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  • Articles  (34,935)
  • Chemistry  (33,069)
  • Polymer and Materials Science  (10,227)
  • 01.01. Atmosphere
  • 04. Solid Earth
  • 04.07. Tectonophysics
  • 05.09. Miscellaneous
  • Wiley-Blackwell  (34,917)
  • Elsevier  (16)
  • American Geophysical Union
  • American Institute of Physics
  • 2020-2022  (18)
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  • Articles  (34,935)
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  • 1
    Publication Date: 2021-04-14
    Description: In February 2016, 47 ingots were found in the seabed of Contrada Bulala (Gela, CL, Italy) near the site where 40 ingots had previously been recovered. The ingots composition was determined to be a Cu - Zn alloy, dated by the archaeologist to the VI century B.C. This specific alloy was then known as Orichalcum. From an archaeological point of view, the first question raised about the new discovery was whether the ingots of the first and the second excavations belonged to the same shipwreck. Following the previous study, an elemental analysis was performed on the ingots from the second finding by using ICP-OS and ICP-MS techniques. The chemometric treatment of the analytical results obtained on both sets, i.e. ingots from first and second discovery, confirms their similarity. Therefore, the two findings can be considered to belong to the same naval load. The lead isotopic ratios were determined on selected/representative ingots to improve the knowledge about this treasure. Results can provide information about probable location of the lead sources, that could be very useful for the reconstruction of the ancient trade routes in the Mediterranean Sea.
    Description: Published
    Description: 102901
    Description: 2IT. Laboratori analitici e sperimentali
    Description: JCR Journal
    Keywords: Orichalcum ingots ; Lead Isotopic ratio ; ICP-OES ICP-MS ; Chemometric approach ; 05.09. Miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
    Type: article
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  • 2
    Publication Date: 2021-05-18
    Description: Anthropogenic emissions of greenhouse gases (GHGs) co-occur with emissions of these gases from volcanic and urban environments. Therefore, it remains a challenge for the scientific community to identify the contamination sources and quantify the specific contributions. Stable isotopes have many applications in different fields under geosciences, including volcanology, environmental surveying, and climatology. Isotopic surveys allow identification of photosynthetic fractionation in tree forests and gas sources in urban zones, and tracking of volcanic degassing. Thus, the stable isotopic composition of the local GHGs allows the evaluation of the environmental impacts and assists in mitigating the emissions. The present study aimed to distinguish the tropospheric sources of CO2 in the different ecosystems based on the stable isotopic composition of CO2. The study relies on field experiments performed in both volcanic and urban zones of the Mediterranean region. Experiments to identify the CO2 origins in the field were designed and conducted in the laboratory. The CO2 in the air in Palermo, the soil CO2 released at Vulcano (Aeolian Islands, Italy), and the CO2 emitted at Cava dei Selci (Rome, Italy) were selected for conducting case studies. Isotope surveying of the CO2-containing air in Palermo revealed that the CO2 content was correlated to human activity. Mobile-based measurements of carbon isotope were conducted to distinguish the different sources of CO2 at the district scale. In particular, the isotopic surveying process distinguished landfill-related CO2 emissions from the fossil fuel burning ones. The underlying geological reservoir was identified as the main source of air CO2 at Cava dei Selci. Finally, partitioning of soil CO2 enabled estimation of the geological CO2 estimation in the Vulcano Porto settled zones. The results of the present study revealed that detailed investigations on stable isotopes assist in tracking the CO2 sources and the fate of gas emissions. The fine-tuned experimental solutions assisted in broadening the research perspectives. In addition, deeper insights into the carbon cycle were obtained.
    Description: Published
    Description: 118446
    Description: 6A. Geochimica per l'ambiente e geologia medica
    Description: JCR Journal
    Keywords: Stable isotopes ; Carbon dioxide ; Greenhouse gas emissions ; Volcanic gases ; Mediterranean region ; 01.01. Atmosphere ; 04.08. Volcanology ; 05.08. Risk
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 3
    Publication Date: 2021-05-12
    Description: InSAR images allow to detect the coseismic deformation, delimiting the epicentral area where the larger displacement has been concentrated. By inspecting the InSAR fringe patterns it is commonly recognized that, for dip-slip faults, the most deformed area is elliptical, or quadrilobated for strike-slip faults. This area coincides with the surface projection of the volume coseismically mobilized in the hanging wall of thrusts and normal faults, or the crustal walls adjacent to strike-slip faults. In the present work we analyzed a dataset of 32 seismic events, aiming to compare the deformation fields in terms of shape, spatial extents, and amount of deformed rock volumes, and the corresponding earthquake type and magnitudes. The dimension of the deformed area detected by InSAR scales with the magnitude of the earthquake, and we found that for M ≥ 6 is always larger than 100 km2, increasing to more than 550 km2 for M ≈ 6.5. Moreover, the comparison between InSAR and Peak Ground Accelerations documents the larger shaking within the areas suffering higher vertical deformation. As well established, the seismic epicenter rarely coincides with the area of larger shaking. Instead, the higher macro- seismic intensity often corresponds to the area of larger vertical displacement (either downward or upward), apart local site amplification effects. Outside this area, the vertical displacement is drastically lower, determining the strong attenuation of seismic waves and the decrease of the peak ground acceleration in the surrounding far- field area. Indeed, the segment of the activated fault constrains the area where the vertical oscillations are larger, allowing the contemporaneous maximum freedom degree of the crustal volume affected by horizontal maximum shaking, i.e., the near-field or epicentral area; therefore, the epicentral area and volume are active, i.e., they coseismically move and are contemporaneously crossed by seismic waves (active volume and surface active domain) where trapped waves and constructive interference are expected, whereas the surrounding far-field area is mainly fixed and passively crossed by seismic waves (passive volume and surface passive domain). All these considerations point out that InSAR images of areas affected by earthquakes are a powerful tool representing the fingerprint of the epicentral area where the largest shaking has taken place during an earthquake. Seismic hazard assessments should primarily rely on the expected future active domains.
    Description: Published
    Description: 103667
    Description: 5T. Sismologia, geofisica e geologia per l'ingegneria sismica
    Description: JCR Journal
    Keywords: InSAR coseismic vertical deformation ; Constructive waves inferference ; Seismic hazard assessment ; Earthquake epicentral area ; Near-field active domain ; 04.07. Tectonophysics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 4
    Publication Date: 2021-05-31
    Description: We analyze the gross crustal structure of the Atlantic Ocean passive continental margins from north to the south, comparing eleven sections of the conjugate margins. As a general result, the western margins show a sharper continental-ocean transition with respect to the eastern margins that rather show a wider stretched and thinner margin. The Moho is in average about 5.7 ±1 dipping toward the interior of the continent on the western side, whereas it is about 2.7 ±1 in the eastern margins. Moreover, the stretched continental crust is on average 244 km wide on the western side, whereas it is up to about 439 km on the eastern side of the Atlantic. This systematic asymmetry reflects the early stages of the diachronous Mesozoic to Cenozoic continental rifting, which is inferred as the result of a polarized westward motion of both western and eastern plates, being Greenland, Northern and Southern Americas plates moving westward faster with respect to Scandinavia, Europe and Africa, relative to the underlying mantle.
    Description: Published
    Description: 101205
    Description: 1T. Struttura della Terra
    Description: JCR Journal
    Keywords: Passive continental margin ; Westward drift of the lithosphere ; Moho dip Continental-ocean transition ; Asymmetric rift ; 04.07. Tectonophysics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 5
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    Elsevier | Amsterdam
    In:  http://aquaticcommons.org/id/eprint/2000 | 130 | 2010-12-14 16:47:43 | 2000
    Publication Date: 2021-07-11
    Description: During October, 1972 the Patuxent River Estuary was monitored intensively and synoptically over two tidal cycles to determine the spatial and temporal patterns of various hydrodynamic, chemical and biological features. Forty-one depths at eleven stations along nine transects were sampled simultaneously at hourly intervals forsalinity, temperature, dissolved oxygen, chlorohyll a, particulate nitrogen, nitrate, nitrite, total kjeldahl nitrogen, ammonia, particulate carbohydrate, dissolved organic carbon, total hydrolizable phosphorous, dissolved inorganic phosphorous, suspended sediment, particle size distribution, and zooplankton. Tidal velocity wascontinuously monitored at each depth by recording current meters. Riverine input and meteorological conditions were relatively stable for two weeks preceeding the deployment.This communication describes the calculation of the intrinsic rates of change of the observed variables from their measured distributions in the Estuary. The steady-state, one-dimensional equation of species continuity is employed to separate the advection and tidal dispersion of a hydrodynamically passive substance frbm its intrinsic rate of change at point. A new spatial transform isintroduced for the purpose of interpolation and extrapolation of data.The intrinsic rate of change profiles reveal a region of heavy bloom activity in the upper estuary and a secondary bloom near the point in the River that most of the suspended material settles out. Thechanges in ammonia and nitrates are highly correlated to the productivity patterns. Phosphorous rates are less closely correlated to productivity. The perturbations that the Chalk Point steam electric power plant have on the heat and oxygen balances are easily discernible.
