monomere, wie Trimellitsäureanhydridchlorid, Benzophenontetracarbonsäuredianhydrid, 4,4′-Diaminodiphenylmethan, 2,4-Toluylendiamin und 4,4′-Diaminodiphenylsulfon eingesetzt. Dabei zeigte sich, daß durch den blockartigen Aufbau die Löslichkeit-und damit die Verarbeitbarkeit-im Vergleich zu den reinen, unlöslichen Polyimiden wesentlich verbessert werden konnte, bei nahezu gleichbleibender Thermostabilität. So wurden BCPs mit guten mechanischen Eigenschaften, Thermostabilitäten bis ca. 480°C (Thermogravimetrie, 5% Gewichtsverlust) und guten Löslichkeiten in Dimethylacetamid und anderen polaren aprotischen Lösungsmitteln erhalten.
    Notes: New poly(amide-imide)-poly(imide) block copolymers (PAI-PI-BCPs) were prepared by polycondensation of amino-terminated PAI-blocks with anhydride-terminated PI-blocks. For the syntheses of the blocks with molecular weights from 2000 to 15000 only commercially available monomers were used, e.g. trimellitic acid anhydride chloride, benzophenone tetracarboxylic acid dianhydride, 4,4′-diaminodiphenylmethane, 2,4-toluenediamine and 4,4′-diaminodiphenylsulfone. The BCPs were shown to have better solubility compared to the pure, insoluble PIs with only minor decrease of the thermostability. Thus, BCPs with good mechanical properties, thermostabilities up to 480°C (thermogravimetric analysis, 5% weight loss) and good solubility in dimethylacetamide and other polar aprotic solvents were obtained.
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    Block and graft copolymers with polysiloxane and poly(N-acyliminoethylene) sequences (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 253 (1997), S. 139-149 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Eine Reihe von Polysiloxan/Poly(N-acetyliminoethylen)-(PSiO/PNAI)-Block- und -Pfropfcopolymeren wurde durch Polymerisation von 2-Methyl-2-oxazolin (MeOZO) mit funktionellen Polysiloxan-Prepolymeren als Initiatoren synthetisiert. Die Copolymeren wurden mit IR- und 1H NMR-Spektroskopie sowie Elementaranalyse, Differentialkalorimetrie und Thermogravimetrie charakterisiert. Der Einbau sowohl von hydrophoben als auch von hydrophilen Sequenzen verleiht den Polymeren amphiphile Eigenschaften. Ihre Eigenschaften in Lösung und als Feststoffe lassen die Produkte für Anwendungen als nichtionische Emulgatoren, Oberflächenmodifikatoren, Gele, usw. geeignet erscheinen.
    Notes: A series of polysiloxane/poly(N-acetyliminoethylene) (PSiO/PNAI) block and graft copolymers were synthesized by the initiation of 2-methyl-2-oxazoline (Me-OZO) polymerization with functional polysiloxane prepolymers. The copolymerization products were characterized by IR- and 1H NMR spectroscopy, elemental analysis, DSC and thermogravimetry. The insertion of both hydrophobic and hydrophilic sequences in the macromolecular structure induces a behavior characteristic of amphiphilic compounds. Their solution and solid state behavior evidenced peculiarities which make them able to act as nonionic emulsifiers, surface modifiers, gels, etc.
    Additional Material: 4 Ill.
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    The state of water in styrene-grafted and sulfonated poly(vinylidene fluoride) membranes (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 253 (1997), S. 151-167 
    Details
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Der Zustand von Wasser in Protonenaustausch-Membranen, hergestellt durch Pfropfen von Styrol auf Polyvinylidenfluorid-Filme (PVDF-g-PS) mittels Elektronenstrahlen und anschließendes Sulfonieren (PVDF-g-PSSA), wurde mittels Differentialkalorimetrie (DSC), Raman-Spektroskopie und Rontgen-Diffraktion (SAXS) ermittelt. Die Raman-Untersuchungen zeigten, daß einzelne Wassermolekule durch hydrophobe Wechselwirkungen an die Polymerketten gebunden sind. Die DSC-Untersuchungen zeigten, daß Wasser in den Membranen in drei verschiedenen Umgebungen vorliegt: nicht gefrierendes ionisch gebundenes Wasser, gefrierendes freies Wasser und gefrierendes gebundenes Wasser. Die Menge an nicht gefrierendem Wasser betragt unabhangig vom Pfropfungsgrad etwa 10 H2O/SO3H (mol/mol). Die Menge an gefrierendem Wasser ist stark vom Pfropfungsgrad abhangig. Oberhalb eines Pfropfungsgrades von 50% werden Werte von 40 H20/S03H (mol/mol) erreicht. Die Leitfahigkeit von nur nicht gefrierendes Wasser enthaltenden Membranen ist gering, d. h., das ionisch gebundene Wasser kann nicht allein die fur den Transport von Protonen und Wasser notwendigen Kanale bilden. Die SAXS Untersuchungen zeigten, daß Wasser/Sulfonsaure-Cluster in Membranen aus hydratisiertem PVDF-g-PSSA mit einem Bragg-Abstand von 25 Å gebildet werden. Diese Cluster formen die Kanale fur den Ionentransport und die Leitfähigkeit.
    Notes: The state of water in proton exchange membranes prepared by pre-irradiation (electron beam, 100 kGy) grafting of styrene onto poly(vinylidene fluoride) films (PVDF-g-PS), followed by sulfonation (PVDF-g-PSSA), has been studied with thermal analysis, Raman spectroscopy and small angle X-ray diffraction (SAXS). Raman spectra show that, in addition to free liquid water in the membranes, single water molecules are weakly bound to the polymer backbone. Thermal analysis shows that there are three types of water molecules in the membrane; non-freezable water associated with the ionic sites, freezable free water, and freezable bound water. The amount of non-freezable water is around 10 H2O/SO3H (mol/mol), and is independent of the degree of grafting (d.o.g.). The amount of freezable water is strongly dependent on the d.o.g. as long as the grafting has not penetrated the whole of the film, and reaches a value of around 40 H2O/SO3H (mol/mol) above a d.o.g. of 50%. The conductivity of membranes containing only the non-freezable water is low, i. e. the ionically bound water alone does not form the domains necessary for proton and water transport. SAXS measurements show that water/sulfonic acid clusters in hydrated PVDF-g-PSSA membranes with a Bragg distance of 25 Å are formed; these form the ion conducting channels in the membrane.
