Observation of the noncovalent assembly and disassembly pathways of the chaperone complex MtGimC by mass spectrometry

PubMed Central

Fändrich, Marcus; Tito, Mark A.; Leroux, Michel R.; Rostom, Adam A.; Hartl, F. Ulrich; Dobson, Christopher M.; Robinson, Carol V.

2000-01-01

We have analyzed a newly described archaeal GimC/prefoldin homologue, termed MtGimC, by using nanoflow electrospray coupled with time-of-flight MS. The molecular weight of the complex from Methanobacterium thermoautotrophicum corresponds to a well-defined hexamer of two α subunits and four β subunits. Dissociation of the complex within the gas phase reveals a quaternary arrangement of two central subunits, both α, and four peripheral β subunits. By constructing a thermally controlled nanoflow device, we have monitored the thermal stability of the complex by MS. The results of these experiments demonstrate that a significant proportion of the MtGimC hexamer remains intact under low-salt conditions at elevated temperatures. This finding is supported by data from CD spectroscopy, which show that at physiological salt concentrations, the complex remains stable at temperatures above 65°C. Mass spectrometric methods were developed to monitor in real time the assembly of the MtGimC hexamer from its component subunits. By using this methodology, the mass spectra recorded throughout the time course of the experiment showed the absence of any significantly populated intermediates, demonstrating that the assembly process is highly cooperative. Taken together, these data show that the complex is stable under the elevated temperatures that are appropriate for its hyperthermophile host and demonstrate that the assembly pathway leads exclusively to the hexamer, which is likely to be a structural unit in vivo. PMID:11087821

Quaternary beetle research: the state of the art

NASA Astrophysics Data System (ADS)

Elias, Scott A.

2006-08-01

Quaternary beetle research has progressed in a variety of ways during the last decade. New kinds of data are being extracted from the fossil specimens themselves, such as ancient DNA and stable isotopes. The ancient DNA studies hold the promise of proving new insights on the stability of beetle genotypes. The study of stable isotopes of H and O from fossil beetle chitin holds the promise of providing an independent proxy for the reconstruction of temperature and precipitation. The discipline is also expanding into previously unstudied regions, such as Australia, New Zealand, and northern Asia. Along with the new study regions, new schools of thought are also forming in the discipline, challenging old research paradigms. This is a necessary step forward for the discipline, as it grows and develops in the 21st Century.

Designing Novel Quaternary Quantum Reversible Subtractor Circuits

NASA Astrophysics Data System (ADS)

Haghparast, Majid; Monfared, Asma Taheri

2018-01-01

Reversible logic synthesis is an important area of current research because of its ability to reduce energy dissipation. In recent years, multiple valued logic has received great attention due to its ability to reduce the width of the reversible circuit which is a main requirement in quantum technology. Subtractor circuits are between major components used in quantum computers. In this paper, we will discuss the design of a quaternary quantum reversible half subtractor circuit using quaternary 1-qudit, 2-qudit Muthukrishnan-Stroud and 3-qudit controlled gates and a 2-qudit Generalized quaternary gate. Then a design of a quaternary quantum reversible full subtractor circuit based on the quaternary half subtractor will be presenting. The designs shall then be evaluated in terms of quantum cost, constant input, garbage output, and hardware complexity. The proposed quaternary quantum reversible circuits are the first attempt in the designing of the aforementioned subtractor.

A facile synthesis of highly stable multiblock poly(arylene ether)s based alkaline membranes for fuel cells

NASA Astrophysics Data System (ADS)

Jasti, Amaranadh; Shahi, Vinod K.

2014-12-01

Herein, we are disclosing simple route for the preparation of alkaline membranes (AMs) based on aminated multiblock poly(arylene ether)s (AMPEs) synthesized by nucleophilic substitution-poly condensation followed by quaternization and alkalization reactions. In this procedure, four quaternary ammonium groups are successfully introduced without use of carcinogenic reagents such as chloromethylmethyl ether (CMME). Hydrophilic/hydrophobic phase separation is responsible for their high hydroxide conductivity (∼150 mS cm-1 at 80 °C) due to development of interconnected ion transport pathway. AMs are exhibiting good alkaline stability due to the presence of two vicinal quaternary ammonium groups and avoid degradation such as Sommelet-Hauser rearrangement and Hofmann elimination. Vicinal quaternary ammonium groups also resist nucleophilic (OH-) attack and suppress the Stevens rearrangement as well as SN2 substitution reaction due to stearic hindrance. Optimized AM (AMPE-M20N15 (55% DCM)) exhibits about 0.95 V open circuit voltage (OCV) and 48.8 mW cm-2 power density at 65 °C in alkaline direct methanol fuel cell (ADMFC) operation. These results suggest promising begin for the preparation of stable and conductive AMs for ADMFC applications and useful for developing hydroxide conductive materials.

Responses of coral reef fishes to past climate changes are related to life-history traits.

PubMed

Ottimofiore, Eduardo; Albouy, Camille; Leprieur, Fabien; Descombes, Patrice; Kulbicki, Michel; Mouillot, David; Parravicini, Valeriano; Pellissier, Loïc

2017-03-01

Coral reefs and their associated fauna are largely impacted by ongoing climate change. Unravelling species responses to past climatic variations might provide clues on the consequence of ongoing changes. Here, we tested the relationship between changes in sea surface temperature and sea levels during the Quaternary and present-day distributions of coral reef fish species. We investigated whether species-specific responses are associated with life-history traits. We collected a database of coral reef fish distribution together with life-history traits for the Indo-Pacific Ocean. We ran species distribution models (SDMs) on 3,725 tropical reef fish species using contemporary environmental factors together with a variable describing isolation from stable coral reef areas during the Quaternary. We quantified the variance explained independently by isolation from stable areas in the SDMs and related it to a set of species traits including body size and mobility. The variance purely explained by isolation from stable coral reef areas on the distribution of extant coral reef fish species largely varied across species. We observed a triangular relationship between the contribution of isolation from stable areas in the SDMs and body size. Species, whose distribution is more associated with historical changes, occurred predominantly in the Indo-Australian archipelago, where the mean size of fish assemblages is the lowest. Our results suggest that the legacy of habitat changes of the Quaternary is still detectable in the extant distribution of many fish species, especially those with small body size and the most sedentary. Because they were the least able to colonize distant habitats in the past, fish species with smaller body size might have the most pronounced lags in tracking ongoing climate change.

The Quaternary Structure of a Glycoside Hydrolase Dictates Specificity toward β-Glucans*

PubMed Central

Lafond, Mickael; Sulzenbacher, Gerlind; Freyd, Thibaud; Henrissat, Bernard; Berrin, Jean-Guy; Garron, Marie-Line

2016-01-01

In the Carbohydrate-Active Enzyme (CAZy) database, glycoside hydrolase family 5 (GH5) is a large family with more than 6,000 sequences. Among the 51 described GH5 subfamilies, subfamily GH5_26 contains members that display either endo-β(1,4)-glucanase or β(1,3;1,4)-glucanase activities. In this study, we focused on the GH5_26 enzyme from Saccharophagus degradans (SdGluc5_26A), a marine bacterium known for its capacity to degrade a wide diversity of complex polysaccharides. SdGluc5_26A displays lichenase activity toward β(1,3;1,4)-glucans with a side cellobiohydrolase activity toward β(1,4)-glucans. The three-dimensional structure of SdGluc5_26A adopts a stable trimeric quaternary structure also observable in solution. The N-terminal region of SdGluc5_26A protrudes into the active site of an adjacent monomer. To understand whether this occupation of the active site could influence its activity, we conducted a comprehensive enzymatic characterization of SdGluc5_26A and of a mutant truncated at the N terminus. Ligand complex structures and kinetic analyses reveal that the N terminus governs the substrate specificity of SdGluc5_26A. Its deletion opens the enzyme cleft at the −3 subsite and turns the enzyme into an endo-β(1,4)-glucanase. This study demonstrates that experimental approaches can reveal structure-function relationships out of reach of current bioinformatic predictions. PMID:26755730

Whirlin and PDZ domain-containing 7 (PDZD7) proteins are both required to form the quaternary protein complex associated with Usher syndrome type 2.