    Description: UMCES (University of Maryland Center for Environmental Science); Contribution No. 766
    Keywords: Ecology ; Biology ; Chemistry
    Repository Name: AquaDocs
    Type: book_section , TRUE
    Format: application/pdf
    Format: application/pdf
    Format: 1-26
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  • 6
    Publication Date: 2020-09-21
    Description: We compare differences and similarities in the annual stratospheric HNO3 cycle derived from ground‐based measurements at the South Pole during 1993 and 1995, after correcting an error in earlier published profile retrievals for 1993 which led to under estimation of mixing ratios. The data series presented here provide profiling over the range ∼16–48 km, and cover the fall‐winter‐spring cycle in the behavior of HNO3 in the extreme Antarctic with a large degree of temporal overlap. With the exception of one gap of 20 days, the combined data sets cover a full annual cycle. The record shows an increase in HNO3 above 30 km occurring about 20 days before sunset, which appears to be the result of higher altitude heterogeneous conversion of NOx as photolysis diminishes. Both years show a strong increase in HNO3 beginning about polar sunset, in a layer peaking at about 25 km, as additional NOx is heterogeneously converted to nitric acid. When temperatures drop to the polar stratospheric cloud (PSC) formation range near the end of May, gas phase HNO3 is rapidly reduced in the lower stratosphere, although at least 2–3 weeks of temperatures ≤192 K appear to be required to complete most of the gas‐phase removal at the upper end of the depletion range (22–25 km). Despite a significant difference in residual sulfate loading from the explosion of Mount Pinatubo, there appears to be little gross difference in the timing and effects of PSC formation in removing gas phase HNO3 in these 2 years, though removal may be more rapid in 1995. Incorporation of gas phase HNO3 into PSCs appears to be nearly complete up to ∼25 km by midwinter. We also see a repeat of the formation of gas phase HNO3 in the middle stratosphere in early midwinter of 1995 with about the same timing as in 1993, suggesting that this phenomenon is driven by a repetition of dynamical transport and appropriate temperatures and pressures in the polar night, and not (as has been suggested) by ion‐based heterogeneous chemistry that requires triggering by large relativistic electron fluxes. High‐altitude HNO3 production peaks during a period of ∼20 days, but appears to persist for up to ∼40 days in the 40–45 km range, ceasing well before sunrise. This HNO3 descends rapidly throughout the production period, at a rate in good agreement with theoretically determined midwinter subsidence rates. As noted in earlier studies, later warming of this region above PSC evaporation temperatures does not cause reappearance of large amounts of HNO3, indicating that most PSCs gravitationally sink out of the stratosphere before early spring. We present evidence that smaller PSCs do evaporate to ∼1 to 3.5 ppbv of HNO3 in the lower stratosphere, however, working downward from ∼25 km as temperatures rise during the late winter. There is a delay of ∼15 days after sunrise before photolysis causes significant depletion in the altitude range below ∼30 km, where subsidence has carried virtually all higher‐altitude HNO3 by polar sunrise. Some continued subsidence and photolysis combine to keep mixing ratios less than ∼5 ppbv below 30 km until the final breakdown of the vortex in November brings larger amounts of HNO3 with air from lower latitudes.
    Description: Published
    Description: 17739-17750
    Description: 5A. Ricerche polari e paleoclima
    Description: JCR Journal
    Keywords: ozone depletion ; HNO3 ; Antarctic stratosphere ; 01.01. Atmosphere
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 7
    Publication Date: 2020-09-07
    Description: While mantle convection is a fundamental ingredient of geodynamics, the driving mechanism of plate tectonics remains elusive. Are plates driven only from the thermal cooling of the mantle or are there further astronomical forces acting on them? GPS measurements are now accurate enough that, on long baselines, both secular plate motions and periodic tidal displacements are visible. The now 〉20 year-long space geodesy record of plate motions allows a more accurate analysis of the contribution of the horizontal component of the body tide in shifting the lithosphere. We review the data and show that lithospheric plates retain a non-zero horizontal component of the solid Earth tidal waves and their speed correlates with tidal harmonics. High-frequency semidiurnal Earth's tides are likely contributing to plate motions, but their residuals are still within the error of the present accuracy of GNSS data. The low-frequency body tides rather show horizontal residuals equal to the relative motion among plates, proving the astronomical input on plate dynamics. Plates move faster with nu- tation cyclicities of 8.8 and 18.6 years that correlate to lunar apsides migration and nodal precession. The high- frequency body tides are mostly buffered by the high viscosity of the lithosphere and the underlying mantle, whereas low-frequency horizontal tidal oscillations are compatible with the relaxation time of the low-velocity zone and can westerly drag the lithosphere over the asthenospheric mantle. Variable angular velocities among plates are controlled by the viscosity anisotropies in the decoupling layer within the low-velocity zone. Tidal oscillations also correlate with the seismic release.
    Description: Published
    Description: 103179
    Description: 1T. Struttura della Terra
    Description: JCR Journal
    Keywords: Body tide ; Plate tectonics ; Geeodynamics ; 04.07. Tectonophysics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 8
    Publication Date: 2020-10-16
    Description: Many long-term monitoring sites in Antarctic regions, which deploy ground-based stratospheric remote sensors and fly radiosondes or ozonesondes on balloons, supported the Airborne Polar Experiment in September and October 1999. Support consisted of supplying data to the campaign in real time, and in some cases by increasing the frequency of measurements during the campaign. The results will strengthen scientific conclusions from the airborne measurements. But results from these sites are allowing important scientific studies of new aspects of the ozone hole in their own right, because like the aircraft and its campaign, many sites traverse the vortex edge and are close to the largest source of lee waves, or measure infrequently observed trace gases such as HNO3. Examples of such studies are the behaviour and value of NO2 in midwinter, ozone filamentation with no apparent horizontal advection, the frequency and amplitude of gravity waves over the Antarctic Peninsula, mixing in the lowest stratosphere in Antarctic spring, the mechanism and frequency of HNO3 enhancement above the ozone peak in midwinter, and trends in UV dose in southern South America.
    Description: Published
    Description: 835–845
    Description: 5A. Ricerche polari e paleoclima
    Description: JCR Journal
    Keywords: ozone depletion ; APE-GAIA ; Antarctic stratosphere ; 01.01. Atmosphere
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 9
    Publication Date: 2020-10-06
    Description: The partitioning of carbon dioxide (CO〈sub〉2〈/sub〉) released by soils at Vulcano Island (Aeolian Islands, Italy) was performed by combining the CO〈sub〉2〈/sub〉 flux and the carbon isotope measurements. Based on this method, the amount of CO〈sub〉2〈/sub〉 of volcanic origin was quantified six times during the period 2015–2018. The data analysis allowed us to establish the correlation between CO〈sub〉2〈/sub〉 soil degassing and changes in the contribution of volcanic fluids. Carbon isotope determinations were performed in situ to enhance the coverage of data collection in space and time. These data were combined with both the CO〈sub〉2〈/sub〉 contents in the ground gases and the soil CO〈sub〉2〈/sub〉 flux. The amount of volcanic CO〈sub〉2〈/sub〉 was distinguished from that of biogenic origin by implementing a three-component mixing model. The results of this study indicate that the increase in CO〈sub〉2〈/sub〉 output in September 2018 reflects the increase in volcanic gas emissions. The measurement method and analysis presented in this work are sufficiently general to be applicable to the monitoring programs of active volcanoes.
    Description: Published
    Description: 106972
    Description: 6V. Pericolosità vulcanica e contributi alla stima del rischio
    Description: JCR Journal
    Keywords: Carbon dioxide ; CO2 flux ; CO2 isotope composition ; Volcano monitoring ; Volcanic unrest ; Volcanic degassing ; 04. Solid Earth ; 04.08. Volcanology
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 10
    Publication Date: 2020-11-18
    Description: Highlights -Gas blowouts from water wells are frequent in the southeastern zone of Rome -Emitted gas killed some pets and families had to be evacuated for security reasons -Gas has a magmatic origin with the highest helium R/Ra of Colli Albani gas discharges -Monitoring of soil CO2 flux and air gas concentration allowed to assess gas hazard -Gas diffusing in soil reached nearby houses creating dangerous indoor conditions
    Description: The southeastern zone of Rome city is located at the northwest periphery of the quiescent Colli Albano volcano. This zone is characterized by the presence of a shallow (depth ~ 45–50 m) gas pressurized aquifer that produces gas blowouts when it is reached by wells. Three gas blowouts occurred in this zone in 2003, 2008 (another one was discovered during the present study) and 2016 and in this paper we describe in detail the latter two. The emitted gas consists mostly of CO2 (〉90 vol%) and contains a low but significant quantity of H2S (0.3–0.5 vol%) and it has the highest helium isotopic R/Ra value (1.90) of all Colli Albani natural gas discharges, suggesting its likely magmatic origin. In both the described gas blowouts, dozens of families had to be prudentially evacuated from their houses and the emitted gas killed some animals. We monitored, continuously or by discrete surveys, the soil CO2 flux, the indoor and outdoor air concentration of CO2 and H2S, the environmental parameters and we checked whether the cementation of the gas releasing wells had been effective. In both cases, the upper part of the wells had been partly closed with an inflating packer to avoid free gas dispersion in atmosphere; as a consequence gas diffused laterally from the wells into the permeable surficial soil up to reach the nearest houses creating hazardous indoor conditions, particularly for CO2 in some basements. During the well cementation operations, and in one case because of the packer rupture, gas and nebulized water were freely discharged from the wells into the atmosphere, and high air CO2 and H2S concentrations were found. Fortunately gas was quickly dispersed by strong winds. The positive results obtained in all the studied gas blowouts demonstrate that our applied geochemistry approach represents a model of intervention useful for the assessment of the hazard associated to accidental endogenous gas release. This model is of fundamental importance also to overcome the risk problems created by accidental gas blowout from wells in an urbanized environment, up to the safe return of the people in their evacuated houses.