    Additional Material: 9 Ill.
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    MITTEILUNGEN/ANNOUNCEMENTS (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 253 (1997), S. 211-211 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/apmc.1997.052530117
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    Tensile and flexural behavior of polypropene sheets with different crystallinities of surface layer (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 253 (1997), S. 201-210 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Zug- und Biegemoduli von preßgeformten Polypropen-Probekörpern mit unterschiedlichen Oberflächenkristallinitäten wurden basierend auf der Annahme eines Schicht-Verbund-Modells untersucht. Es zeigte sich, daß die Spannungs-Dehnungs-Kurven der Zugversuche und die Werte der Biegeablenkung im wesentlichen von der Oberfächenkristallinität abhängen, jedoch erwiesen sich die Bruchspannungen als von der Oberflächenkristallinität unabhängig. Es wird angenommen, daß das beobachtete Zug- und Biegeverhalten der Proben auf der Grundlage eines Schicht-Verbund-Modells, bei dem eine massive, starre Platte zwischen zwei weichen Schichten eingebettet ist, charakterisiert werden kann.
    Notes: The tensile and flexural moduli of the compression-molded sheets of polypropene with different surface layer crystallinity were investigated based on a layered composite model. It was found that the tensile stress-strain curve and flexural deflection depended largely on the surface layer crystallinity, but the ultimate strain-at-break values were independent of the surface layer crystallinity. It is suggested that the tensile and flexural behavior can be characterized using a layered composite model in which a bulk plate was sandwiched between two surface layers.
    Additional Material: 4 Ill.
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    The role of charge transfer complexes in the photodegradation of polyolefins (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 252 (1997), S. 45-54 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Addition of HALS-stabilisers, the cut-off wavelength of the light source, the temperature and the oxygen pressure have an influence on the UV-degradation mechanism of polyolefins. All these parameters influences the conversion of oxygen into polymeric carbonyls. The results are explained assuming that the initiation of the UV-degradation of pololefins is due to substrate-oxygen charge transfer complexes (CTCs).
    Additional Material: 10 Ill.
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    Fracture behavior of exposed HDPE specimens with an embrittled layer due to UV-exposure (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 252 (1997), S. 69-88 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The applicability of fracture mechanics was studied on UV-exposed HDPE Charpy specimens. The failure distribution of the stress at failure measured in three-points bending tests showed a bifurcation in failure processes. At high stresses yielding occurs, resulting in large strain at failures. At lower stresses crack propagation causes low strain at failures. Due to the bifurcation in failure processes the ductile-brittle transition temperature of exposed specimens is hard to determine.Specimens notched after exposure showed a decrease in the critical stress intensity values. The effective notch depth of exposed specimens was found to be larger than the thickness of the oxidized layer measured by FT-IR and density measurements.
    Additional Material: 21 Ill.
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    Deactivation processes of 2-hydroxyphenyl-1,3,5-triazines  -  polymeric and monomeric UV absorbers of the benzotriazole and triazine class (1997)
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 252 (1997), S. 119-138 
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    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: In the 2-hydroxyphenyl-1,3,5-triazines, the intramolecular hydrogen bond is stronger than in the corresponding 2-hydroxyphenylbenzotriazoles. Compounds with only one aryl group in the 2-hydroxyphenyl-1,3,5-triazine series show proton-transferred fluorescence with large Stokes shift and high quantum yield. No such fluorescence is observed, in contrast, for compunds with three aryi groups bearing no electrondonating groups on the aryl moieties. When the hydrogen atom of the intramolecular hydrogen bond is replaced by CH3, the respective derivative shows fluorescence with a normal Stokes shift.Various copolymers of MA-TIN 1 (2-[2-hydroxy-3-tert.-butyl-5-(O-[2-hydroxy-3-(2-methylpropenoyloxy)propyl]-2-carbonyloxyethyl)phenyl]benzotriazole), and MA-TZ 1 (2,4-Bis(2,4-dimethyl-phenyl)-6-[2-hydroxy-4-(2-hydroxy-3-[2-methylpropenoyloxy])propoxyphenyl]-1,3,5-triazine) with styrene, methyl methacrylate, and methacrylic acid have been synthesized by radical polymerization. The absorption spectra in the longwavelength UV region appear unchanged compared to those of the monomeric UV absorbers indicating that the stabilizer chromophores are conserved intact in the polymer. Both the monomeric and the polymeric stabilizers exhibit a strongly Stokesshifted, temperature-dependent, low-quantum-yield, proton-transferred fluorescence. This may be taken as evidence that the intramolecular hydrogen bond, which is essential for the photostability of this type of UV absorber, remains intact also in the copolymers. Activation energies of the radiationless deactivation process can be evaluated from the temperature dependence of this fluorescence. These energies lie between 4 and 5 kJ/mol for most of the benzotriazole and triazine stabilizers investigated.Fluorescence-decay measurements with crystalline MA-TIN 1 at different temperatures reveal a close correspondence of the temperature dependence between decay times and relative quantum yields. The radiationless process is thence concluded to originate from the proton-transferred level S1'. The decay time at room temperature is estimated at 70 ps, close to the value for crystalline TIN P (2-(2-hydroxy-5-methylphenyl)benzotriazole). The proton-transferred fluorescence of MA-TIN 1 exhibits a biexponential decay profile whereas solid TIN P, in contrast, displays only one single lifetime.
    Additional Material: 9 Ill.