PubMed

Chen, Qian; Zou, Junhuang; Shen, Zuolian; Zhang, Weiping; Yang, Jun

2014-12-26

Usher syndrome (USH) is the leading genetic cause of combined hearing and vision loss. Among the three USH clinical types, type 2 (USH2) occurs most commonly. USH2A, GPR98, and WHRN are three known causative genes of USH2, whereas PDZD7 is a modifier gene found in USH2 patients. The proteins encoded by these four USH genes have been proposed to form a multiprotein complex, the USH2 complex, due to interactions found among some of these proteins in vitro, their colocalization in vivo, and mutual dependence of some of these proteins for their normal in vivo localizations. However, evidence showing the formation of the USH2 complex is missing, and details on how this complex is formed remain elusive. Here, we systematically investigated interactions among the intracellular regions of the four USH proteins using colocalization, yeast two-hybrid, and pull-down assays. We show that multiple domains of the four USH proteins interact among one another. Importantly, both WHRN and PDZD7 are required for the complex formation with USH2A and GPR98. In this USH2 quaternary complex, WHRN prefers to bind to USH2A, whereas PDZD7 prefers to bind to GPR98. Interaction between WHRN and PDZD7 is the bridge between USH2A and GPR98. Additionally, the USH2 quaternary complex has a variable stoichiometry. These findings suggest that a non-obligate, short term, and dynamic USH2 quaternary protein complex may exist in vivo. Our work provides valuable insight into the physiological role of the USH2 complex in vivo and informs possible reconstruction of the USH2 complex for future therapy. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

High-resolution analysis of Quaternary calcretes: a coupled stable isotope and micromorphological approach

NASA Astrophysics Data System (ADS)

Adamson, Kathryn; Candy, Ian; Whitfield, Liz

2015-04-01

Pedogenic calcretes are abundant in arid and semi-arid regions, and they are widely used as proxy records of palaeoclimatic change. Calcrete oxygen (δ18O) and carbon (δ13C) isotopic signatures are indicative of temperature, aridity, or vegetation at the time of calcrete formation. Their microfabrics also reflect carbonate formation mechanisms in response to the prevailing environmental conditions. Many studies have explored calcrete micromorphology or stable isotope composition, but these techniques have not yet been applied simultaneously. This co-analysis is important as it allows us to establish whether calcrete morphology directly reflects environmental change. This study tests the potential of combining these analyses to examine the relationships between calcrete microfabrics, their isotopic signals, and Quaternary climate change. Calcretes from four river terraces of the Rio Alias in southeast Spain have been analysed in detail. On the basis of morphostratigraphic correlation (Maher et al., 2007) and Uranium-series ages (Candy et al., 2005), these span the period from 304 ± 26 ka (MIS 9) to the Holocene. The oldest profiles have therefore been exposed to multiple glacial-interglacial cycles. A total of 37 micromorphological profiles have been used to extract stable oxygen and carbon isotopic indicators from 77 microfacies. The morphological and isotopic complexity of the calcrete profiles increases with progressive age. The oldest samples display multiple calcretisation phases, and their microfabrics have a larger isotopic range than the younger samples. Alpha (non-biogenic) fabrics have higher δ13C and δ18O values than beta (biogenic) fabrics. Strong positive covariance between δ13C and δ18O within all profiles suggests that both isotopes are responding to the same environmental parameter. We suggest that this is relative aridity. The study demonstrates that the detailed co-analysis of calcrete micromorphology and stable isotope signatures allows calcrete formation patterns to be placed into a wider palaeoclimatic context. Importantly, this technique provides a level of detail that is not possible through bulk isotope sampling alone. It demonstrates the potential of this technique to more reliably constrain the palaeoenvironmental significance of secondary carbonates in dryland settings where other proxy records may be poorly preserved.

Hydrogeochemical processes in the Plio-Quaternary Remila aquifer (Khenchela, Algeria)

NASA Astrophysics Data System (ADS)

Aouidane, Laiche; Belhamra, Mohamed

2017-06-01

The Remila Plain is a synclinal structure in northeast Algeria, situated within a semi-arid climate zone and composed of Mio-Pliocene-Quaternary deposits. Within the syncline, the Plio-Quaternary aquifer is the main source of drinking water for cattle and for agricultural irrigation water. This work aims to investigate the origin of groundwater mineralization and to identify the primary hydrogeochemical processes controlling groundwater evolution in the Remila aquifer. A total of 86 water samples from boreholes were analyzed for major, minor and stable isotopes (18O, 2H) over three seasons: first during low water levels in 2013, second during high water levels in 2014 and third for stable isotopes during low water levels in 2015. The analysis showed that the aquifer is controlled by five principal geochemical processes: (I) the dissolution of evaporite rocks, (II) cation exchange and reverse exchange reactions, (III) congruent dissolution of carbonates (calcite, dolomite) coupled with the dissolution of gypsum and calcite precipitation, (IV) sulfate reduction under anaerobic conditions, and (V) saltwater intrusion in the northeastern Sabkha plains. The 18O and deuterium concentrations in groundwater are very low, indicating that the aquifer is recharged by evaporated rainfall originating from the north slope of the Aurès Mountains which confirms that the aquifer is recharged in the southern part of the plain.

Physical Studies of P450–P450 Interactions: Predicting Quaternary Structures of P450 Complexes in Membranes from Their X-ray Crystal Structures

PubMed Central

Reed, James R.; Backes, Wayne L.

2017-01-01

Cytochrome P450 enzymes, which catalyze oxygenation reactions of both exogenous and endogenous chemicals, are membrane bound proteins that require interaction with their redox partners in order to function. Those responsible for drug and foreign compound metabolism are localized primarily in the endoplasmic reticulum of liver, lung, intestine, and other tissues. More recently, the potential for P450 enzymes to exist as supramolecular complexes has been shown by the demonstration of both homomeric and heteromeric complexes. The P450 units in these complexes are heterogeneous with respect to their distribution and function, and the interaction of different P450s can influence P450-specific metabolism. The goal of this review is to examine the evidence supporting the existence of physical complexes among P450 enzymes. Additionally, the review examines the crystal lattices of different P450 enzymes derived from X-ray diffraction data to make assumptions regarding possible quaternary structures in membranes and in turn, to predict how the quaternary structures could influence metabolism and explain the functional effects of specific P450–P450 interactions. PMID:28194112

Peptides derivatized with bicyclic quaternary ammonium ionization tags. Sequencing via tandem mass spectrometry.