    Description: Published
    Description: 104769
    Description: 6V. Pericolosità vulcanica e contributi alla stima del rischio
    Description: JCR Journal
    Keywords: Rome gas blowouts zone ; Hazard assessment of endogenous gas blowouts from wells ; 04. Solid Earth
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 11
    Publication Date: 2020-11-25
    Description: In this paper a new approach for processing arrays of data is proposed. It is based on fuzzy logic and the concepts of cellular computation. Arrays of simple, identical processing elements (called fuzzy cells) are defined by using fuzzy rules. Moreover, each fuzzy cell interacts with its local neighbors. The overall behavior of these locally interacting fuzzy systems is used to process arrays of data. Some examples of practical applications are proposed. Among these, the new approach is applied to image-processing problems, and to the simulation of heat diffusion phenomena.
    Description: This work was partially supported by the Italian National Research Council (C.N.R.) under the special project "Reti neurali per i sistemi di controllo".
    Description: Published
    Description: 47-52
    Description: 3IT. Calcolo scientifico
    Description: JCR Journal
    Keywords: fuzzy logic ; partial differential equations ; 05.09. Miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 12
    Publication Date: 2021-06-25
    Description: Recent measurements of surface vertical displacements of the European Alps show a correlation between vertical velocities and topographic features, with widespread uplift at rates of up to ~2–2.5 mm/a in the North-Western and Central Alps, and ~1 mm/a across a continuous region from the Eastern to the South-Western Alps. Such a rock uplift rate pattern is at odds with the horizontal velocity eld, characterized by shortening and crustal thickening in the Eastern Alps and very limited deformation in the Central and Western Alps. Proposed me- chanisms of rock uplift rate include isostatic response to the last deglaciation, long-term erosion, detachment of the Western Alpine slab, as well as lithospheric and surface de ection due to mantle convection. Here, we assess previous work and present new estimates of the contributions from these mechanisms. Given the large range of model estimates, the isostatic adjustment to deglaciation and erosion are su cient to explain the full observed rate of uplift in the Eastern Alps, which, if correct, would preclude a contribution from horizontal shortening and crustal thickening. Alternatively, uplift is a partitioned response to a range of mechanisms. In the Central and Western Alps, the lithospheric adjustment to deglaciation and erosion likely accounts for roughly half of the rock uplift rate, which points to a noticeable contribution by mantle-related processes such as detachment of the European slab and/or asthenospheric upwelling. While it is di cult to independently constrain the patterns and magnitude of mantle contributions to ongoing Alpine vertical displacements at present, future data should provide additional insights. Regardless, interacting tectonic and surface mass redistribution processes, rather than an individual forcing, best explain ongoing Alpine elevation changes.
    Description: Published
    Description: 589-604
    Description: 1T. Struttura della Terra
    Description: 2T. Deformazione crostale attiva
    Description: JCR Journal
    Keywords: 04. Solid Earth ; 04.03. Geodesy ; 04.07. Tectonophysics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 13
    Publication Date: 2020-09-21
    Description: [1] We present the first intercomparison between the two most comprehensive records of gas‐phase HNO3 profiles in the Antarctic stratosphere, covering the greater part of 1993 and 1995. We compare measurements by the Stony Brook Ground‐Based Millimeter‐wave Spectrometer (GBMS) at the South Pole with Version 5 HNO3 data from the Microwave Limb Sounder (MLS) aboard the Upper Atmospheric Research Satellite. Trajectory tracing was used to select MLS measurements in the 70°–80°S latitude band that sampled air observed by the GBMS during passage over the Pole. When temperatures were near the HNO3 condensation range, additional screening was performed to select MLS measurements that sampled air parcels within 1.5 K of the temperature they experienced over the Pole. Quantitative comparisons are given at 7 different potential temperature levels spanning the range ∼19–30 km. Agreement between the data sets is quite good between 465 and 655 K (∼20–25 km) during a large fraction of the year. Agreement is best during winter and spring, when seasonally averaged differences are generally within 1 ppbv below ∼25 km. At higher altitudes, and during summer and fall, the agreement becomes worse, and GBMS measurements can exceed MLS values by more than 3 ppbv. We provide evidence that differences occurring in the lower stratosphere during fall are due to lack of colocation between the two data sets during a period of strong poleward gradients in HNO3. Remaining discrepancies between GBMS and MLS V5 HNO3 measurements are thought to be due to instrumental or retrieval biases.
    Description: Published
    Description: id 4809
    Description: 5A. Ricerche polari e paleoclima
    Description: JCR Journal
    Keywords: MLS ; Nitric acid ; polar stratosphere ; 01.01. Atmosphere
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 14
    Publication Date: 2020-10-19
    Description: The chemical and isotopic features of the fluids (water and gases) in the Lucane thermal area (southern Italy) have been investigated in order to verify their origin, water temperature in the geothermal reservoir, and to recognize the main natural processes concerning the water composition during ascent towards the surface. The Lucane geothermal system is placed in the southern sector of the Apennines chains, a seismically active area, close to the southern base of the Mt. Alpi carbonate massif. Along the study area, two main sets of high-angle faults form an almost orthogonal fault system that, as suggested by local structural geology, acts as a preferential pathway for uprising deep fluids. Here, we recognized two different types of waters: (i) cold shallow waters having a meteoritic origin and interacting with carbonate rocks (dolomite and calcite), whose dissolved gases show a dominant atmospheric contribution and (ii) hypothermal waters (average temperature of 21 °C), having a meteoritic origin and interacting with both carbonate rocks and inter-bedded evaporitic deposit. Geochemical data allow estimating a geothermal reservoir temperature between 30 °C and 60 °C, according to silica and Ca/ Mg geothermometers, respectively. A heat discharge related to hypothermal groundwater flow between 7.75E +06 and 2.00E+07 J/s was computed. δ18O and δ2Η data allowed recognizing a meteoric origin for hypothermal (hereafter TL) waters, with mean recharge (infiltration) elevations between 1300 and 1700 m a.s.l. These waters are gas-rich (e.g., CO2 and He), which amounts are higher than those in air-saturated water (ASW). Carbon and helium isotope signature in the TL waters indicate their mainly crustal origin and involve a tectonic control on fluid migration through the crust. Furthermore, we observe that the He isotopic signature in gases dissolved in TL waters is stable over time and its monitoring could be a powerful tool to assess the seismogenetic processes since their preparatory phases.
    Description: Published
    Description: 106618
    Description: 2T. Deformazione crostale attiva
    Description: JCR Journal
    Keywords: geochemistry ; tectonics ; geothermy ; earthquakes ; 04. Solid Earth
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 15
    Publication Date: 2020-06-10
    Description: Understanding how long-term subduction dynamics relates to the short-term seismicity and crustal tec tonics is a challenging but crucial topic in seismotectonics. We attempt to address this issue by linking long-term geodynamic evolution with short-term seismogenic deformation in the Northern Apennines. This retreating subduction orogen displays tectonic and seismogenic behaviors on various spatiotemporal scales that also characterize other subduction zones in the Mediterranean area. We use visco-elasto-plastic seismo-thermo-mechanical (STM) modeling with a realistic 2D setup based on available geological and geophysical data. The subduction dynamics and seismicity are coupled in the numerical modeling, and driven only by buoyancy forces, i.e., slab pull. Our results suggest that lower crustal rheology and lithospheric mantle temperature modulate the crustal tectonics of the Northern Apennines, as inferred by previous studies. The observed spatial distribution of upper crustal tectonic regimes and surface displacements requires buoyant, highly ductile material in the subduction channel beneath the internal part of the orogen. This allows protrusion of the asthenosphere in the lower crust and lithospheric delamination associated with slab retreat. The resulting surface velocities and principal stress axes generally agree with present-day observations, suggesting that slab delamination and retreat can explain the dynamics of the orogen. Our simulations successfully reproduce the type and overall distribution of seismicity with thrust faulting events in the external part of the orogen and normal faulting in its internal part. Slab temperatures and lithospheric mantle stiffness affect the cumulative seismic moment release and spatial distribution of upper crustal earthquakes. The properties of deep, sub-crustal material are thus shown to influence upper crustal seismicity in an orogen driven by slab retreat, even though the upper crust is largely decoupled from the lithospheric mantle. Our simulations therefore highlight the effect of deep lower crustal rheologies, self-driven subduction dynamics and mantle properties in controlling shallow deformation and seismicity.
    Description: Published
    Description: 228481
    Description: 1T. Struttura della Terra
    Description: 2T. Deformazione crostale attiva
    Description: JCR Journal
    Keywords: Numerical modeling ; Geodynamics ; Seismotectonics orogen ; Delamination ; Northern Apennines ; 04.06. Seismology ; 04.03. Geodesy ; 05.01. Computational geophysics ; 04.07. Tectonophysics
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 16
    Publication Date: 2020-03-03
    Description: The elevation of an orogenic belt is commonly related to crustal/lithosphere thickening. Here, we discuss the Apennines as an example to show that topography at a plate margin may be controlled not only by isostatic adjustment but also by dynamic, mantle-driven processes. Using recent structural constraints for the crust and mantle we find that the expected crustal isostatic component explains only a fraction of the topography of the belt, indicating positive residual topography in the central Apennines and negative residual topography in the northern Apennines and Calabria. The trend of the residual topography matches the mantle flow induced dynamic topography estimated from regional tomography models. We infer that a large fraction of the Apennines topography is related to mantle dynamics, producing relative upwellings in the central Apennines and downwellings in the northern Apennines and Calabria where subduction is still ongoing. Comparison between geodetic and geological data on vertical motions indicates that this dynamic process started in the early Pleistocene and the resulting uplift appears related to the formation and enlargement of a slab window below the central Apennines. The case of the Apennines shows that at convergent margins the elevation of a mountain belt may be significantly different from that predicted solely by crustal isostasy and that a large fraction of the elevation and its rate of change are dynamically controlled by mantle convection.