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    Influence of fluctuations in electron density on the excess small-angle X-ray scattering from dilute solutions of macromolecules (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 67-80 
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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 influence on the excess scattering function P(μ) of flutuations in the electron density ρ within a macromolecule is treated, to the approximation that the solvent is a structureless medium of constant electron density ρ0. The results for P(μ) and the apparent value of the mean square radius Rapp2, can be expressed as functions of the excess electron density Δρ: P(μ) = X(μ) + (Δρ)-1Y(μ) + (Δρ)-2Z(μ) and Rapp2 = Rx2 + (Δρ)-1Ry2 + (Δρ)-2Rz2, where X(μ) and Rx2 depend only on the shape of the macromolecule, while Y(μ) and Ry2 as well as Z(μ) and Rz2 depend on the shape and the fluctuations in ρ. By varying the electron density of the solvent, the contributions of the shape and the internal structure of the macromolecule can be resolved. The quantities Rx2, Ry2, and Rz2 are evaluated for seven models to illustrate the relative importance of these contributions for representative structures.
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    The optical properties of tyrosine-containing cyclic dipeptides (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 121-142 
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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 chiroptical properties of the cyclic dipeptides cyclo (L-alanyl-L-tyrosine) and cyclo(L-tyrosyl-L-tyrosine) have been investigated as a function of molecular conformation. Theoretical optical calculations and conformational energy calculations have been carried out as a function of the side-chain dihedral angles χ1 and χ2, and as a function of the angle of fold of the cyclic dipeptide backbone. The results of these theoretical calculations have been compared with experimental circular dichroism (CD) data. Theoretical predictions are in very good agreement with experiment for c(L-Tyr-L-Tyr). Agreement was not quite as good for c(L-Ala-L-Tyr), although the signs of all of the Cotton effects were apparently predicted correctly except for that associated with the lowest energy tyrosine absorption band.
    Additional Material: 12 Ill.
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    Kinetic analysis of the annealing period in the formation of the poly(A)·2poly(U) triple helix (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 289-298 
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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 slow kinetics of annealing processes in multistranded nucleic acids is spectrophotometrically investigated using poly(A)·2poly(U) as a model system. The absorbance changes at specific wavelengths show that double-helical (A·U) base pairs appear as transient intermediates. The annealing process is identified by the enlargement of triple-helical sequences at the cost of (A·U) base pairs and unpaired (U) residues. A large time range in the reorganization of mismatched chain configurations is characterized by a logarithmic dependence on time. This observation is quantitatively described by a kinetic model developed by Jackson. In Jackson's model the rate-limiting process in the slow annealing phase of maximizing triple-helical sequences, is the removal of strand entanglements, knots, and hairpin loops by complete unwinding of those helical stretches which stabilize the mismatched configurations. The results of the present study are briefly discussed in terms of optimum conditions for hybridization experiments and for the preparation of polynucleotide complexes commonly used to produce interferons.
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    Fluorescence of proteins in aqueous neutral salt solutions. I. Influence of anions (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 341-368 
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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 effects of anions of neutral salts on the fluorescence emission of six proteins as well as on tryptophan and tyrosine were studied in relation to the structure of proteins. Most anions are good quenchers of tryptophyl and tyrosyl fluorescence, free or in proteins. The results with tryptophan and tyrosine indicate involvement of a collisional quenching mechanism due to agreement with Stern-Volmer law. The deactivation of fluorescence probably occurs because of the transition from singlet state to triplet state. Lehrer's modification of Stern-Volmer law was applied to proteins. The effective quenching constants ([KQ]eff) and the fraction of fluorescence available ([fa]eff) to the quencher are also calculated.In contrast to its effect on tryptophan, CH3COO- quenches tyrosyl fluorescence and ClO4- does not. The effects on fluorescence of ribonuclease and free tyrosine are similar and without any changes in emission maximum. The anions are divided into three groups based on the effect they have on tryptophan-containing proteins. (1) NO3-, NO2-, Br-, and I- have high [KQ]eff values and readily quench tryptophyl fluorescence of proteins causing a shift of emission maximum to a shorter wavelength. This change is due to the specific quenching of “exposed” tryptophan residues which are accessible to quenchers and the observed residual fluorescence is from the “buried” tryptophyls. (2) ClO4- and SCN- also quench fluorescence of tryptophan in proteins and have lower ([KQ]eff) values. In their presence the fluorescence maximum is shifted to a longer wavelength, which indicates the unfolding of a protein with [(fa)eff] = 1. (3) Cl-, CH3COO-, and SO4— do not have a direct effect on the fluorescence of tryptophan. Besides the “direct” effects, “indirect” effects on fluorophors in protein are also seen, pointing out that the neutral salts can interact in more than one manner with proteins. The effectiveness of anions in quenching fluorescence of proteins follows similar sequences which almost resemble the Hofmeister series, viz., SO4=, CH3COO- ≃ Cl- 〈 ClO4- 〈 SCN- 〈 Br- 〈 I- 〈 NO3- 〈 NO2-.
    Additional Material: 15 Ill.
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    Co-oligopeptides of aromatic amino acids and glycine with a variable distance between the aromatic residues. V. pH-Dependent conformational changes in peptides containing two adjacent tryptophyl residues as evidenced by circular dichroism studies (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 437-448 
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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 influence of pH upon CD spectra of H-Trp-Trp-OH, H-Trp-Trp-Gly-OH, and H-Gly-Trp-Trp-OH is investigated and data are compared with those obtained for peptides containing only one tryptophyl residue. A negative Cotton effect at around 225 nm, which in previous work has been related to an increase of the conformational rigidity in compounds having the sequence -CO-Trp-Trp, is also observed in the case of H-Trp-Trp-OH and H-Trp-Trp-Gly-OH upon deprotonation of the terminal α-amino group. These data, together with observations arising from solvent and temperature effects, give evidence that H-Trp-Trp-OH undergoes a conformational change upon going from acid to alkaline conditions, where the two aromatic side chains become conformationally more rigid relative to each other. This rigidity generates an exciton coupling between the Bb transitions of the two indoles. Hydrophobic forces, including stacking interactions, do not appear important in stabilizing this conformationally rigid structure. Rather, intramolecular electrostatic interactions (e.g., hydrogen bondings or polar interactions between the aromatic side chain and the peptide backbone) as well as interactions with the OH group(s) of the solvent, are suggested to be the salient forces. Possible structures which obey these requisites are discussed.
    Additional Material: 7 Ill.