PubMed

Setner, Bartosz; Rudowska, Magdalena; Klem, Ewelina; Cebrat, Marek; Szewczuk, Zbigniew

2014-10-01

Improving the sensitivity of detection and fragmentation of peptides to provide reliable sequencing of peptides is an important goal of mass spectrometric analysis. Peptides derivatized by bicyclic quaternary ammonium ionization tags: 1-azabicyclo[2.2.2]octane (ABCO) or 1,4-diazabicyclo[2.2.2]octane (DABCO), are characterized by an increased detection sensitivity in electrospray ionization mass spectrometry (ESI-MS) and longer retention times on the reverse-phase (RP) chromatography columns. The improvement of the detection limit was observed even for peptides dissolved in 10 mM NaCl. Collision-induced dissociation tandem mass spectrometry of quaternary ammonium salts derivatives of peptides showed dominant a- and b-type ions, allowing facile sequencing of peptides. The bicyclic ionization tags are stable in collision-induced dissociation experiments, and the resulted fragmentation pattern is not significantly influenced by either acidic or basic amino acid residues in the peptide sequence. Obtained results indicate the general usefulness of the bicyclic quaternary ammonium ionization tags for ESI-MS/MS sequencing of peptides. Copyright © 2014 John Wiley & Sons, Ltd.

Direct evidence of an elongation factor-Tu/Ts·GTP·Aminoacyl-tRNA quaternary complex.

PubMed

Burnett, Benjamin J; Altman, Roger B; Ferguson, Angelica; Wasserman, Michael R; Zhou, Zhou; Blanchard, Scott C

2014-08-22

During protein synthesis, elongation factor-Tu (EF-Tu) bound to GTP chaperones the entry of aminoacyl-tRNA (aa-tRNA) into actively translating ribosomes. In so doing, EF-Tu increases the rate and fidelity of the translation mechanism. Recent evidence suggests that EF-Ts, the guanosine nucleotide exchange factor for EF-Tu, directly accelerates both the formation and dissociation of the EF-Tu-GTP-Phe-tRNA(Phe) ternary complex (Burnett, B. J., Altman, R. B., Ferrao, R., Alejo, J. L., Kaur, N., Kanji, J., and Blanchard, S. C. (2013) J. Biol. Chem. 288, 13917-13928). A central feature of this model is the existence of a quaternary complex of EF-Tu/Ts·GTP·aa-tRNA(aa). Here, through comparative investigations of phenylalanyl, methionyl, and arginyl ternary complexes, and the development of a strategy to monitor their formation and decay using fluorescence resonance energy transfer, we reveal the generality of this newly described EF-Ts function and the first direct evidence of the transient quaternary complex species. These findings suggest that EF-Ts may regulate ternary complex abundance in the cell through mechanisms that are distinct from its guanosine nucleotide exchange factor functions. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

Reconstruction of Late Quaternary Climate in Central Europe - A Comparison of Stable Isotope and Trace Element Variations in Speleothems From Different Cave Systems in Germany.

NASA Astrophysics Data System (ADS)

Nordhoff, P.; Wiegand, B.; Simon, K.; Rosendahl, W.; Hansen, B. T.; Kempe, S.

2003-12-01

Speleothems (stalagmites, stalactites, flowstones) are important archives for Late Quaternary continental climatic and paleo-environmental reconstruction. Speleothems form when calcium carbonate precipitates from solutions seeping into caves hosted e.g. in limestone or dolomite complexes. Information of past climate variability and changes in local environmental conditions can be obtained from signatures of the stable isotopes of oxygen and carbon as well as trace element pattern recorded in speleothems. Reconstruction of paleo-temperature and past environmental conditions from stable isotopes, however, require isotopic equilibrium between the drip water and the precipitating calcium carbonate. Results from Dietzel et al. (1992) and Johnson and Ingram (2001) indicate that the formation of modern travertine and speleothem calcite occurs under isotopic equilibrium. Factors that influence the stable oxygen and carbon isotope composition during speleothem precipitation include e.g. the moisture source and precipitation, photosynthetic pathways, the bedrock proportion, and the drip rate. This often leads to a situation with several variables. However, a specific interpretation is possible when dealing with environments where only one of the factors is dominant, or specific settings are assumed to be invariant, or further proxies like trace element variations help to define the frame conditions during speleothem formation. Concentrations of trace elements (e.g. Sr, Mg) which are co-precipitated with calcite are related to changes in the composition of the solution and strongly depend on the dissolution/precipitation dynamics along drip water flow paths. In a multiproxy approach they are a valuable tool for the interpretation of the recorded stable isotope variations. We present first results from different cave systems located in the Swabian Alps and the Harz Mountains (Germany). Our study includes a high-resolution multiproxy approach, using U/Th-TIMS data, stable oxygen/carbon isotope data, and geochemical compositions of speleothems, covering ages from the Late Pleistocene to the Early Holocene. The results are compared to geochemical data from host rocks, soil zones, cave sediments, drip water compositions, and recent calcium carbonate precipitates. Understanding the response of a cave system to the actual climatic, hydrologic and environmental regimen is a main requirement for the interpretation of "paleo-information" conserved in speleothems in order to lead to a coherent picture of past continental climate dynamics. References: Dietzel M., Usdowski E., and Hoefs J., (1992): Applied Geochemistry 7: 177-184. Johnson, K.R. and Ingram, B.L. (2001): Abstract volume, 4th Internat. Symp. On Applied Isotope Geochemistry, Pacific Groove, USA: 70-72.

Quaternary Glacial Mapping in Western Wisconsin Using Soil Survey Information

ERIC Educational Resources Information Center

Oehlke, Betsy M.; Dolliver, Holly A. S.

2011-01-01

The majority of soils in the western Wisconsin have developed from glacial sediments deposited during the Quaternary Period (2.6 million years before present). In many regions, multiple advances and retreats have left a complex landscape of diverse glacial sediments and landforms. The soils that have developed on these deposits reflect the nature…

Numerical study of the electronic structure, elastic and optical properties of defect quaternary semiconductor CuGaSnSe4

NASA Astrophysics Data System (ADS)

Shen, Kesheng; Lu, Hai; Zhang, Xianzhou; Jiao, Zhaoyong

2018-06-01

The electronic structure, elastic and optical properties of the defect quaternary semiconductor CuGaSnSe4 in I 4 bar structure are systematically investigated using first-principles calculations. We summarize and discuss some of the studies on CuGaSnSe4 in partially ordered chalcopyrite structure and find that there are three atomic arrangements so far, but it is still uncertain which is the most stable. Through detailed simulation and comparison with the corresponding literature, we get three models and predict that M1 model should be the most stable. The band structure and optical properties of compound CuGaSnSe4, including dielectric constant, refractive index and absorption spectrum, are drawn for a more intuitive understanding. The elastic constants are also calculated, which not only prove that CuGaSnSe4 in I 4 bar structure is stable naturally but also help solve the problem of no data to accurately predict axial thermal expansion coefficients. The calculated values of the zero frequency dielectric constant and refractive index are comparable to those of the corresponding chalcopyrite structure but slightly larger.

Influence of late Quaternary climate change on present patterns of genetic variation in valley oak, Quercus lobata Née.