    Description: Published
    Description: 163-174
    Description: 1T. Struttura della Terra
    Description: 2T. Deformazione crostale attiva
    Description: JCR Journal
    Keywords: 04. Solid Earth ; 04.03. Geodesy
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 17
    Publication Date: 2020-07-13
    Description: A multidisciplinary field campaign was carried out at Nisyros Island (Greece). Hydrothermal gases were sampled and analysed, and CH4 and CO2 fluxes from the soils were measured with the accumulation chamber method. The sampling area (Lakki plain) covers an area of about 0.08 km2, and includes the main fumarolic areas of Kaminakia, Stefanos, Ramos, Lofos and Phlegeton. Flux values measured at 130 sites range from −3.4 to 1420 mg m−2 d−1 for CH4 and from 0.1 to 383 g m−2 d−1 for CO2. The fumarolic areas show very different CH4 degassing patterns, Kaminakia showing the highest CH4 output values (about 0.8 t a−1 from an area of about 30,000 m2) and Phlegeton the lowest (about 0.01 t a−1 from an area of about 2500 m2). The total output from the entire geothermal system of Nisyros should not exceed 2 t a−1. Previous indirect estimates of the CH4 output at Nisyros, based on soil CO2 output and CH4/CO2 ratios in fumarolic gases, were more than one order of magnitude higher. The present work further underscores the utmost importance of direct CH4 flux data because indirect methods totally disregard methanotrophic activity within the soil. Ten soil samples were collected for CH4 consumption experiments and for metagenomic analysis. Seven of the soil samples showed small but significant CH4 consumption (up to 39.7 ng g−1 h−1) and were positive for the methanotrophs-specific gene (pmoA) confirming microbial CH4 oxidation in the soil, notwithstanding the harsh environmental conditions (high temperature and H2S concentrations and low pH).
    Description: Published
    Description: 119546
    Description: 6A. Geochimica per l'ambiente e geologia medica
    Description: JCR Journal
    Keywords: Methanotrophy ; Soil degassing ; Hydrothermal systems ; Methane output ; Greenhouse gases ; 05.09. Miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 18
    Publication Date: 2020-07-13
    Description: Greece is a region characterised by intense geodynamic activity that favours the circulation of hydrothermal fluids in the crust transporting volatiles from either the deep crust or the mantle to the surface. Elevated heat flow values are detectable at Sperchios Basin and North Euboea (central Greece), two areas defined by a system of deeply rooted extensional faults and Quaternary volcanic activity. This setting contributed to the formation of numerous hydrothermal systems, which are mostly expressed as CO2-rich thermal springs with intense bubbling. The CO2 output from six bubbling pools has been determined by flux measurements with the use of the floating chamber method. The highest bubbling CO2 output has been found at Thermopyles and Psoroneria (0.6 and 0.84 t/d, respectively), where the outgoing channels have an elevated flow (〉250 l/s) of gas-charged water (〉15 mmol/l of CO2). Although no bubbling is noticed along the stream, the CO2 content decreases by an order of magnitude after few hundreds of metres, indicating an intense degassing from the water. Taking into account the water flow and the amount of CO2 lost to the atmosphere, the CO2 output of the outgoing channels is quantified in 12.5 t/d for Thermopyles and 9.23 t/d for Psoroneria. Output estimation has also been made for the other springs of the area. The diffuse CO2 release from the outgoing channels has always been higher respect to that of the visible bubbling, suggesting that most of the degassing is “hidden”. Furthermore, the loss of CO2 from the water has determined a shift in dissolved carbonate species as demonstrated by the pH increase along the channel that led eventually to an oversaturation in carbonate minerals and therefore travertine deposition. The total CO2 output to the atmosphere of the study area is estimated at ~27 t/d, with the major contribution deriving from the degassing along the outflow channels of the thermal springs. Such output is comparable to that of the single active volcanic systems along the South Aegean Active Volcanic Arc and highlights the importance of “hidden” degassing along CO2-oversaturated streams.
    Description: Published
    Description: 104660
    Description: 6A. Geochimica per l'ambiente e geologia medica
    Description: JCR Journal
    Keywords: C-cycle ; degassing sources ; stream outgassing ; 05.09. Miscellaneous
    Repository Name: Istituto Nazionale di Geofisica e Vulcanologia (INGV)
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  • 19
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    Biopolymers 8 (1969) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 20
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    Biopolymers 8 (1969), S. 21-27 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An increase in temperature causes an increase in the amplitudes of intramolecular and intermolecular motions and mainfests itself as an increase in the effective radii of the various atoms, especially hydrogen atoms. If one uses a Lennard-Jones 6-12 potential function to account for nonbonded interactions, this increase in the radius of the hydrogen atom is equivalent to a modification of the coefficient of the repulsive part of the Lennard-Jones potential. Accordingly, this effect of increasing temperature on the helix sense of several polyamino acids is computed by allowing the effective radius of the hydrogen atom to increase. It is found that the preferred sense of several polyamino acid helices changes from right- to left-handed as the temperature is increased. This accounts for recent experimental observations of changes in helix sense with temperature.
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  • 21
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    Biopolymers 8 (1969), S. 57-68 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Potentiometric titrations and some complementary optical rotation data are presented for solutions of poly(L- glutamic acid) (PGA) in several H2O-ethanol mixtures. The data allow the determination of the intrinsic pK (pK0), slope of the apparent. pK (pKapp), versus degree of ionization curves and of the enthalpy of ionization as a function of ethanol concentration. The variation of the degree of ionization at which the helix-coil transformation occurs with ethanol and temperature is also determined. Finally free energy, enthalpy, and intropy changes associated with the helix-coil transformation for the uncharged conformers are determined from the titration curves. The effect of the ethanol is to increase the stability of the helical conformation of PGA for both the charged and the uncharged forms of the polymer. The stabilization of the uncharged helix is essentially an entropic effect.
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  • 22
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    Biopolymers 8 (1969), S. 91-99 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Infrared spectra of polypeptides were measured in the region of 1800-400 cm-1. For the α-helical form, disordered form, and antiparallel-chain β-form, amide V band- arising from N-H out-of-plane bending models were observed at 610-620, around 650, and 700-705 cm-1, respectively, and amide V′ bands arising from N-D out-of-plane bending modes were observed at 455-465, around 510, and a 515-530 cm-1, respectively. These correlations are useful for conformation diagnoses, particularly for copolyamino-acids or proteins which are not oriented. The nature of low-frequency amide bands are discussed with reference to potential energy distributions calculated for the α-helical form and β form.
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  • 23
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Some experimental data are given on the infrared spectra between 3300 and 3500 cm-1 of dilute solutions in carbon tetrachloride of three types of model compounds: CH3-CONH-CH(R1)-CONH(R2), (I); CH3-CON(CH3)-CH(R1)-CONH(R2), (II) and CH3-CONH-CH(R1)-CON(R2)2, (III). In studying the N-H stretching bands, it was found that there are two types of intramolecular hydrogen bonds in these molecules; these result in two different cyclized conformations, C5 and C7, which contain respectively, five and seven atoms in the ring. By using model substances I, II, and III, in which the nitrogen atoms are unequally substituted, it is possible to identify the N-H stretching bands which are to be ascribed to the N-H oscillators included in the two different chelated conformations. It is found also that the stretching frequency of a free N-H oscillator depends upon the substituent on the nitrogen atom. Thus, it is possible to observe, with some of the model compounds I, four different absorption bands located at 3340, 3420, 3440, and 3460 cm-1. The first two are ascribed to the N-H oscillators included in the H—bonds which lock the C7 and C5 conformations; the last two correspond to free N-H which differ with the substituent on the nitrogen atom.
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  • 24
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    Biopolymers 8 (1969), S. 153-155 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 25
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    Biopolymers 7 (1969), S. 207-213 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Molecular orbital calculations of the extended Hückel type have been used to study the conformations of glycyl and alanyl residues in ground and excited states. The ground-state surfaces show features similar to those obtained with the standard calculational methods in which the total energy is partitioned into components such as torsions, nonbonded and electrostatic interactions. The molecular orbital calculations provide the first independent theoretical check on such calculations. The excited-state surfaces, Uniquely available from the molecular orbital calculations, exhibit a better definition and sharpening of potential minima in the sterically allowed regions.
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  • 26
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: We derive equations for calculating the number-, weight-, and z-average lengths between single-strand breaks in DNA molecules. Provision is made for the existence of preformed breaks under genetic control: these are assumed to be fixed in number in each molecule, but may be variable in position. Breaks due to random degradation may be superimposed on the pre-existing breaks. An example is given for illustrative purposes.
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  • 27
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    Biopolymers 7 (1969), S. 223-239 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The conformation in solution of fractionated 30 S and 19 S ribosomal RNA from rabbit reticulocytes has been studied by optical rotatory dispersion, analysis of thermal melting profiles and their derivatives, and spectrophotometric acid-base titration. From a consideration of the limitations of these methods, it has been possible to set limiting values on the degree of base-pairing and the lengths of the double helices: between 60 and 80% of the bases in 19 S and 30 S RNA are estimated to be paired. The paired segments are not shorter than 4 base pairs, and evidence from other sources is available which indicates that they are not longer than 8-16 base pairs. The spread of helix lengths is greater in the 30 S than in 19 S RNA; and other differences are noted. Several distinct populations of double helices, differing in their thermal stability, are present. Estimates are presented from spectrophotometric and titration data for the base compositions of the paired and unpaired regions.