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    Spectral analysis on the melting fine structure of λ DNA and T2 DNA (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 427-435 
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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 fine structure of the thermal denaturation of viral DNA's was analyzed with the spectral method established by Felsenfeld and Hirschman, and Fresco et al. A fully automated system measuring melting curves at four wavelengths at the same time was developed for this purpose. With this device, (G + C)-contents of melting components of λ DNA's were determined. The correlation between the (G + C)-content and the melting temperature of each melting component is found to be well described by the linear relationship given by Marmur and Doty. The denaturation of each component is regarded as cooperative. The Marmur-Doty relation also stands for the local denaturation of T2 DNA, which has a narrow melting range.
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    Relaxation times manifested by the Rouse-Zimm model in dynamic light-scattering experiments (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 461-464 
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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.1977.360160218
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    Measurement of diffusion coefficient and electrophoretic mobility with a quasielastic light-scattering-band-electrophoresis apparatus (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 1473-1488 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: We have constructed an apparatus for the simultaneous measurement of electrophoretic mobility, μ, and diffusion coefficient, D, of macromolecules and cells. It combines band electrophoresis in a vertical, sucrose-gradient stabilized column, with quasielastic laser light-scattering determination of the diffusion coefficient of the species within the band. The entire electrophoresis cell is scanned through the laser beam of the quasielastic laser light-scattering apparatus by a vertical translation stage. Total intensity light-scattering measurement at each point in the cell gives the macromolecular concentration at that point. Solvent viscosity and electrical potential are measured at each point in the cell. Application of this apparatus to resealed red blood cell ghosts and to bovine hemoglobin indicates that measurements of field, viscosity, and migration distance are reliable, and that electroosmosis is insignificant. Application to T4D bacteriophage gives μ20,w = (-1.05 ± 0.05) × 10-4 cm2/V sec and D20,w = (3.35 ± 0.10) × 10-8 cm2/sec for fiberless particles, and μ20,w = -(0.59 ± 0.03) × 10-4 cm2/V sec and D20,w = (2.86 ± 0.09) × 10-8 cm2/sec for whole phage with 6 fibers. Approximate analysis of these results with the Henry electrophoresis theory for spheres in dicates that each fiber contributes about 193 positive charges to the phage particle, compared with 327 from amino-acid analysis. The advantages and disadvantages of this apparatus, relative to conventional electrophoresis and to electrophoretic light scattering, are discussed.
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    Viscosity and potentiometric measurements of poly(L-histidyl-L-alanyl-α-L-glutamic acid) and poly(L-lysyl-L-alanyl-α-L-glutamic acid) (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 1541-1555 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Poly(His-Ala-Glu) and poly(Lys-Ala-Glu) were examined by viscosity and potentiometric titration. These measurements were interpreted in terms of the hydrodynamic size of the above sequential polypeptides. Effects of polymer, size and concentration, and solution-salt concentration were demonstrated. Although the sequential polypeptides generally behave like polyampholytes, they do demonstrate some differences. These differences my be attributed to the ability of ionized side chains three residues apart to repel themselves, in the order His 〈 Glu 〈 Lys.
    Additional Material: 8 Ill.
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    Etude experimentale de L′auto-association des molécules modèles dipeptidiques. III. Influence de la dimerisation stéréosélective sur les spectres de résonance magnétique protonique (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 715-729 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Proton magnetic resonance spectra of model dipeptide molecules R1-C′1O1-N2H2-C2αH2αR2-C′2O2-N3H3-R3 in CCl4 solutions exhibit splited signals when investigating on mixtures of L and D enantiomers differing from the racemic composition. The major effect is observed on amide proton signals which are the ones most sensitive to the ratio of aggregation. The stereoselective dimerization of enantiomeric molecules in the so-called C5 conformational state is shown to be responsible for such a phenomenon, the intensity of which depends on the bulkiness of the side chain R2. A theoretical approach is proposed which gives predictions in close agreement with our own experimental findings.
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    Water in keratin: Study of the depolarization thermal current peak II (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 1725-1733 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The depolarization thermal current method is applied to the study of the polarization phenomena in the keratin-water system. Three depolarization thermal current peaks have been evidenced in hair keratin. This paper deals with the detailed study of peak II. For the first time, the mechanism responsible for this peak is ascribed to molecular reorientation. The effect of water upon the characteristics of peak II is also described, and an activation energy of 8.4 kcal/mol is computed. These results, in connection with other studies, lead us to interpret peak II as due to the reorientation in the bound or intermediate water molecules. The effect of copper confirms that the carboxyl groups are hydration sites.
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    Determination of the base-pairing content of four specific tRNAs by infrared spectroscopy (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 1735-1745 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Infrared spectroscopy was used for the determination of the base-pairing content of four specific tRNAs in deuterium oxide solution. Infrared spectra were obtained in the 1750-1550 cm-1 region at various temperatures ranging from about 15 to 90°C. Melting curves were constructed by plotting the molar extinction coefficient at ν = 1657 cm-1 versus temperature. These transition curves enabled us to determine the ranges of temperature which correspond to the ordered (partially double-stranded) or randomly coiled structure of the tRNA. For a set of wavenumbers the extinction coefficients at these temperatures were used for the calculation of the base-pairing content. The procedure employed here is based on a method described earlier by Thomas [(1969) Biopolymers 7, 325-334]. For the conditions selected for this investigation (Mg2+-free D2O-buffer; 0.01M tris-DCl, 0.015M NaCl, pD 7.5) the results of this determination agree within the limits of errors with the number of base pairs predicted by the cloverleaf model.
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    Hydrodynamics of macromolecular complexes. III. Bacterial viruses (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 1779-1793 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We have calculated the translational and rotational frictional coefficients of structures related to T2 and T4 bacteriophage, using the theoretical framework developed in the preceding two papers. The structures considered were models for tail-fiberless phage, and for whole phage with fibers in the extended and retracted portions. We also computed and compared with the experiment the changes in translational frictional coefficient produced by successive addition of 1-6 fibers to the fiberless particle. Agreement with experimental results is markedly improved over previous theoretical efforts, especially with respect to the effect of tail-fiber extension. Some significant discrepancies remain, however, in the comparison of fiber-retracted and fiberless phage.