PubMed

Gugger, Paul F; Ikegami, Makihiko; Sork, Victoria L

2013-07-01

Phylogeography and ecological niche models (ENMs) suggest that late Quaternary glacial cycles have played a prominent role in shaping present population genetic structure and diversity, but have not applied quantitative methods to dissect the relative contribution of past and present climate vs. other forces. We integrate multilocus phylogeography, climate-based ENMs and multivariate statistical approaches to infer the effects of late Quaternary climate change on contemporary genetic variation of valley oak (Quercus lobata Née). ENMs indicated that valley oak maintained a stable distribution with local migration from the last interglacial period (~120 ka) to the Last Glacial Maximum (~21 ka, LGM) to the present compared with large-scale range shifts for an eastern North American white oak (Quercus alba L.). Coast Range and Sierra Nevada foothill populations diverged in the late Pleistocene before the LGM [104 ka (28-1622)] and have occupied somewhat distinct climate niches, according to ENMs and coalescent analyses of divergence time. In accordance with neutral expectations for stable populations, nuclear microsatellite diversity positively correlated with niche stability from the LGM to present. Most strikingly, nuclear and chloroplast microsatellite variation significantly correlated with LGM climate, even after controlling for associations with geographic location and present climate using partial redundancy analyses. Variance partitioning showed that LGM climate uniquely explains a similar proportion of genetic variance as present climate (16% vs. 11-18%), and together, past and present climate explains more than geography (19%). Climate can influence local expansion-contraction dynamics, flowering phenology and thus gene flow, and/or impose selective pressures. These results highlight the lingering effect of past climate on genetic variation in species with stable distributions. © 2013 John Wiley & Sons Ltd.

Quaternary geology and geomorphology of the lower Deschutes River Canyon, Oregon.

Treesearch

Jim E. O' Connor; Janet H. Curran; Robin A. Beebee; Gordon E. Grant; Andrei Sarna-Wojcicki

2003-01-01

The morphology of the Deschutes River canyon downstream of the Pelton-Round Butte dam complex is the product of the regional geologic history, the composition of the geologic units that compose the valley walls, and Quaternary processes and events. Geologic units within the valley walls and regional deformation patterns control overall valley morphology. Valley bottom...

Thermally stable surfactants and compositions and methods of use thereof

DOEpatents

Chaiko, David J [Woodridge, IL

2008-09-02

There are provided novel thermally stable surfactants for use with fillers in the preparation of polymer composites and nanocomposites. Typically, surfactants of the invention are urethanes, ureas or esters of thiocarbamic acid having a hydrocarbyl group of from 10 to 50 carbons and optionally including an ionizable or charged group (e.g., carboxyl group or quaternary amine). Thus, there are provided surfactants having Formula I: ##STR00001## wherein the variables are as defined herein. Further provided are methods of making thermally stable surfactants and compositions, including composites and nanocomposites, using fillers coated with the surfactants.

Palladium-Catalyzed Asymmetric Alkylation in the Synthesis of Cyclopentanoid and Cycloheptanoid Core Structures Bearing All-Carbon Quaternary Stereocenters

PubMed Central

Hong, Allen Y.; Bennett, Nathan B.; Krout, Michael R.; Jensen, Thomas; Harned, Andrew. M.

2011-01-01

General catalytic asymmetric routes toward cyclopentanoid and cycloheptanoid core structures embedded in numerous natural products have been developed. The central stereoselective transformation in our divergent strategies is the enantioselective decarboxylative alkylation of seven-membered β-ketoesters to form α-quaternary vinylogous esters. Recognition of the unusual reactivity of β-hydroxyketones resulting from the addition of hydride or organometallic reagents enabled divergent access to γ-quaternary acylcyclopentenes through a ring contraction pathway or γ-quaternary cycloheptenones through a carbonyl transposition pathway. Synthetic applications of these compounds were explored through the preparation of mono-, bi-, and tricyclic derivatives that can serve as valuable intermediates for the total synthesis of complex natural products. This work complements our previous work with cyclohexanoid systems. PMID:22347731

Nucleoplasmin-like domain of FKBP39 from Drosophila melanogaster forms a tetramer with partly disordered tentacle-like C-terminal segments

PubMed Central

Kozłowska, Małgorzata; Tarczewska, Aneta; Jakób, Michał; Bystranowska, Dominika; Taube, Michał; Kozak, Maciej; Czarnocki-Cieciura, Mariusz; Dziembowski, Andrzej; Orłowski, Marek; Tkocz, Katarzyna; Ożyhar, Andrzej

2017-01-01

Nucleoplasmins are a nuclear chaperone family defined by the presence of a highly conserved N-terminal core domain. X-ray crystallographic studies of isolated nucleoplasmin core domains revealed a β-propeller structure consisting of a set of five monomers that together form a stable pentamer. Recent studies on isolated N-terminal domains from Drosophila 39-kDa FK506-binding protein (FKBP39) and from other chromatin-associated proteins showed analogous, nucleoplasmin-like (NPL) pentameric structures. Here, we report that the NPL domain of the full-length FKBP39 does not form pentameric complexes. Multi-angle light scattering (MALS) and sedimentation equilibrium ultracentrifugation (SE AUC) analyses of the molecular mass of the full-length protein indicated that FKBP39 forms homotetrameric complexes. Molecular models reconstructed from small-angle X-ray scattering (SAXS) revealed that the NPL domain forms a stable, tetrameric core and that FK506-binding domains are linked to it by intrinsically disordered, flexible chains that form tentacle-like segments. Analyses of full-length FKBP39 and its isolated NPL domain suggested that the distal regions of the polypeptide chain influence and determine the quaternary conformation of the nucleoplasmin-like protein. These results provide new insights regarding the conserved structure of nucleoplasmin core domains and provide a potential explanation for the importance of the tetrameric structural organization of full-length nucleoplasmins. PMID:28074868

Dynamic covalent chemistry enables formation of antimicrobial peptide quaternary assemblies in a completely abiotic manner

NASA Astrophysics Data System (ADS)

Reuther, James F.; Dees, Justine L.; Kolesnichenko, Igor V.; Hernandez, Erik T.; Ukraintsev, Dmitri V.; Guduru, Rusheel; Whiteley, Marvin; Anslyn, Eric V.

2018-01-01

Naturally occurring peptides and proteins often use dynamic disulfide bonds to impart defined tertiary/quaternary structures for the formation of binding pockets with uniform size and function. Although peptide synthesis and modification are well established, controlling quaternary structure formation remains a significant challenge. Here, we report the facile incorporation of aryl aldehyde and acyl hydrazide functionalities into peptide oligomers via solid-phase copper-catalysed azide-alkyne cycloaddition (SP-CuAAC) click reactions. When mixed, these complementary functional groups rapidly react in aqueous media at neutral pH to form peptide-peptide intermolecular macrocycles with highly tunable ring sizes. Moreover, sequence-specific figure-of-eight, dumbbell-shaped, zipper-like and multi-loop quaternary structures were formed selectively. Controlling the proportions of reacting peptides with mismatched numbers of complementary reactive groups results in the formation of higher-molecular-weight sequence-defined ladder polymers. This also amplified antimicrobial effectiveness in select cases. This strategy represents a general approach to the creation of complex abiotic peptide quaternary structures.

Pleistocene land bridges act as semipermeable agents of avian gene flow in Wallacea.