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  • 28
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    Biopolymers 7 (1969), S. 251-263 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A small perturbation analysis is carried out to determine the stability of a fluid containing two layers of diffusing solutes in a common solvent and acted upon by a uniform gravitational field. It is found that instability can arise even though the unperturbed diffusion does not lead to the formation of a density inversion within the fluid.
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  • 29
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 30
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    Biopolymers 7 (1969), S. 475-493 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of denaturation of DNA have been studied by relaxation techniques. Examination of the terminal relaxation times for a variety of DNA's under a variety of conditions has shown that DNA denaturation is principally a hydrodynamically limited process. Measurements within the helix-coil transition have demonstrated that the experimentally measured terminal relaxation times are a function of the following: (1) position in the helix-coil transition; (2) ionic strength of the solvent; (3) solvent viscosity; (4) DNA concentration; (5) molecular weight; (6) number and position of single-strand breaks. The dependence of the terminal relaxation time on the above mentioned factors can be attributed to hydrodynamic effects. Thus a hydrodynamic model for DNA unwinding is required. The model which best fits the data involves the assumption of a rotational frictional coefficient independent of molecular weight. This assumption is suggested by the fact that the relaxation time is proportional to the first power of the molecular weight.
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  • 31
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    Biopolymers 7 (1969), S. 495-502 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sodium counterion association with partially neutralized poly(D-glutamic acid) or poly(DL-glutamic acid) was measured by use of Wall's transference method with radioactive sodium. In the region where both polyacids are in completely random coil form, fractions of association were considerably less than that with poly(acrylic acid) in the same region of degree of neutralization. Even in the region where poly (D-glutamic acid) is in the helical form, the fraction of association was less than that with poly(acrylic acid) in the same region. No pronounced characteristics attributable to counterion association corresponding to the helix-coil transition could be found. The association phenomena were discussed on the basis of a rodlike model of polyelectrolyte.
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  • 32
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    Biopolymers 7 (1969), S. 411-415 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The isomerization of poly-L-proline in different solvents has been studied by NMR spectroscopy. Different resonance signals for the CHα protons have been obtained for the two different helical conformations of thus compound, namely form I and form II.
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  • 33
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    Biopolymers 7 (1969), S. 417-422 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly-β-N-diphenylmethyl-L-asparagine and poly-γ-N-diphenylmethyl-L-glutamine were prepared from the corresponding N-carboxyanhydrides. Poly-L-aspuragine and poly-L-glutamine were obtained by removal of the diphenylmethyl protecting groups with liquid anhydrous hydrofluoric acid.
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  • 34
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    Biopolymers 7 (1969), S. 379-393 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Hydrogen-tritium exchange character of poly-D,L-alanine was studied in detail as a model for the hydrogen exchange behavior of the unhindered, polymeric peptide group. The random chain nature of poly-D,L-alanine was evident in the uniformity of exchange rate of all its hydrogens and in the similarity between this rate and that of random chain poly-D,L-lysine and other known, unhindered secondary amide groups. An equilibrium isotope effect favoring the binding of tritium over protium to the extent of 21% was measured. Specific acid and base catalysis of the exchange and the absence of detectable general catalysis were demonstrated. Apparent energy of activation is 17 kcal/mole for deprotonation, largely due to dependence of Kw on temperature, and 15 kcal/mole for protonation, which correlates with the extreme apparent pK. The hydrogen -tritium exchange half-time rate; of poly-D,L-alamine at any pH and temperature (T: °C) is given by the equation: \documentclass{article}\pagestyle{empty}\begin{document}$$ \[t_{\frac{1}{2}} \,(\min )\, = \,200\,\, \times \,10^{0.05{\rm T}} /\,[10^{{\rm pH} - 3} \, + \,10^{3 - {\rm pH}} ]\] $$\end{document}
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  • 35
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    Biopolymers 7 (1969), S. 581-593 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The specific rotation of starch components, corrected for refractive index variation, exhibits a discontinuity in the region of the water-dimethyl sulfoxide (H2O-DMSO) system that corresponds to the composition of the complex 2H2O-DMSO. This discontinuity is a property dependent upon the presence of a number of consecutively linked α-1,4 glucose units and, therefore, must reflect a change in symmetry of a segment, of polymer chain. The optical rotation of amylose between 26.5 and 92.5°C. does not change in DMSO and is only slightly lowered in water at the higher temperature. The behavior of amylose in both DMSO and H2O is like that of a random coil, as indicated by viscosity and sedimentation measurements. These results may be interpreted either as being compatible with models of amylose in solution in which the polymer backbone has helical twist, or as indicating removal of strong interactions between polymer chain segments by a good solvent.
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  • 36
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 7 (1969), S. 614-618 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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    Biopolymers 7 (1969) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 39
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    Biopolymers 7 (1969), S. 1-3 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 40
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    Biopolymers 7 (1969), S. 5-19 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The osmotic pressure equation for nonideal, associating systems of the type nA +mB ⇄ AnBm, has been derived, by using the assumption yAnBm/yAnyBm = 1. This treatment can also be applied to related associations such as nA + mB ⇄ AB + AB2 + A2B + …. From osmotic pressure experiments on the pure reactants it is possible to obtain the molecular weights (MA and MB) of the reactants and also the virial coefficients (BAA and BBB) of the reactants. The osmotic pressure of a nonreacting mixture of A and B can be calculated from these measurements. It can be used along with osmotic pressure measurements on equilibrium mixtures of A and B to obtain expressions containing the equilibrium constant (or constants) and the cross-virial coefficients (BAB and BBA). Several procedures are described for the evaluation of the equilibrium constant (or constants) and the BAB or BBA terms. It appears that this procedure is a general one which is applicable to associations of the type nA + mB ⇄ AB + A2B + AB2 + …. By correcting for nonideal behavior, one should then be able to apply it to any method available for analyzing ideal associations of the types considered here. In addition it is possible, subject to certain restrictions, to analyze associations of the type 3A + B ⇄ A2 + AB.
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  • 41
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    Biopolymers 7 (1969), S. 39-58 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method has been developed for characterizing at, submicrogram levels the heterogeneity of histones from purified nuclei. The histones are eluted with a smooth concentration gradient from nuclei trapped in polyacrylamide-gel threads and are collected in a micro fraction collector suitable for volumes in the 10-100 μl range. The gradient and fraction collection systems are governed by cam driven syringes. Samples obtained are subjected to electrophoresis in a starch-gel system and the gels are stained with a highly sensitive stain specific for guanidinium groups. Seven major and a similar number of minor components are demonstrated in the histones. The method of differential elution of trapped macromolecules is suitable for use with systems other than nuclei and histones.
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  • 42
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method is presented for the treatment of distribution functions obtained by ultra-centrifugal sedimentation velocity experiments on the plasma lipoproteins, so that adequate corrections can he made for the effects of diffusion and concentration dependence of the sedimentation coefficient. The method involves the use of modified equations derived from those presented in 1952 by Gosting for the transform from g* (S) to g(S) distributions. The evaluation of the molecular parameters of lipoprotein density and size, from a set of g(Si°) distribution functions obtained in solvents of varying density, is also outlined. Preparations of the β-lipoprotein of human plasma are found to follow a bivariate normal distribution that requires evaluation of five parameters, x̄1, σ1, x̄2, σ2and p. The first two represent the mean and standard deviation of the lipoprotein density, the third and fourth the same quantities for the size, expressed as ft “logarithmic diameter parameter”, and the final value is a measure of the correlation between these two variables.
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  • 43
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    Biopolymers 7 (1969), S. 133-133 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
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  • 44
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    Biopolymers 7 (1969) 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Biopolymers 7 (1969), S. 155-171 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: High-resolution nuclear magnetic resonance spectra at 100 MHz and 220 MHz have been obtained on two samples of poly-L-alanine of differing molecular weights (2500 and 42 500) in the chloroform-trifluoroacetic acid system under various conditions of solvent composition, temperature, and polypeptide concentration. Separate helix and random coil peaks are observed for the α-CH and peptide NH backbone proton resonances, thereby permitting the determination of helix content. This observation of separate peaks demonstrates that the lifetimes of the helix and random coil portions of poly-L-alanine have lower limits of about 10-1 sec. It is suggested that solvent-peptide versus peptide-peptide hydrogen bond competition, coupled with a destabilizing effect of the trifluoroacetic acid on the helix, is responsible for the helix-random coil transformation.
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    Biopolymers 7 (1969), S. 135-153 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The combination of an agarose gel (Bio-Gel A) and a dioxane-water (1:1) solvent system allowed the fractionation, on a preparative scale, of a very polydisperse, non-derivatized lignin preparation (enzymatically liberated lignin prepared from sweetgum sapwood with Lenzites trabea). Three fractions differing markedly in molecular weight were obtained. A gel of crosslinked alkylated dextran (Sephadex LH-20) with the same solvent system allowed division of the lowest molecular weight fraction into two fractions. These materials were characterized by measurements of intrinsic viscosity and number-average molecular weights in dimethylformamide and dioxane-water. It was established that the two highest molecular weight fractions were associated in an average trimeric form in dioxane-water (1:1) as compared to the form (considered to be molecular) that occurred in dimethylformamide. Molecular size distributions and eluant volumes of the fractions were determined with a Sephadex G-100-formamide system, the latter being one of the most powerful nonaqueous solvents for lignin. Adsorption effects were known to be absent in this case, and the lignin molecules were considered to be unassociated in formamide. The four fractions were distinguishable with the formamide-G-100 system, thus indicating that the original fractionation was based on molecular size. The enzymatically liberated lignin contained molecules that comprised a continuum of molecular weights from approximately monomeric to molecules that were at the limit of the solvating power of dioxane-water (1:1) and dimethylformamide. Limited physicochemical data were consistent with a compact, approximately spherically symmetric shape of the lignin in solution.