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    Hydrodynamics of macromolecular complexes. II. Rotation (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 1765-1778 
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    Notes: We have used the modified Oseen hydrodynamic interaction tensor along with iterative numerical solution of the coupled hydrodynamic interaction equations to calculate the rotational diffusion coefficients of macromolecular complexes composed of nonidentical spherical subunits. For the one structure, a prolate ellipsoid of revolution, for which exact solutions are available, a subunit model with the same length and volume gives asymptotic agreement with the Perrin equations. Other structures considered include plane polygonal rings, lollipops, and dumbbells.
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    Masthead (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977) 
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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.1977.360160501
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    Characterization of meningococcal polysaccharides by optical mixing spectroscopy. II. Effects of temperature, EDTA, and ionic strength on aggregation of group C polysaccharides in solutionWork supported by FDA. (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 945-963 
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    Topics: Chemistry and Pharmacology
    Notes: We have studied the effects of temperature, EDTA, and ionic strength on C-polysaccharides in solution by examining the details of the time-correlation function using a 96-channel single-clipped photon correlation spectrometer. Our linewidth results have shown that the C-polysaccharides in buffer solution form aggregates of very broad distributions. Thus, fractionation by gel-filtration chromatography is only mildly effective. Although the aggregate sizes seem to remain relatively constant from 4 to 25°C, a fraction of those aggregates break up to form smaller fragments or monomers at higher temperatures. However, the dissolution-association process is quite slow and takes days even at room temperatures before the equilibrium is reached. We have also shown that by adding an excess amoutn of EDTA, the aggregates can be broken up. Again the dramatic changes occur only at short delay times suggesting that a protion of the larger aggregates remains. Finally, the amount and size of aggregates depend upon the ionic strength which exhibit a maximum ΓT/sin2 (θ/2) around 0.1-0.2 M KCl.If the activities of polysaccharides in solution depend upon molecular size, the standard techniques such as gel-permeation chromatography and ultracentrifugation cannot properly characterize the detailed size distribution. Quasielastic laser light scattering can provide us with a qualitative model. The quantitative details must necessarily await more extensive investigations using a combination of the techniques and better fractionation procedures in an appropriate buffer solution.
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    Experimental and theoretical investigations on the folding modes of depsipeptide molecules (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 1033-1052 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The coupling of N-acyl-α-amino-acids with α-hydroxyacid-methyl amides results in depsipeptide molecules containing two chiral centers and one ester function inserted between two amide functions. Their conformational features have been investigated by IR spectroscopy, proton magnetic resonance, X-ray diffraction, and theoretical P.C.I.L.O. calculations.It is shown that most of these molecules are folded by an intramolecular 4 → 1 hydrogen bonding. Two folded conformations, similar to the well known β turn in peptides, are described, the stability of which depends on the configurational sequence in the investigated molecule.LL and LD species are folded in two different ways whereas LG sequences containing an achiral hydroxy-acid residue accommodate both of them. The presence of a N-terminal achiral amino acid noticeably decreases the folding ratio.The above conclusions are then compared with the conformational features of homologous tripeptide molecules.
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    An improved method of computation of density distributions (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 1153-1158 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1977.360160514
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    Kinetics of complex formation between fluorescein mercuric acetate and DNA (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 2105-2111 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of complex formation between fluorescein mercuric acetate and heat-denatured DNA were studied by measuring the fluorescence quenching of this reagent. This quenching process involved no immeasurably rapid phase and it was shown that this reaction follows simple second-order kinetics. The rate constant at 25°C was estimated to be 2.9 × 104M-1 sec-1 for calf-thymus DNA (42% G + C) and 1.1 × 104M-1 sec-1 for Micrococcus lysodeikticus DNA (72% G + C). Activation parameters for this reaction were calculated from the temperature dependence of the reaction rate, and the activation entropy was found to be highly negative (-27.5 cal/mol deg for calf-thymus DNA and -25.5 cal/mol deg for M. lysodeikticus DNA). The binding of fluorescein mercuric acetate to native DNA, which requires the opening of the double-helical structure, was also followed by measuring the absorbance change of this reagent. There was a lag phase in this binding process, and the enthalpy change for the opening step corresponded roughly to that for the opening of one base pair. These findings are discussed in relation to the results of a similar study with formaldehyde.
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    The mechanism of nucleation for in vitro collagen fibril formationPart of this work was presented at the 171st Meeting of the American Chemical Society in Chicago, Illinois, August 1975. (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 2113-2131 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The formation of collagen fibrils from soluble monomers and aggregates by thermal gelation at neutral pH can be divided into two distinct stages: a nucleation phase and a growth phase. Turbidity studies of the kinetics of the precipitation reaction show that the lag-phase time or nucleation reaction time, t′l, is markedly temperature dependent while the growth reaction time is temperature independent. The activation energy of the nucleation reaction is essentially constant over the temperature range studied. In monitoring the nucleation-phase reaction by various physicochemical techniques, including viscosity, sedimentation equilibrium, and light scattering, no evidence for the formation of aggregates was observed. Enrichment of the initial collagen solution with aggregates accelerates nucleation, but de novo nuclei formation is still required even in highly aggregated collagen preparations. Removal of pepsin and pronase susceptible peptides lengthens the nucleation reaction time and increases the sensitivity of the rate of nuclei formation to changes in ionic strength. Electron microscope studies show the fibrils formed from the protease-treated collagen to be less well organized. With pepsin-treated collagen, subfibrils and obliquely striated fibrils are seen, showing that while microfibrils are formed interactions between them are modulated by the enzyme susceptible peptides in the same way that these regions modulate nuclei assembly. It appears that pepsin and pronase susceptible peptide regions of collagen play a more prominent role in the in vitro assembly of collagen molecules to form D-stagger nuclei and fibrils than do ionic interactions between helical molecular regions. A mechanism of nucleation of collagen fibrillogenesis is discussed.