PubMed

Garg, Kritika M; Chattopadhyay, Balaji; Wilton, Peter R; Malia Prawiradilaga, Dewi; Rheindt, Frank E

2018-08-01

Cyclical periods of global cooling have been important drivers of biotic differentiation throughout the Quaternary. Ice age-induced sea level fluctuations can lead to changing patterns of land connections, both facilitating and disrupting gene flow. In this study, we test if species with differing life histories are differentially affected by Quaternary land connections. We used genome-wide SNPs in combination with mitochondrial gene sequences to analyse levels of divergence and gene flow between two songbird complexes across two Wallacean islands that have been repeatedly connected during glaciations. Although the two bird complexes are similar in ecological attributes, the forest and edge-inhabiting golden whistler Pachycephala pectoralis is comparatively flexible in its diet and niche requirements as compared to the henna-tailed jungle-flycatcher Cyornis colonus, which is largely restricted to the forest interior. Using population-genomic and coalescent approaches, we estimated levels of gene flow, population differentiation and divergence time between the two island populations. We observed higher levels of differentiation, an approximately two to four times deeper divergence time and near-zero levels of gene flow between the two island populations of the more forest-dependent henna-tailed jungle-flycatcher as compared to the more generalist golden whistler. Our results suggest that Quaternary land bridges act as semipermeable agents of gene flow in Wallacea, allowing only certain taxa to connect between islands while others remain isolated. Quaternary land bridges do not accommodate all terrestrial species equally, differing in suitability according to life history and species biology. More generalist species are likely to use Quaternary land connections as a conduit for gene flow between islands whereas island populations of more specialist species may continue to be reproductively isolated even during periods of Quaternary land bridges. Copyright © 2018 Elsevier Inc. All rights reserved.

THE INTERSECTION OF STABLE AND NON-EQUILIBRIUM TETRAHEDRA IN A MUTUAL 7- COMPONENT SYSTEM OF Li, Na, Rb, T1/Br, C1, NO$sub 3$, SO$sub 4$ (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dombrovskaya, N.S.; Khakhlova, N.V.; Alekseeva, E.A.

1961-04-21

The most stable configuration of the mixture of the 16 salts formed from Li, Na, Rb, Tl/Br, Cl, NO/sub 3/, and S0/sub 4/ con ture which however interact, resulting in a stable mixture. On the basis of exchange reactions the following equation has been derived: LiBr + NaNO/sub 3/ + RbCl + 1/2Tl/sub 2/SO/sub 4/ = 1/ 2LiSO/sub 4/ + NaCl + RbNO/sub 3/ + TlBr. In addition, several binary complexes are also formed, such as Li/sub 2/SO/sub 4/ - Rb/sub 2/SO/sub 4/, 4Li/sub 2/SO/ sub 4/ - RbSO /sub 4/, RbCl - 2Li/sub 2/SO/sub 4/ and possible others. Inmore » view of the great interest, the intersection of stable and non-equilibrium tetrahedra consisting of components of both, was experimentally studied by thermai analysis. On the basis of cooling curves the following deflection points have been observed: 453 deg C, precipitation of the first Li/sub 2/SO/sub 4/ crystals; 409 deg , coprecipitation of Li/sub 2/SO/sub 4/ and NaCl; 391 deg , coprecipitation of Li/sub 2/SO/sub 4/, NaCl snd TlBr; and finally at 107 deg , formation of the quaternary eutectic with the previously mentioned salts + RbNO/sub 3/. The microstructures of the stable and non-equilibrium phases are quite similar. (TTT)« less

Oxalates as Activating Groups for Alcohols in Visible Light Photoredox Catalysis: Formation of Quaternary Centers by Redox-Neutral Fragment Coupling.

PubMed

Nawrat, Christopher C; Jamison, Christopher R; Slutskyy, Yuriy; MacMillan, David W C; Overman, Larry E

2015-09-09

Alkyl oxalates are new bench-stable alcohol-activating groups for radical generation under visible light photoredox conditions. Using these precursors, the first net redox-neutral coupling of tertiary and secondary alcohols with electron-deficient alkenes is achieved.

Effect of chain structure on hydrogen bonding in vinyl acetate - vinyl alcohol copolymers

NASA Astrophysics Data System (ADS)

Merekalova, Nadezhda D.; Bondarenko, Galina N.; Denisova, Yuliya I.; Krentsel, Liya B.; Litmanovich, Arkadiy D.; Kudryavtsev, Yaroslav V.

2017-04-01

FTIR spectroscopy and semi-empirical AM1 method are used to study hydrogen bonding in multiblock and random equimolar copolymers of vinyl acetate and vinyl alcohol. An energetically beneficial zip-holder complex, built on multiple inter- and intrachain hydroxyl-hydroxyl bonds and an intrachain hydroxyl-acetyloxy bond, can be formed between two vinyl alcohol sequences. As a result, multiblock copolymers reveal stronger degree of association that affects crystallinity, as well as various rheological and relaxation properties discussed in the literature. Macromolecular complexes in random copolymers are weak and tend to be destroyed in the presence of residual DMF solvent and adsorbed water. Nevertheless, a rather stable interchain quaternary complex can be formed that includes vinyl alcohol and vinyl acetate units and DMF and water molecules. For a single chain it is shown that an H-bond between neighboring vinyl alcohol and vinyl acetate monomer units mostly engages a carbonyl oxygen atom of the vinyl acetate, if the vinyl alcohol belongs to a short (<5 units) sequence, and an ether oxygen atom in the other case. On the whole, the quantum chemistry calculations shed much light on the origin of distinctions in the copolymer FTIR spectra, which may seem subtle when considered standalone.

Deformation and Quaternary Faulting in Southeast Missouri across the Commerce Geophysical Lineament

USGS Publications Warehouse

Stephenson, W.J.; Odum, J.K.; Williams, R.A.; Pratt, T.L.; Harrison, R.W.; Hoffman, D.

1999-01-01

High-resolution seismic-reflection data acquired at three sites along the surface projection of the Commerce geophysical lineament in southeast Missouri reveal a complex history of post-Cretaceous faulting that has continued into the Quaternary. Near Qulin, Missouri, approximately 20 m of apparent vertical fault displacement has occurred in the Quaternary. Reflection data collected at Idalia Hill, about 45 km to the northeast, reveal a series of reverse and possibly right-lateral strike-slip faults with Quaternary displacement. In the Benton Hills, 45 km northeast of Idalia Hill, seismic data image a complicated series of anticlinal and synclinal fault-bounded blocks immediately north of the Commerce fault. We infer that most of the deformation imaged in the upper 400 m of these three data sets occurred since post-Cretaceous time, and a significant portion of it occurred during Quaternary time. Collectively, these seismic data along with geomorphic and surface-geologic evidence suggest (1) the existence of at least one potential seismogenic structure in southeastern Missouri outside the main zones of New Madrid seismicity, and (2) these structures have been active during the Quaternary. The geographic location of the imaged deformation suggests it is related to structures along with the Commerce geophysical lineament.

Infrared spectroscopy of protonated trimethylamine-(benzene)(n) (n = 1-4) as model clusters of the quaternary ammonium-aromatic ring interaction.

PubMed

Shishido, Ryunosuke; Kawai, Yuki; Fujii, Asuka

2014-09-04

The essence of the molecular recognition of the neurotransmitter acetylcholine has been attributed to the attractive interaction between a quaternary ammonium and aromatic rings. We employed protonated trimethylamine-(benzene)n clusters (n = 1-4) in the gas phase as a model to study the recognition mechanism of acetylcholine at the microscopic level. We applied size-selective infrared spectroscopy to the clusters and observed the NH and CH stretching vibrational regions. We also performed density functional theory calculations of stable structures, charge distributions, and infrared spectra of the clusters. It was shown that the methyl groups of protonated trimethylamine are solvated by benzene one at a time in the n > 1 clusters, and the validity of these clusters as a model system of the acetylcholine recognition was demonstrated. The nature of the interactions between a quaternary ammonium and aromatic rings is discussed on the basis of the observed infrared spectra and the theoretical calculations.

Quaternary ammonium isobaric tag for a relative and absolute quantification of peptides.