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  • 47
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    Biopolymers 7 (1969), S. 189-197 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A comparison has been made of the intrachain potential energy of an infinite straight α-helix of poly-L-alanine with that of the distorted form adopted in a coiled coil conformation. The energy terms included were the van der Waal's, electrostatic, hydrogen-bond, and the rotational potential terms. The results indicate that the potential energies of the structures investigated are almost the same, and so a transformation from one state to another may occur without significant changes in potential energy. Particular care has been taken to ensure that the electrostatic and van der Waal's interaction terms are fully convergent. The values obtained for the α-helix were compared with those already published, and some significant differences were found.
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  • 48
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    Topics: Chemistry and Pharmacology
    Notes: Ultraviolet optical rotatory dispersion curves of mucopolysaccharides exhibit particular Cotton effects in the spectral region of the n-π and π-π amide transitions. Two general patterns emerge: (1) enhancement of negative rotation and of the first negative Cotton effect (troughs 217-220 mμ) and (2) relative dominance of the positive Cotton effect in the π-π transition region (peak ∼198 mμ). Groups (1) and (2) can be correlated with a structural difference in the linkages of the amino sugars: (1) occurs with polymers containing 3-1-linked glycosamino sugars and (2) with glycosamino moieties linked 4-1 by either α- or β-glycosidie bonds. Measurements of the circular dichroic absorption bands support the qualitative conclusions from optical rotation. All mucopolysaccharides exhibit a first, negative band centered at 208-211 mμ, while only those in group (2) show, in addition, a positive band centered at 189-192 mμ. A suggested unifying model considers that difference in kind and/or degree of preferred geometry of the amide groups obtains from two forms of secondary order: (1) having a linear hydrogen bond from the N (acceptor) to the (C2)O - H of the preceding uronic acid and (2) having a linear hydrogen bond from the N (acceptor) to the (C2 or 3) O - H of the following sugar. The hydrogen bonds would have similar strength but opposite directions in two systems towards the nonreducing end (1) or towards the reducing end (2)], closing eight-membered rings
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  • 49
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    Biopolymers 7 (1969), S. 99-106 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The myosin molecule was extracted from the smooth muscle parts of horse esophagus and purified by ammonium sulfate fractionation. The schlieren pattern of the sedimentation velocity run showed a very sharp single peak of.5.9. S (s20,w). Molecular weight of the protein was measured by means of the Archibald and sedimentation equilibrium methods, both in 0.5M KCI buffered by 1/150 M phosphate at pH 7.5 and at 5°C. The values obtained were 6.25 × 105 and 5.81 × 105respectively, for the two methods. The second virial coefficients were 1.1 × 104 and 1.2 × 10-4 ml/g. Denatured smooth muscle myosin was prepared in a solution of 5M guanidine HC1 containing 0.4 M KC1 and 0.2 M β-mercaptoet hanol buffered at pH 8.0. The weight-average molecular weight of the denatured smooth muscle myosin was 2.24 × 105 and the second virial coefficient was 7.6 × 10-4 ml/g. The values described above are in good agreement with those reported for rabbit skeletal myosin with ammonium sulfate fractionation. The molecular dimension of the molecule is estimated as the value for an axial ratio of 100, assuming a rigid rod molecular model for this molecule, both the thermodynamical and hydrodynamical treatment being in a good agreement with this estimation.
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  • 50
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    Biopolymers 7 (1969) 
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    Keywords: Chemistry ; Polymer and Materials Science
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  • 51
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    Biopolymers 7 (1969), S. 433-434 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 52
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    Notes: The enthalpy change accompanying the double helix-coil transition of polyriboadenylic acid (poly A) in aqueous solution has been measured optically and calorimetrically in the pH range 5.7-4.5. The course of this cooperative transition was followed optically by measuring changes in ultraviolet absorption as a function of temperature at different pH values, and calorimetrically by determining the heat capacity of the solution through the transition region. From the latter measurements, the enthalpy of transition was calculated. It is shown, that ΔH is dependent on pH as it is expected from the influence of protonation of the double helix of poly A.
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  • 53
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    Biopolymers 7 (1969), S. 453-458 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The interaction between ionizable carboxyl groups and the conformation of poly-(glutamic acid) (PGA) in aqueous solution were investigated by the mechanical method. The dynamic rigidity of the PGA solution has a maximum value at the pH corresponding to about 50% neutralization point. This may be due to establishing of a maximum attractive force by proton/charge fluctuation between ionizable carboxyl groups at that pH. The dynamic viscosity has a sharp change in the region of pH 5.5-6.5. It is suggested that this behavior is due to the helix-coil transition.
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  • 54
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    Biopolymers 7 (1969), S. 447-452 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: By use of D2O we found that the shortening of the longitudinal proton relaxation time which occurs in the investigated aqueous yeast DNA solutions (≦ 2.4% with 2% protein) was not based on a hydration effect, but was caused by magnetic impurities only. An estimate shows that the mobility of the hydrated water molecules is reduced by less than two orders of magnitude in comparison with the free water molecules.
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  • 55
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    Biopolymers 7 (1969), S. 435-445 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A general approach to the determination of relative stability of any pair of con-formational states of biological macromolecules or their complexes (in particular, to the determination of relative stability of native and disordered states of the macromolecule) has been suggested. For determining the free energy difference of the two states under the conditions when one of them is considerably more advantageous than the other, it is necessary for the macromolecule to be influenced by the transforming agent which levels free energies of both the conformational states, and to determine the external parameter derivative of the free energy difference in the region of the conformational transition induced by the change in this parameter. If the character of the dependence of this derivative on the external parameter (temperature, solvent composition, etc.) is known, then this allows the determination of the free energy difference of the two states under the conditions considered, even including conditions far from the transition region. The value of the derivative of the free energy difference in the transition region in many cases can be measured directly (in particular, when using calorimetry), while in cases when a direct measurement of the derivative is impossible, it can often he estimated experimentally from the steepness of the conformational transition. The methods of this estimation and also a possible character of the change of the considered derivative during variation of the external parameter are considered for the case when the transforming agent is one of the components of the solvent and, consequently, the derivative of the free energy difference is equal to the difference of number of molecules of this component hound with the macromolecule in two conformational states.
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  • 56
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    Biopolymers 7 (1969), S. 459-474 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Wool-water systems, at water contents above a threshold value of 22.7 g of water per 100 g of wool keratin, yielded curves of specific heat against temperature showing peaks that are ascribed to the fusion of the absorbed water. Integral and incremental heats of fusion were obtained. Integral heats increase as the square of the water content above the threshold, and incremental heats follow a linear relationship. The incremental heat reaches a value of 55 cal/absorbed water, at the saturation water content, at 0°C of 33.9 g of water per 100 g of keratin. The state of the absorbed water is discussed. Clustering of water molecules takes place only above the threshold water content.
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    Biopolymers 8 (1969), S. 173-179 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The laser-excited Raman spectra have been obtained of poly-L-proline in the solid and aqueous solution. In the solid state, the Raman spectra are of the form II which is the left-handed helical form with the peptide bonds in the trans configuration. Dissolution of this form in water produced only minor changes in the Raman spectra. The differences in frequencies produced by dissolving the polymer are associated with vibrational modes of the pyrrolidine ring as indicated by comparison with the Raman spectrum of L-proline. The similarity of the Raman spectra dictates that, the conformations of poly-L-proline chain are similar in the solid and aqueous solution.
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    Biopolymers 8 (1969), S. 181-185 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: A comparative study on sonicated calf thymus DNA was made by using electron microscopy and sedimentation methods. The length distribution, established by electron microscopy by using Kleinschmidt's technique, is related to the sedimentation curve obtained with the same solution. The relation permits a determination of the sedimentation constant corresponding to a given length up to 8000 Å and vice versa.
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  • 59
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    Biopolymers 8 (1969), S. 199-216 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The π-electron polarizability of conjugated base molecules such as uracil and adenine are calculated semiempirically by using molecular orbital theories. The Hüekel method and the self-consistent-field (SCF) theory are used in the present calculation. The theoretical values obtained by the Hüekel method are consistently larger than the experimental results. The values obtained by the SCF theory are in good agreement with observed values. It is clearly demonstrated that the SCF method is better than the Hükel method for the calculation of polarizability. The polarizability of the adenine-uracil pair is calculated as the sum of the polarizabilities of adenine and uracil and also calculated by solving the eigenvalue problem for the A-U pair as an entity. The second method gives considerably larger polarizability than the first method. Discussions are presented and it is demonstrated that the second method is the correct way to calculate the polarizability of the A-U pair.
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  • 60
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    Topics: Chemistry and Pharmacology
    Notes: The reversibility of the thermal denaturation of a low-sulfur fraction of solubilized wool keratin (SCMKA) has been studied under a variety of conditions of time, protein concentration, and pH. Two types of irreversibility for the transition have been encountered. One of these is associated with an aggregation of the protein on denaturation to give a product which may contain elements of a β conformation. This type of irreversibility is favored by high protein concentration, and the original conformation may in fact be regained if the aggregated structure is broken down by a solvent such as 8M urea and the urea subsequently removed by dialysis. The other type of irreversibility appears to be due to racemization of the protein. It does not seem to be dependent on protein concentration and is apparent only at temperatures beyond the actual transition range (∼40-65°C) at pH values below 11, At pH 12, however, racemization appears to proceed slowly even at 4°C. The thermal transition at pH 9 and pH 10 has been shown to be multistage in nature. Over the pH range 9-12 there is a progressive decrease in thermal stability with increase of pH. Addition of NaCl at pH 10 leads to an increase in thermal stability of the molecule.