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    Circular dichroism of the nucleic acid monomers (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 2243-2264 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Circular dichroism spectra of the nucleic acid monomers have been measured in aqueous solution and extended into the vacuum ultraviolet region to about 166 nm. Measurements were made on ribo and deoxyribo derivatives of adenine, guanine, hypoxanthine, cytosine, thymine, and uracil derivatives both with and without the 5′-phosphate (with the exception of ribosyl thymine 5′-phosphate). Absorption spectra of the deoxyribonucleotides measured to about 175 nm are also presented. The results demonstrate that both the circular dichroism and absorption spectra observed below 200 nm are no more complicated than the spectra normally recorded above 200 nm. In most cases, the circular dichroism spectra of the various derivatives of a given base are similar, indicating that the conformations are similar. On the other hand, the differences among the circular dichroism spectra of the various derivatives of a given base are sufficient to identify a particular derivative. The average circular dichroism for the deoxyribonucleotides is compared with the circular dichroism of native E. coli DNA. The comparison reveals that the circular dichroism of DNA below 200 nm is due principally to the interaction between the bases rather than the intrinsic circular dichroism of the monomers. The monomer transitions are discussed in relationship to the absorption and circular dichroism spectra presented.
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    A theory for polarized fluorescence microscopy of chromosome structures (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 2281-2298 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A theory for the determination of DNA arrangements in DNA-containing specimens, using planar aromatic dye molecules as probes for plane polarization of fluorescence, has been described. At low dye-to-DNA concentrations, the dye molecules are sandwiched between the stacked bases of DNA; hence, the fluorescence from the dye bound to a local region of DNA helix is plane-polarized with the polarization direction perpendicular to the local axis of DNA. The degree of such polarization from an aligned DNA-specimen complexed with dye is determined both by the DNA orientation and the conformational state (e.g., base tilt) of DNA into that specimen. Analysis has been made of the relationship between the degree of polarization and the orientation of the emitting dipoles of dye. The dye complexes may be aligned in a mechanical shear or electric field. However, any change in the orientation distribution of the emitting dipoles due to force fields should be taken into account. With some assumptions and approximations, the magnitude and the direction of maximum polarization can be related to different orders of DNA coiling and to their various combinations. Since the measured polarization is averaged over all DNA regions of the specimen, if the magnitude of polarization is appreciable and the polarization occurs in the specific direction of the specimen, the theory helps to eliminate several probable arrangements of DNA. The predominant molecular features of the actual DNA arrangement can be determined through this process of elimination, as explained in two subsequent papers with T-even bacteriophage and chromosome systems.
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    Masthead (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977) 
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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.1977.360161101
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    Interaction of amylose and other α-glucans with hydrophobic fluorescent probe (2-p-toluidinylnaphthalene-6-sulfonate) (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 2363-2370 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Notes: Fluorescence of 2-p-toluidinylnaphthalene-6-sulfonate (TNS) was enhanced in the presence of maltooligosaccharides, amylose, and other α-glucans. The dependence of relative TNS fluorescence intensity per glucose unit on chain length of oligosaccharides was examined. The values of binding constant and thermodynamic parameters, assuming the 1:1 complex for TNS-amylose (number-average degree of polymerization, DPN = 17), were determined by the fluorescence titration. The values of thermodynamic parameters for 1:1 complex formation of TNS-α- and β-cyclodextrins were also determined and compared with those of TNS-amylose (DPN = 17). The fluorescence intensity of TNS in the presence of amylose (DPN = 600) decreased by the action of glucoamylase and taka-amylase A. The fluorescence of TNS-amylose (DPN = 17) system increased with the increased ionic strength. In the presence of pullulan, TNS fluorescence was also enhanced and decreased by the action of pullulanase. Amylopectin enhanced TNS fluorescence rather more strongly than amylose (DPN = 17) at the same concentration. In the presence of dextran, the fluorescence of TNS was scarcely enhanced. The degree of fluorescence enhancement of TNS in the presence of α-glucans seems to reflect the structures of α-glucans in solution, since TNS fluorescence is enhanced in the hydrophobic environment or by the disturbance of free intramolecular rotation.
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    Helix-coil stability constants for the naturally occuring amino acids in water. XIV. Methionine parameters from random poly(hydroxypropylglutamine,L-Methionine) (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 2447-2467 
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    Notes: Water-soluble, random copolymers containing L-methionine and N5-(3-hydroxypropyl)-L-glutamine have been prepared, fractionated, and characterized. The thermally induced helix-coil transitions of these copolymers in water have been investigated, and it has been found that incorporation of L-methionine increases the helix content of the polymers at all temperatures in the range of 0-60°C. The Zimm-Bragg parameters σ and s for the helix-coil transition in poly(L-methionine) in water were deduced from an analysis of the melting curves of the copolymers using the methods described in earlier papers.
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    Vibrational modes of A-DNA, B-DNA, and A-RNA backbones: An application of a green-function refinement procedure (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 2491-2506 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Normal vibrational analysis was carried out for DNA molecules in both A and B conformations as well as for A-RNA. A simplified backbone model was examined and expanded to include the backbone phosphate-group and the ribose ring. We applied the new force-constant refinement procedure discussed in the preceeding paper [Van Zandt, L. L., Lu, K.-C. & Prohofsky, E. W. (1977) Biopolymers, 16, 2481-90] to fit some observed frequencies in the Raman spectra for all three nucleic acids with the same set of force constants. The results indicate that the observed frequency shift can be attributed to the conformational change solely. We ignored the second-order differences in force constants for the different geometries. The agreement between the observed and calculated frequencies derived from the final refined set of force constants is good and apparently justifies this assumption. Two modes previously assigned to the symmetric diester O-P-O stretch and the symmetric dioxy O‥P‥O stretch are actually fitted. They are mainly backbone phosphate-group modes. The refined ribose-ring force-constants were transferred to the calculation of the vibrational spectrum of tetrahydrofuran. The overall agreement is again good. We discuss these calculations and the resulting normal modes. We also discuss the application of the Green-function refinement scheme and several strategies adopted to bias the convergence of the procedure.
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    Conformational energy calculations for dinucleotide molecules: A study of the nucleotide coenzyme nicotinamide adenine dinucleotide (NAD+) (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 1971-1986 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: A study of the conformational states of the dinucleotide coenzyme NAD+ has been made using semiempirical energy calculations. Taking low-energy mononucleotide structures as starting conformations, energy minimizations have been performed. The lowest energy states are stacked structures, with interactions between the adenine and nicotinamide rings. Some structures show stabilization gained from electrostatic attractions between the positively charged nicotinamide and negatively charged phosphate oxygens. These predictions correlate well with the available experimental data.