PubMed

Setner, Bartosz; Stefanowicz, Piotr; Szewczuk, Zbigniew

2018-02-01

Isobaric labeling quantification of peptides has become a method of choice for mass spectrometry-based proteomics studies. However, despite of wide variety of commercially available isobaric tags, none of the currently available methods offers significant improvement of sensitivity of detection during MS experiment. Recently, many strategies were applied to increase the ionization efficiency of peptides involving chemical modifications introducing quaternary ammonium fixed charge. Here, we present a novel quaternary ammonium-based isobaric tag for relative and absolute quantification of peptides (QAS-iTRAQ 2-plex). Upon collisional activation, the new stable benzylic-type cationic reporter ion is liberated from the tag. Deuterium atoms were used to offset the differential masses of a reporter group. We tested the applicability of QAS-iTRAQ 2-plex reagent on a series of model peptides as well as bovine serum albumin tryptic digest. Obtained results suggest usefulness of this isobaric ionization tag for relative and absolute quantification of peptides. Copyright © 2017 John Wiley & Sons, Ltd.

Surface Induced Dissociation Yields Quaternary Substructure of Refractory Noncovalent Phosphorylase B and Glutamate Dehydrogenase Complexes

NASA Astrophysics Data System (ADS)

Ma, Xin; Zhou, Mowei; Wysocki, Vicki H.

2014-03-01

Ion mobility (IM) and tandem mass spectrometry (MS/MS) coupled with native MS are useful for studying noncovalent protein complexes. Collision induced dissociation (CID) is the most common MS/MS dissociation method. However, some protein complexes, including glycogen phosphorylase B kinase (PHB) and L-glutamate dehydrogenase (GDH) examined in this study, are resistant to dissociation by CID at the maximum collision energy available in the instrument. Surface induced dissociation (SID) was applied to dissociate the two refractory protein complexes. Different charge state precursor ions of the two complexes were examined by CID and SID. The PHB dimer was successfully dissociated to monomers and the GDH hexamer formed trimeric subcomplexes that are informative of its quaternary structure. The unfolding of the precursor and the percentages of the distinct products suggest that the dissociation pathways vary for different charge states. The precursors at lower charge states (+21 for PHB dimer and +27 for GDH hexamer) produce a higher percentage of folded fragments and dissociate more symmetrically than the precusors at higher charge states (+29 for PHB dimer and +39 for GDH hexamer). The precursors at lower charge state may be more native-like than the higher charge state because a higher percentage of folded fragments and a lower percentage of highly charged unfolded fragments are detected. The combination of SID and charge reduction is shown to be a powerful tool for quaternary structure analysis of refractory noncovalent protein complexes, as illustrated by the data for PHB dimer and GDH hexamer.

Small-angle neutron scattering reveals the assembly mode and oligomeric architecture of TET, a large, dodecameric aminopeptidase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Appolaire, Alexandre; Girard, Eric; Colombo, Matteo

2014-11-01

The present work illustrates that small-angle neutron scattering, deuteration and contrast variation, combined with in vitro particle reconstruction, constitutes a very efficient approach to determine subunit architectures in large, symmetric protein complexes. In the case of the 468 kDa heterododecameric TET peptidase machine, it was demonstrated that the assembly of the 12 subunits is a highly controlled process and represents a way to optimize the catalytic efficiency of the enzyme. The specific self-association of proteins into oligomeric complexes is a common phenomenon in biological systems to optimize and regulate their function. However, de novo structure determination of these important complexesmore » is often very challenging for atomic-resolution techniques. Furthermore, in the case of homo-oligomeric complexes, or complexes with very similar building blocks, the respective positions of subunits and their assembly pathways are difficult to determine using many structural biology techniques. Here, an elegant and powerful approach based on small-angle neutron scattering is applied, in combination with deuterium labelling and contrast variation, to elucidate the oligomeric organization of the quaternary structure and the assembly pathways of 468 kDa, hetero-oligomeric and symmetric Pyrococcus horikoshii TET2–TET3 aminopeptidase complexes. The results reveal that the topology of the PhTET2 and PhTET3 dimeric building blocks within the complexes is not casual but rather suggests that their quaternary arrangement optimizes the catalytic efficiency towards peptide substrates. This approach bears important potential for the determination of quaternary structures and assembly pathways of large oligomeric and symmetric complexes in biological systems.« less

In situ analysis of corrosion inhibitors using a portable mass spectrometer with paper spray ionization.

PubMed

Jjunju, Fred P M; Li, Anyin; Badu-Tawiah, Abraham; Wei, Pu; Li, Linfan; Ouyang, Zheng; Roqan, Iman S; Cooks, R Graham

2013-07-07

Paper spray (PS) ambient ionization is implemented using a portable mass spectrometer and applied to the detection of alkyl quaternary ammonium salts in a complex oil matrix. These salts are commonly used as active components in the formulation of corrosion inhibitors. They were identified in oil and confirmed by their fragmentation patterns recorded using tandem mass spectrometry (MS/MS). The cations of alkyl and benzyl-substituted quaternary ammonium salts showed characteristic neutral losses of CnH2n (n carbon number of the longest chain) and C7H8, respectively. Individual quaternary ammonium compounds were detected at low concentrations (<1 ng μL(-1)) and over a dynamic range of ∼5 pg μL(-1) to 500 pg μL(-1) (ppb). Direct detection of these compounds in complex oil samples without prior sample preparation or pre-concentration was also demonstrated using a home-built miniature mass spectrometer at levels below 1 ng μL(-1).

Stable isotopes in yellow-bellied marmot (Marmota flaviventris) fossils reveal environmental stability in the late Quaternary of the Colorado Rocky Mountains

NASA Astrophysics Data System (ADS)

Reynard, Linda M.; Meltzer, David J.; Emslie, Steven D.; Tuross, Noreen

2015-03-01

High elevation plant and animal communities are considered extremely sensitive to environmental change. We investigated an exceptional fossil record of yellow-bellied marmot (Marmota flaviventris) specimens that was recovered from Cement Creek Cave (elev. 2860 m) and ranged in age from radiocarbon background circa 49.8 cal ka BP to ~ 1 cal ka BP. We coupled isotopic and radiocarbon measurements (δ18O, δD, δ15N, δ13C, and 14C) of bone collagen from individually-AMS dated specimens of marmots to assess ecological responses by this species to environmental change over time in a high elevation basin in the Rocky Mountains of southwestern Colorado, USA. We find little change in all four isotope ratios over time, demonstrating considerable environmental stability during periods when the marmots were present. The stable ecology and the apparent persistence of the small mammal community in the cave fauna throughout the late Quaternary are in marked contrast to the changes that occurred in the large mammal community, including local extirpation and extinction, at the end of the Pleistocene.

Antimicrobial activity of betaine esters, quaternary ammonium amphiphiles which spontaneously hydrolyze into nontoxic components.