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    Biopolymers 8 (1969), S. 217-235 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: We report studies of the optical properties of the proflavine-DNA complex, using absorbance and circular dichroism spectroscopy. From comparison of the absorption spectra of proflavine complexed with calf thymus and T2 DNA, we conclude that stacking of the dyes external to the double helix is comparatively much weaker with T2 DXA, probably because of its glucosylation. Several sources are found for the circular dichroism induced in proflavine when it is complexed with DNA. There is a relatively weak circular dichroism induced when the dye is infinitely dilute on the DNA lattice; this presumably arises from the environmental asymmetry of the binding site. Stronger circular dichroism effects are induced by interaction of intercalated and stacked dyes; studies with T2 DNA, for which stacking seems to be blocked, permit a tentative resolution of effects due to the two modes of binding. One recurring theme of these studies is the observation that the optical properties are quite dependent on environment. The most dramatic example is a strong variation with salt concentration of the amplitude of the circular dichroism induced in the isolated (intercalated) monomer by the surrounding DNA. This suggests that the structure of the intercalated complex is quite sensitive to external conditions.
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  • 62
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    Topics: Chemistry and Pharmacology
    Notes: The binding of n-butanol, benzyl alcohol, and trifluoroethanol to polyproline I (all peptide bonds in cis configuration) and II (all peptide bonds in trans configuration) has been demonstrated. It was found by infrared spectroscopy that hydrogen bonds are formed between the CO groups of the polymer and the OH groups of the alcohols. Their strength increases from n-butanol via benzyl alcohol to trifluoroethanol. The binding of benzyl alcohol could also be followed by optical rotatory dispersion due to the fact that the electronic transitions of the benzyl ring are rendered optically active by the binding to the polymer.
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    Biopolymers 8 (1969), S. 259-274 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The statistical mechanics of the effect of a small number of randomly occurring defects on the melting of a polypeptide chain is developed by using a perturbation of Boltzmann factors technique. The method is illustrated by an example where a second-component impurity contributes more to the energy of the hydrogen-bonded superstructure of the polypeptide chain than does the dominant amino acid residue, resulting in the overall destabilization of the helical conformation.
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    Biopolymers 8 (1969), S. 275-287 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Biological membranes consist mainly of lipids and proteins. At present, the structure of the lipid phase appears to be established, but hypotheses on the molecular organization of the protein are difficult to support. Thus the deformation behavior of whole human erythrocyte ghosts, ghosts after the selective removal of lipids and ghosts stripped of lipids as well as nonlipid components have been examined in the hope of securing indirect information on the organization of the protein. It has been found that large localized deformations result in partial membrane failure and long uniformly wide fibrils, frequently in excess of 3000 Å, are drawn across the rupture. These data are interpreted in terms of currently favored membrane models and the possibility of a fibrous membrane framework consisting predominantly of protein is reviewed. The behavior of the membrane in its various stages of extraction is compared and contrasted to that of synthetic polymer films of known organization.
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    Biopolymers 8 (1969), S. 247-257 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The thermally induced conformational changes of poly-N5-(3-hydroxypropyl)-L-glutamine in water and in methanol-water (3:7 v/v) have been analyzed in terms of the Lifson-Roig theory. The transitions in both solvents can be described by using v = 0.017. The thermodynamic parameters for the random coil-to-helix transition of one amino acid residue at room temperature were found to be: in water, ΔH = - 130 cal/mole and ΔS = - 0.45 e.u.; in methanol-water (3:7 v/v), ΔH = - 170 cal mole and ΔS = - 0.45 e.u. The size distribution of helical segments is broad, and the results of numerical calculations are presented for three degrees of polymerization (DP = 100, 300, and 750).
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    Biopolymers 8 (1969), S. 289-292 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Biopolymers 8 (1969), S. 293-295 
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    Biopolymers 8 (1969), S. 297-299 
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    Biopolymers 8 (1969), S. 303-304 
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    Biopolymers 8 (1969), S. 301-301 
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    Biopolymers 8 (1969), S. 304-304 
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    Biopolymers 8 (1969) 
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    Biopolymers 7 (1969), S. 595-610 
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    Topics: Chemistry and Pharmacology
    Notes: The cyclic dipeptide, L-alanylglycyl anhydride, has been studied by optical rotatory dispersion; both L-alanylglycyl anhydride and the lactam, L-3-aminopyrrolidin-2-one, have been studied by circular dichroism. In hydroxylic solvents the circular dichroism spectra of 3-aminopyrrolidin-2-one can be attributed to an n-π* transition near 220 mμ and a π-π* transition near 190 mμ. In these solvents the optical activity of L-alanylglycyl anhydride can be explained as being due to contributions of n-π* transitions and a split π-π* transition. In acetonitrile, however, the circular dichroism spectrum of 3-aminopyrrolidin-2-one shows an additional apparent minimum near 200 mμ. The CD spectrum of the dipeptide is also quite distinctive in this solvent. The possible nature of the band at 200 mμ and the implications of these findings are discussed.
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    Biopolymers 7 (1969), S. 619-623 
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    Biopolymers 7 (1969) 
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    Biopolymers 7 (1969), S. 627-648 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: The flow birefringence, extinction angles, and intrinsic viscosity have been determined at low velocity gradients for a complex of T2 bacteriophage DNA and methylated serum albumin prepared in dilute solution to a stoichiometry of approximately 90 proteins per DNA molecule. Comparative data upon equivalent solutions of pure uncomplexed T2 DNA are also presented, and these data are completely in accord with the results of previous study. The experimental data are interpreted in terms of current dynamical theory and indicate that the complex has an essentially linear chain structure, consisting of approximately two DNA molecules, which is hydrodynamically indistinguishable from the pure DNA and that extensive internal or intramolecular binding in the complex does not occur. Although interpretation of the results is hampered by an apparent moderate degree of polydispersity in the complex preparations and by relatively large shear extrapolations, the data for both DNA and the complex are substantially in accord with dynamical theory for a nondraining bead subchain model having high kinetic segmental rigidity.
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    Biopolymers 7 (1969), S. 649-658 
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    Keywords: Chemistry ; Polymer and Materials Science
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    Topics: Chemistry and Pharmacology
    Notes: Far-infrared spectra in the region from 700 to 60 cm-1 have been measured for the α-helix structures of poly(L-α-amino-n-butyric acid), poly-L-norvaline, poly-L-norleucine, and poly-L-leucine and for the β-form structures of poly(L-α-amino-n-butyric acid), poly-L-valine, poly(DL-amino-n-butyric acid), poly-DL-norvaline, and poly-DL-norleucine. The changes of the spectra on N-deuteration have been measured in the region between 700 and 400 cm-1. It is concluded that, the α-helix has characteristic bauds near 690, 650, 610, 380, 150, and 100 cm-1, and that the β-form has characteristic bands near 700, 240, and 120 cm-1. The main-chain vibrations in the region from 600 to 200 cm-1 are strongly coupled with the side-chain deformation vibrations.
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    Biopolymers 7 (1969), S. 681-693 
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    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Single-strand breaks (ssb) in opposite strands of DNA can be sufficiently near that a double-strand break (dsb) results. A theory is presented by which the maximum number h of base pairs which cannot prevent double-strand breakage can be determined from the rates of production of ssb and dsb. The assumptions required to derive the necessary equations as well as the range of validity of the equations are discussed in detail. In the experiments ssb and dsb were produced by x-irradiation in buffers which do not eliminate indirect effects and were measured by analytical ultracentrifugation. Values of h have been determined in low and high ionic strength and in low ionic strength over a range of temperatures. The values, 2.64 and 15.8, were obtained for high and low ionic strength, respectively.
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    Biopolymers 7 (1969), S. 695-705 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The nature of a specific association between acriflavine and cellular DNA was investigated by subjecting the DNA of intact cells to denaturation, ultraviolet radiation, and base analog substitution. The predictable modifications of DNA structure were then correlated with the quantitative alterations in dye adsorption by the cells. It was concluded that, under experimental conditions of limited dye availability, the bonding of dye was restricted to sites of highest bonding affinity. These were shown to be situated between adjacent thymine molecules on a single strand of DNA. The 5-methyl groups of thymine may endow the bond with its specificity.
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  • 81
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    Biopolymers 7 (1969), S. 659-670 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The theory of polyelectrolyte solution of Alexandrowicz: and Katchalsky is used to calculate the electrostatic potential of single stranded polynucleotides for different ionic strength. We have considered the potential of double stranded DNA as the superposition of the different potentials produced by each chain, provided the average distance between the strands is higher than an ionic strength-dependent parameter b. For ionic strength lower than 5 × 10-2M, the assumption is no longer valid, and a cylindrical model with a uniform charge density must be used. The continuity between the two models was tested, and thus we can calculate the electrical potential at the vicinity of a phosphate group in the whole range of ionic-strength where the double helix is stable. It was therefore possible to determine the theoretical number of ions bound electrostatically to DNA and we found an increase of ion binding with a decrease of ionic strength. Such a model was further applied to the change of specific volume in different salt solutions. Comparison is made with recent pycnometric data on Na- and Cs- salts of DNA. Agreement is good in the case of Cs+, but for Na+, cation binding is likely to be accompanied by a change of the hydration of DNA, which depends on ionic strength. With the same model we can see easily the ion-trapping properties of DNA which play an important role in any formation of complex between heavy ions and bases.