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    Block copolymers of amino acids. I. Synthesis and structure of copolymers of L-alanine or L-phenylalanine with D,L-lysine-d7 or D,L-lysine (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 2005-2028 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Water-soluble block copolymers of the type (A)m-(B)n-(A)p, where (A)m,p was either poly(D,L-lysine-α,β,β,γ,γ,δ,δ-d7) or poly(D,L-lysine) and (B)n was either poly(L-alanine) or poly(L-phenylalanine), were synthesized for conformational studies by proton magnetic resonance spectroscopy. Analytical determination of the amount of the initiator fragment (n-hexylamine) at the C-terminus of the copolymers was used to obtain the number-average degrees of polymerization, DPn, and thereby, together with the amino acid composition, to establish the covalent structures of the polymers. The values of DPn were found to be much lower than those deduced from sedimentation equilibrium or form viscosity measurements. These deviations, which also are thought to have arisen in similar studies reported in the literature, are attributable to intermolecular aggregation; the relation of such aggregation to covalent structure (and its effect on the polymerization reaction) is discussed in terms of the conditions and mechanism of synthesis of block copolymers of amino acids.
    Additional Material: 5 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1977.360160914
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    The analysis of circular dichroism spectra of natural DNAs using spectral components from synthetic DNAs (1978)
    New York : Wiley-Blackwell
    Biopolymers 17 (1978), S. 85-106 
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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 tested 21 different basis sets of synthetic DNA circular dichroism spectra and have slected one for use in spectral analyses of natural DNAs. This “standard” set consists of spectra of eight polymers: poly[d(A-A-T)·d(A-T-T)], poly[d(A-G-G)·d(C-C-T)], poly[d(A-T)·d(A-T)], poly[d(G-C)·d(G-C)], poly[d(A-G)·d(C-T)], poly[d(A-C)·d(G-T)], poly[d(A-T-C)·d(G-A-T)], and poly[d(A-G-C)·d(G-C-T)]. This basis set, applied according to the first-neighbor polymer procedure of Gray and Tinoco, allows a more uniformly accurate spectral analysis of six natural complex DNAs and eight (A+T)-rich satellite DNAs for base composition and first-neighbor frequencies than was previously possible. We find that spectra of poly[d(A)·d(T)] and/or poly[d(A-C-T-)·d(A-G-T)] are not generally required for good analysis results but we show in this and the following paper that these spectra are needed for the most accurate analyses of some satellite DNAs.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1978.360170107
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  • 89
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    Masthead (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (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
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1977.360160901
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  • 90
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    Interaction between poly(L-lysine48, L-histidine52) and DNA (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 1879-1894 
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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(Lys48, His52), a random copolypeptide of L-lysine (48%) and L-histidine (52%), was used as a model protein for investigating the effects of protonation on the imidazole group of histidines on protein binding to DNA. The complexes formed between poly(Lys48, His52) and DNA were examined using absorbance, circular dichroism (CD), and thermal denaturation. Although increasing pH reduces the charges on histidine side chains in the model protein, the protein still binds the DNA with approximately one positive charge per negative charge in protein-bound regions. Nevertheless, CD and melting properties of poly(Lys48, His52)-DNA complexes still depend upon the solution pH which determines the protonation state of imidazole group of histidine side chains. At pH 7.0, the complexes show two characteristic melting bands with a tm (46-51°C) for free base pairs and a t′m (94°C) for protein-bound base pairs. The t′m of the complexes is reduced to 90°C at pH 9.2, although at this pH there is still one lysine per phosphate in protein-bound regions. Presumably, the presence of deprotonated histidine residues destabilizes the native structure of protein-bound DNA. The binding of this model protein to DNA causes a red shift of the crossover point and both a red shift and a reduction of the positive CD band of DNA near 275 nm. This phenomenon is similar to that caused by polylysine binding. These effects, however, are greatly diminished when histidine side chains in the model protein are deprotonated. The structure of already formed poly(Lys48, His52)·DNA complexes can be perturbed by changing the solution pH. However, the results suggest a readjustment of the complex to accommodate charge interactions rather than a full dissociation of the complex followed by reassociation between the model protein and DNA.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1977.360160905
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  • 91
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    Theoretical conformational analysis of Asn1, Val5 angiotensin II (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 1929-1943 
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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 theoretical analysis of the conformation of the octapeptide hormone Asn1, Val5 angiotensin II has been carried out by semiempirical potential energy calculations. A preliminary study of the Ala6-Pro-Ala molecule, which mimics the angiotensin backbone, provided us with likely backbone structures on which the effect of the full side chains of the hormone could be assessed. For angiotensin II, the calculations show that only a small number of folded, compact conformations have a high probability of existence. This is the consequence of favorable packing and of the presence of proline in position 7. These results are consistent with various experimental data, both structural and biological. This method is readily applicable to the study of analogs of the hormone or to other peptides of comparable size.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1977.360160908
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  • 92
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    Effect of charge density of cationic polyelectrolytes on complex formation with DNA (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 1993-2004 
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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 interaction between DNA and ionen polymers, -[N+(CH3)2(CH2)mN+(CH3)2(CH2)n]l-, with m-n of 3-3, 6-6, and 6-10 were examined in order to know how the binding behavior of cationic polymers with DNA depends on the charge density of polycation. The ionen polymer has no bulky side chain and the binding forces with DNA would be attributed mainly to electrostatic interaction. When 3-3 ionen polymers were added to DNA solution, precipitable complexes with the ratio of cationic residue to DNA phosphate (+/-) of 1/1 and the free DNA molecules were segregated, while 6-6 and 6-10 ionen polymers formed soluble complexes with DNA molecules up to (+/-) = 0.5. This suggests that 3-3 ionen polymers bind cooperatively with DNA while 6-6 and 6-10 ionen polymers bind noncooperatively. The cooperative binding of 3-3 ionen polymer and the noncooperative binding of 6-6 ionen polymer were also supported by the thermal melting and recooling profiles from the midpoint between first and second meltings. It was concluded that the charge density of DNA phosphate is a critical value determining whether the ionen polymers bind to DNA by a cooperative or by a noncooperative binding, since the distance between successive cationic charges of 3-3 ionen polymer is shorter than that between successive phosphate charges on DNA double helix and those of 6-6 and 6-10 ionen polymers are longer.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1977.360160913