PubMed Central

Lindstedt, M; Allenmark, S; Thompson, R A; Edebo, L

1990-01-01

A series of quaternary ammonium compounds that are esters of betaine and fatty alcohols with hydrocarbon chain lengths of 10 to 18 carbon atoms were tested with respect to antimicrobial activities and rates of hydrolysis. When the tetradecyl derivative was tested against some selected microorganisms, the killing effect was comparable to that of the stable quaternary ammonium compound cetyltrimethylammonium bromide. At higher pH values, both the antimicrobial effect and the rate of hydrolysis of the esters increased. However, whereas at pH 6 greater than 99.99% killing of Salmonella typhimurium was achieved with 5 micrograms/ml in 3 min, the rate of hydrolysis was less than 20% in 18 h. At pH 7, a similar killing effect was achieved in 2 min and 50% hydrolysis occurred in ca. 5 h. Thus, it is possible to exploit the rapid microbicidal effect of the compounds before they hydrolyze. The rate of hydrolysis was reduced by the presence of salt. The bactericidal effect of the betaine esters increased with the length of the hydrocarbon chain of the fatty alcohol moiety up to 18 carbon atoms. Since the hydrolysis products are normal human metabolites, the hydrolysis property may extend the use of these quaternary ammonium compounds as disinfectants and antiseptics for food and body surfaces. PMID:2291660

Atomic-scale properties of Ni-based FCC ternary, and quaternary alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tamm, Artur; Aabloo, Alvo; Klintenberg, Mattias

2015-08-26

The aim of our study is to characterize some atomic-scale properties of Ni-based FCC multicomponent alloys. For this purpose, we use Monte Carlo method combined with density functional theory calculations to study short-range order (SRO), atomic displacements, electronic density of states, and magnetic moments in equimolar ternary NiCrCo, and quaternary NiCrCoFe alloys. The salient features for the ternary alloy are a negative SRO parameter between Ni Cr and a positive between Cr Cr pairs as well as a weakly magnetic state. For the quaternary alloy we predict negative SRO parameter for Ni Cr and Ni Fe pairs and positive formore » Cr Cr and Fe Fe pairs. Atomic displacements for both ternary and quaternary alloys are negligible. In contrast to the ternary, the quaternary alloy shows a complex magnetic structure. The electronic structure of the ternary and quaternary alloys shows differences near the Fermi energy between a random solid solution and the predicted structure with SRO. Despite that, the calculated EXAFS spectra does not show enough contrast to discriminate between random and ordered structures. Finally, the predicted SRO has an impact on point-defect energetics, electron phonon coupling and thermodynamic functions and thus, SRO should not be neglected when studying properties of these two alloys.« less

Arctic systems in the Quaternary: ecological collision, faunal mosaics and the consequences of a wobbling climate.

PubMed

Hoberg, E P; Cook, J A; Agosta, S J; Boeger, W; Galbreath, K E; Laaksonen, S; Kutz, S J; Brooks, D R

2017-07-01

Climate oscillations and episodic processes interact with evolution, ecology and biogeography to determine the structure and complex mosaic that is the biosphere. Parasites and parasite-host assemblages are key components in a general explanatory paradigm for global biodiversity. We explore faunal assembly in the context of Quaternary time frames of the past 2.6 million years, a period dominated by episodic shifts in climate. Climate drivers cross a continuum from geological to contemporary timescales and serve to determine the structure and distribution of complex biotas. Cycles within cycles are apparent, with drivers that are layered, multifactorial and complex. These cycles influence the dynamics and duration of shifts in environmental structure on varying temporal and spatial scales. An understanding of the dynamics of high-latitude systems, the history of the Beringian nexus (the intermittent land connection linking Eurasia and North America) and downstream patterns of diversity depend on teasing apart the complexity of biotic assembly and persistence. Although climate oscillations have dominated the Quaternary, contemporary dynamics are driven by tipping points and shifting balances emerging from anthropogenic forces that are disrupting ecological structure. Climate change driven by anthropogenic forcing has supplanted a history of episodic variation and is eliminating ecological barriers and constraints on development and distribution for pathogen transmission. A framework to explore interactions of episodic processes on faunal structure and assembly is the Stockholm Paradigm, which appropriately shifts the focus from cospeciation to complexity and contingency in explanations of diversity.

Mapping monomeric threading to protein-protein structure prediction.

PubMed

Guerler, Aysam; Govindarajoo, Brandon; Zhang, Yang

2013-03-25

The key step of template-based protein-protein structure prediction is the recognition of complexes from experimental structure libraries that have similar quaternary fold. Maintaining two monomer and dimer structure libraries is however laborious, and inappropriate library construction can degrade template recognition coverage. We propose a novel strategy SPRING to identify complexes by mapping monomeric threading alignments to protein-protein interactions based on the original oligomer entries in the PDB, which does not rely on library construction and increases the efficiency and quality of complex template recognitions. SPRING is tested on 1838 nonhomologous protein complexes which can recognize correct quaternary template structures with a TM score >0.5 in 1115 cases after excluding homologous proteins. The average TM score of the first model is 60% and 17% higher than that by HHsearch and COTH, respectively, while the number of targets with an interface RMSD <2.5 Å by SPRING is 134% and 167% higher than these competing methods. SPRING is controlled with ZDOCK on 77 docking benchmark proteins. Although the relative performance of SPRING and ZDOCK depends on the level of homology filters, a combination of the two methods can result in a significantly higher model quality than ZDOCK at all homology thresholds. These data demonstrate a new efficient approach to quaternary structure recognition that is ready to use for genome-scale modeling of protein-protein interactions due to the high speed and accuracy.

First-principles study of half-metallic properties in RbCaNZ (Z = O, S, and Se) quaternary Heusler compounds

NASA Astrophysics Data System (ADS)

Rezaei, S.; Ahmadian, F.

2018-06-01

On the basis of first principles calculations, the electronic structures and magnetic properties of quaternary Heusler alloys RbCaNZ (Z = O, S, and Se) were studied. The negative formation energies indicated that all these compounds were thermodynamically stable and thus may be experimentally synthesized at appropriate conditions in the future. The results showed that YI structure was the most favorable configuration among the three possible structures. All compounds were found to be half-metallic ferromagnets. The characteristic of energy bands and origin of half-metallicity were also verified. The total magnetic moments of RbCaNZ (Z = O, S, and Se) compounds were obtained 2μB per formula unit, which were in an agreement with Slater-Pauling rule (Mtot = 12 - Ztot). Half-metallicity was preserved at ranges of 5.06-8.36 Å, 5.96-8.81 Å, and 6.13-8.73 Å for RbCaNO, RbCaNS, and RbCaNSe compounds, respectively, which show that these quaternary Heusler compounds may be potential candidates in spintronic applications.

Paleoenvironmental dynamics of Western Beringia - New studies from the Yedoma key site Duvanny Yar (Lower Kolyma River, Siberia)

NASA Astrophysics Data System (ADS)