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  • 82
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    Biopolymers 7 (1969), S. 671-680 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Preferential adsorption of cations occurs in the solvated shell surrounding polyanions, especially polynucleotides and nucleic acids. The solvation parameter Γ is determined from sedimentation coefficients which are considered as pienometric determinations of the specific volume of the sample. By comparing two identical concentrations (0.1M) of monovalent salts, NaCl and CsCl, and using the model of DNA described in the preceding paper, one can relate the ratio SCs/SNa to solvation parameters ΓCs, and ΓNa.On the other hand, Γ can be related to the difference of energy W, between cation and water, to be extracted from the solution and placed in the vicinity of the polyanion. One finds generally a preferential solvation of the polarizable caesium ion by means of London-van der Waals interactions with bases. With reasonable assumptions, an estimate of W can be made, and the predicted value of Γ can be compared to the experimental one. An average of six sites is found around each base in a single-stranded polymer, but-only one in the double-stranded structure. The amount of secondary structure can thus be estimated from the simple measurement of the ratio of two sediment constants.
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  • 83
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    Chemie in unserer Zeit 3 (1969), S. 163-170 
    ISSN: 0009-2851
    Keywords: Chemistry ; Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 84
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 319-341 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Reaktivität des 3-Äthoxy-1.2-diphenyl-cyclopropenylium-Kations (1) gegenüber C-Anionen des Malodinitrils, Cyanessigesters, Benzylcyanids etc. wird systematisch untersucht. Das Nucleophil kann sowohl am C-3 als auch am C-1 von 1 angreifen; diese Konkurrenz ist von Solvens und Substituenteneffekten determiniert. Die entstehenden Produkte - Δ1-resp. Δ2-Cyclopropen-3-äthyläther 9 bzw. 10, Methylencyclopropen-Derivate (16) oder ringoffene 1 : 1-Addukte (20) - werden in ihrer Struktur aufgeklärt und ihr Bildungsmechanismus diskutiert.
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 374-375 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 86
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    Berichte der deutschen chemischen Gesellschaft 102 (1969) 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 87
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 23-30 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die protonenkatalysierte Umsetzung von Arylcyanaten mit Dimethylsulfoxid liefert im ersten Reaktionsschritt Carbamidsäureester, die bei längerer Reaktionsdauer oder erhöhter Temperatur durch intermediär gebildeten Formaldehyd zu N.N′-Methylen-bis-[carbamidsäurearylestern] (5) kondensieren. Der Mechanismus des Primärschritts wird als ein der Pummerer-Reaktion analoger Zerfall eines aktivierten Komplexes aus Arylcyanat, Dimethylsulfoxid und Proton erkannt.
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 38-49 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Phosphine können bei der Reaktion mit Aziden in α- oder γ-Position der Stickstoffkette angreifen. Für das in Substanz faßbare Staudinger-Addukt von Triphenylphosphin an Tosylazid belegen Infrarotspektren 15N-isotopenmarkierter Derivate eine unverzweigte R3P=Nγ—Nβ=Nα—X-Struktur. Bei der thermischen Zersetzung in Benzol zu N-Tosyl-P-triphenyl-phosphazen (4) wird nach massenspektroskopischen Untersuchungen ausschließlich γ.β-N2 abgespalten.
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 77-82 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Umsetzungen von Cl3-nFnCSCl (n = 1,2,3) mit F3CCO2Ag liefern in guten Ausbeuten Verbindungen vom Typ , die bei 20° unbegrenzt haltbar sind. Erhitzt man (1) im Bombenrohr auf 170°, so bilden sich Kohlendioxid und F3CSCF3, während beim Bestrahlen mit UV-Licht Perfluoracetanhydrid, F3CSSCF3 und F3CSO2SCF3 entstehen. Bestrahlt man mit (2) UV-Licht, so bilden sich CO2 und Cl2FCSCF3. Aus Thionylchlorid und Cl3-nFnCCO2Ag (n = 2,3) konnten nur die entsprechenden Anhydride und SO2 isoliert werden. Analog liefert Silberperfluorbutyrat mit F3CSCl die Zersetzungsprodukte F3CSSCF3, F3CSO2SCF3 und (C3F7CO)2O.
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 104-111 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bis-[β-chlor-β-alkoxy-äthyl]-sulfoxide 5 entstehen unter milden Bedingungen bei der Umsetzung von Thionylchlorid mit Vinyläthern im Molverhältnis 1:3. Bei der Reaktion C-substituierter Vinyläther mit Thionylchlorid sind nur 1 : 1-Additionsverbindungen isolierbar. - 5a bildet mit prim. und sek. Aminen Bis-[β-amino-vinyl]-sulfoxide 7, mit Triäthylamin das Eliminierungsprodukt 9 und durch intramolekulare Redox-Reaktion 10.
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 118-125 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Darstellung der zum trans-Pinansystem gehörenden Pinandiole-(2.3) (1 und 2) wird der konfigurative Zusammenhang der vier diastereomeren Pinandiole-(2.3) klar ersichtlich.
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 167-179 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Derivate des Hexahydro-1.2.4.5.3.6-tetrazadiborins (1a) entstehen bei der Einwirkung von Organylhydrazinen auf Diaminoborane oder Phenylbordichlorid. Physikalische Untersuchungen legen eine aplanare Ringstruktur mit Bevorzugung der Wannenform nahe.Die Hydrazinolyse von HB[N(CH3)2]2 mit CH3HN—NHCH3 und CH3HN—NH2 ergibt Dimere dieses Ringsystems. Es sind Methylderivate der pentacyclischen Käfigverbindung 20. Das aus Hydrazin und Bis(dimethylamino)-boran zugängliche polymere (HB-NH-NH)n zersetzt sich oberhalb von 110° unter N2-Abspaltung zu (H2B-NH-NH-BH2)n.
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 196-204 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Das Dinucleotid 9 wurde aus dem Nucleotid 8 und einem Guanidinium-Salz des Adenosin-5′-phosphorsäure-amids zusammengesetzt. 8 erhielt man aus dem Silbersalz des 3-Carbamoyl-pyridons-(6) (1) und 2.3.5-Tri-O-benzoyl-D-ribofuranosylchlorid über die O-Verbindung (2), die zum N-Ribosid (3) umgelagert und nach Entbenzoylierung und Acetonierung in 2′.3′-Stellung des Ribosids 4a mit Cyanäthylphosphat und Dicyclohexylcarbodiimid in 5′-Stellung zum Nucleotid 8 phosphoryliert wurde. Die β-Verknüpfung in 4a (und damit in 9) wurde u. a. durch Korrelation mit dem analogen Glucosid 4b so gut wie sichergestellt.
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 243-254 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 6-Dimethylamino-fulven (1) wird von CH3OD im Sinne einer elektrophilen Substitution in 2- und 5-Stellung deuteriert; unter der Annahme einer Reaktion 1. Ordnung ergab sich in CH3OD/CDCl3 (3 : 1) bei 60° eine Halbwertszeit von 3.7 Stdn. H-3 und H-4 werden langsamer gegen Deuterium ausgetauscht, ebenso das Proton in der 4-Position von 6-Dimethylamino-2.3-benzo-fulven (15). Die π- und J-Werte von 1, 10, 15, 17 und 18 wurden ermittelt; die vicinalen Kopplungskonstanten der Fulvenprotonen erlauben Aussagen über die Beteiligung polarer Grenzstrukturen am Grundzustand.
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  • 95
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 289-296 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tetrakis(diphenylphosphinomethyl)-methan, C[CH2P(C6H5)2]4, sowie Tetrakis(diphenylarsinomethyl)-methan, C[CH2As(C6H5)2]4, reagieren mit Halogenen zu Verbindungen des allgemeinen Typs C[CH2E(X)2(C6H5)2]4 (E = P, As; X = Cl, Br, J), in denen sämtliches Halogen im Festzustand und in Dichlormethan-Lösung kovalent gebunden ist. In stärker polaren Lösungsmitteln wie Dimethylformamid oder Acetonitril verhalten sich die Chlorderivate wie 1:2-, die Bromderivate wie 1 : 3- und die Jodverbindungen wie 1 : 4-Elektrolyte. Die aus sterischen Gründen mögliche Bildung von chlorverbrückten spirocyclischem, bromverbrückten bicyclischen und jodbrückenfreien Phosphonium- und Arsoniumkationen wird diskutiert.
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 342-350 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Phenyl-pyrrolidon (1b) wird durch UV-Licht in N-Phenyl-pyrrol (9) übergeführt. N-Phenyllactame mit mindestens 7 Ringgliedern (1d-f) lassen sich photochemisch in guten Ausbeuten in die Benz-aza-cycloalkenone 4d-f umlagern. Die Struktur der Photolyseprodukte wird spektroskopisch, durch Derivate und durch Abbau zu Anthranilsäure gesichert.
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 378-379 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 380-381 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Berichte der deutschen chemischen Gesellschaft 102 (1969), S. 383-387 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Synthese von α-Pyridyl-glyoxal (2) (in Lösung) und einige Eigenschaften werden beschrieben.
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    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Solvolyse der Titelverbindungen ergibt ausschließlich Fragmentierung zu den entsprechenden Cycloalkenen, wenn Tosylat- und Aldehyd-Gruppe eine anti-periplanare Konformation einnehmen können. Ist dies ausgeschlossen, treten neben der Fragmentierung Ausweichreaktionen unter Wagner-Meerwein-Umlagerung ein.
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