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  • 93
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    Masthead (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977) 
    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.1977.360161001
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  • 94
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    Quasielastic light scattering: Effect of ionic strength on the internal dynamics of DNA (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 2091-2104 
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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: Quasielastic light scattering is used to study the effect of ionic strength on the dynamic behaviour of DNA. In a first approach the spectrum of scattered light is analyzed in terms of a single relaxation process. The large difference between the observed behaviour and that expected according to a pure diffusional process reflects the contribution associated with internal modes, which increases with decreasing ionic strength. Such behaviour is better analyzed in terms of a double relaxation process by using two relaxation times, the reciprocals of which are equal to DK2 and DK2 + τi-1 (K), respectively, where τi (K) is an average value describing the set of modes observed at a given K value. Relative intensity and relaxation times, which are the more accurate parameters, were used to interpret the results. The observed increase of the relative contribution of internal modes with decreasing ionic strength is actually a relative decrease of the diffusional contribution induced by a corresponding increase of the radius of gyration RG. On the other hand, the reciprocal τi-1 (K) of the relaxation time is a linear function of K2 in the analyzed KRG range and is insensitive to ionic strength between 10-2M and 1M. These results, when discussed according to Rouse's model, lead to define for each value of τi-1 (K) a corresponding mean-squared equilibrium length 〈μi2〉 which is found to be a linear function of K-2.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1977.360161002
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    Proton magnetic resonance and model peptides conformations (1977)
    New York : Wiley-Blackwell
    Biopolymers 16 (1977), S. 2755-2771 
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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 and peptides of β-nitrobenzyl-L-aspartates were studied with high-field nmr. Differences were observed between the chemical shifts of protons located near the extremity of the principal chain as a function of the terminal group. These differences are explained by conformational calculations which exclude the existence of an hydrogen bond and demonstrate the influence of the aromatic ring position on the protons of the main chain. Both nmr experiments and conformational analysis indicate that conformations are nearly the same for ortho, meta, and para nitro substitution. These conclusions are in good agreement with Karplus relationship applied to the α and β protons.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1977.360161213
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  • 96
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    A semiempirical extension of polyelectrolyte theory to the treatment of oligoelectrolytes: Application to oligonucleotide helix-coil transitions (1978)
    New York : Wiley-Blackwell
    Biopolymers 17 (1978), S. 159-166 
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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 interaction of counterions with a suitably long, charged oligomer appears susceptible to treatment in the context of polyelectrolyte theory by the introduction of an end-effect parameter that reflects the reduced association of counterions with the terminal regions of the oligo-ion. Use of a physically reasonable value for the end-effect parameter provides excellent agreement between theory and the experimental data of Elson, Scheffler, and Baldwin [J. Mol. Biol. 54, 401-415 (1970)] on the dependences of melting temperature on salt concentration and chain length for a series of hairpin helices formed by d(TA) oligomers. The differences in behavior expected for hairpin, dimer, and oligomer-polymer helices are discussed. The salt dependence of the end-joining equilibrium investigated for λ DNA by Wang and Davidson [Cold Spring Harbor Symp. Quant. Biol. 33, 409-415 (1968)] is treated as an oligomer-polymer interconversion. The dependence of equilibrium constant for this reaction on counterion concentration is in good agreement with that predicted by theory for an end-region totalling 24 nucleotides, the known length of the λ ends.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/bip.1978.360170112
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    Solvent denaturationThis paper is an expanded version of a paper dedicated to J. Sturtevant at the symposium held on March 25, 1977 in honor of his achievement of emeritus status at Yale University. (1978)
    New York : Wiley-Blackwell
    Biopolymers 17 (1978), S. 1305-1322 
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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: Solvent denaturation is developed along thermodynamic lines rather than from multiple-binding theory. Almost all the relations derivable from site-binding theory have their counterparts in the thermodynamic formulation showing that the details of binding models may be sufficient but are not necessary for the general description of solvent denaturation. Equations are derived for the effect of denaturant concentration on stability at constant temperature and on tm. It is recommended that the thermodynamic treatment be used instead of binding models unless stoichiometric interactions are demonstrable experimentally.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1978.360170515
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  • 98
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    Base stacking in A fluorescent dinucleoside monophosphate: εApεA (1978)
    New York : Wiley-Blackwell
    Biopolymers 17 (1978), S. 1361-1372 
    Details
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optical properties of the 1,N6 - etheno derivative of ApA (εApεA) have been studied. Absorbance and CD measurements suggest that (1) neutral salts tend to unstack this molecule and (2) the stacking interaction is weaker than in ApA. εApεA is found to be quenched strongly with respect to the monomer. (εAMP); this quenching is solvent dependent (1M NaCl 〉 5M NaClo4〉40%glycerol) and increases with the ratio of temperature to viscosity (T/η) in each case. Fluorescence lifetime measurements also reveal a temperature- and solvent-dependent decay which is nonlinear on a semilog plot. In the presence of 95% glycerol, this decay return to linearity. These data have been considered from two points of view: (1) two-state pictures which are based on thermodynamic least-squares fit to quatum yield and CD curves, together with two exponential fits to the decay curves and (2) a dynamical model in which relatives fluorophore motion leads to deexcitation via intramolecular collision. A simple model of type (2) gives qualitative agreement with the observed behavior.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/bip.1978.360170519
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  • 99
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    Characterization of receptor affinity heterogeneity by scatchard plots (1978)
    New York : Wiley-Blackwell
    Biopolymers 17 (1978), S. 1385-1386 
    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.1978.360170522
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  • 100
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    Masthead (1978)
    New York : Wiley-Blackwell
    Biopolymers 17 (1978) 
    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.1978.360170601
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