Strauss, Jens; Schirrmeister, Lutz; Wetterich, Sebastian

2010-05-01

Duvanny Yar is a stratigraphic key site for the late Quaternary in Western Beringia. It is characteristic for ice-rich permafrost sequences of the so-called Yedoma Suite in north-east Siberia (e.g. KAPLINA et al. 1978; SHER et al. 1979) and is an important reference site for the late Pleistocene history of Beringia (HOPKINS 1982). The aim of our study was to reconstruct the paleoenvironmental dynamics at the Duvanny Yar site during the late Quaternary using its terrestrial archive. A multidisciplinary approach using geocryological, geochronological, sedimentological, hydrochemical, isotope geochemical, and paleoecological methods was applied to obtain multiproxy records. Sediment samples were analysed for ice contents, grain size parameters, biogeochemistry (total carbon, total organic carbon, total nitrogen, stable carbon isotopes), mineral density, mass specific magnetic susceptibility, and for radiocarbon age. Stable isotopes of water were measured for ground ice (ice wedges, segregated ice, and pore ice), modern surface waters and modern precipitation. Six profiles along the riverbank were sampled in August 2008. They contained Eemian lacustrine deposits, long sequences of Ice Complex deposits of the Late Pleistocene Yedoma, Holocene lacustrine and boggy deposits in thermokarst depressions. All profiles showed very bad sorted sediment of fine to coarse silt. A homogenous and polymodal grain size distribution for the ice rich (~30 to 60 wt %) Yedoma Suite revealed a polygenetic origin and disproves the pure "arctic loess" hypothesis for these deposits. Measurements of bulk density, ice content and total organic carbon content (TOC) enable for a relative TOC content in Ice Complex deposits at Duvanny Yar. The mean value of organic carbon at Duvanny Yar is 16 ± 11 kg/m^3. Geochronological results based on 11 new AMS ages revealed that the Yedoma Suite was continuously formed from the end of the Middle Weichselian (~ 40000 years BP) and at least until the Late Glacial Maximum (~ 20000 years BP). Stable water isotopes measured in ice wedges, segregated ice and ice lenses were used to estimate paleotemperature changes. Isotopic signals revealed cold temperatures for the whole period with relative warm peaks in the Eemian and Holocene times. During Yedoma Suite formation the climate was stable and cold. A better understanding of the paleoenvironmental dynamics at Duvanny Yar may provide a basis for more reliable predictions of future reaction on global warming of organic-bearing ice-rich permafrost in Siberia which is considered as a potential greenhouse gas source permafrost (DUTTA et al. 2006; ZIMOV et al. 2006). References Dutta, K., Schuur, E.A.G., Neff, J.C. and Zimov, S.A. (2006). "Potential carbon release from permafrost soils of Northeastern Siberia", Global Change Biology 12(12): 2336-2351. Hopkins, D.M. (1982). Aspects of the paleogeography of Beringia during the Late Pleistocene. In: Paleoecology of Beringia. Hopkins, D. M., Matthews, J. V., Schweger, C. E. and Young, S. B., Academic Press: 3-28. Kaplina, T.N., Giterman, R.E., Lakhtina, O.V., Abrashov, B.A., Kiselyov, S.V. and Sher, A.V. (1978). "Duvannyy Yar - a key section of Upper Pleistocene deposits of the Kolyma lowland", Bulletin of Quaternary Research Commission 48: 49-65. (in Russian) Sher, A.V., Kaplina, T.N., Giterman, R.E., Lozhkin, A.V., Arkhangelov, A.A., Kiselyov, S.V., Kouznetsov, Y.V., Virina, E.I. and Zazhigin, V.S. (1979). Late Cenozoic of the Kolyma Lowland. 14th Pacific Science Congress, Khabarovsk, Academy of Science, USSR. Zimov, S.A., Davydov, S.P., Zimova, G.M., Davydova, A.I., Schuur, E.A.G., Dutta, K. and Chapin III, F.S. (2006). "Permafrost carbon: Stock and decomposability of a globally significant carbon pool", Geophysical Research Letters 33(20): L20502.

Selective detection of carbohydrates and their peptide conjugates by ESI-MS using synthetic quaternary ammonium salt derivatives of phenylboronic acids.

PubMed

Kijewska, Monika; Kuc, Adam; Kluczyk, Alicja; Waliczek, Mateusz; Man-Kupisinska, Aleksandra; Lukasiewicz, Jolanta; Stefanowicz, Piotr; Szewczuk, Zbigniew

2014-06-01

We present new tags based on the derivatives of phenylboronic acid and apply them for the selective detection of sugars and peptide-sugar conjugates in mass spectrometry. We investigated the binding of phenylboronic acid and its quaternary ammonium salt (QAS) derivatives to carbohydrates and peptide-derived Amadori products by HR-MS and MS/MS experiments. The formation of complexes between sugar or sugar-peptide conjugates and synthetic tags was confirmed on the basis of the unique isotopic distribution resulting from the presence of boron atom. Moreover, incorporation of a quaternary ammonium salt dramatically improved the efficiency of ionization in mass spectrometry. It was found that the formation of a complex with phenylboronic acid stabilizes the sugar moiety in glycated peptides, resulting in simplification of the fragmentation pattern of peptide-derived Amadori products. The obtained results suggest that derivatization of phenylboronic acid as QAS is a promising method for sensitive ESI-MS detection of carbohydrates and their conjugates formed by non-enzymatic glycation or glycosylation.

Selective Detection of Carbohydrates and Their Peptide Conjugates by ESI-MS Using Synthetic Quaternary Ammonium Salt Derivatives of Phenylboronic Acids

NASA Astrophysics Data System (ADS)

Kijewska, Monika; Kuc, Adam; Kluczyk, Alicja; Waliczek, Mateusz; Man-Kupisinska, Aleksandra; Lukasiewicz, Jolanta; Stefanowicz, Piotr; Szewczuk, Zbigniew

2014-06-01

We present new tags based on the derivatives of phenylboronic acid and apply them for the selective detection of sugars and peptide-sugar conjugates in mass spectrometry. We investigated the binding of phenylboronic acid and its quaternary ammonium salt (QAS) derivatives to carbohydrates and peptide-derived Amadori products by HR-MS and MS/MS experiments. The formation of complexes between sugar or sugar-peptide conjugates and synthetic tags was confirmed on the basis of the unique isotopic distribution resulting from the presence of boron atom. Moreover, incorporation of a quaternary ammonium salt dramatically improved the efficiency of ionization in mass spectrometry. It was found that the formation of a complex with phenylboronic acid stabilizes the sugar moiety in glycated peptides, resulting in simplification of the fragmentation pattern of peptide-derived Amadori products. The obtained results suggest that derivatization of phenylboronic acid as QAS is a promising method for sensitive ESI-MS detection of carbohydrates and their conjugates formed by non-enzymatic glycation or glycosylation.

Seismic evidence of Quaternary faulting in the Benton Hills area, southeast Missouri

USGS Publications Warehouse

Palmer, J.R.; Shoemaker, M.; Hoffman, D.; Anderson, N.L.; Vaughn, J.D.; Harrison, R.W.

1997-01-01

Two reflection seismic profiles at English Hill, across the southern edge of the Benton Hills escarpment, southeast Missouri, establish that geologic structures at English Hill are of tectonic origin. The lowland area to the south of the escarpment is relatively undisturbed. The geology at English Hill is structurally complex, and reflection seismic and geologic data indicate extensive and episodic faulting of Paleozoic, Cretaceous, Tertiary, and Quaternary strata. The individual faults have near-vertical fault surfaces with maximum vertical separations on the order of 15 m. They appear to be clustered in north-northeast trending zones that essentially parallel one of the dominant Benton Hills structural trends. These observations suggest that previously mapped Quaternary faults at English Hill are deep-seated and tectonic in origin. This paper documents recent faulting at English Hill and is the first time late Quaternary, surface-rupture faulting has been recognized in the middle Mississippi River Valley region outside of the New Madrid seismic zone. This has important implications for earthquake assessment in the midcontinent.

Partitioning the Quaternary

NASA Astrophysics Data System (ADS)

Gibbard, Philip L.; Lewin, John

2016-11-01

We review the historical purposes and procedures for stratigraphical division and naming within the Quaternary, and summarize the current requirements for formal partitioning through the International Commission on Stratigraphy (ICS). A raft of new data and evidence has impacted traditional approaches: quasi-continuous records from ocean sediments and ice cores, new numerical dating techniques, and alternative macro-models, such as those provided through Sequence Stratigraphy and Earth-System Science. The practical usefulness of division remains, but there is now greater appreciation of complex Quaternary detail and the modelling of time continua, the latter also extending into the future. There are problems both of commission (what is done, but could be done better) and of omission (what gets left out) in partitioning the Quaternary. These include the challenge set by the use of unconformities as stage boundaries, how to deal with multiphase records in ocean and terrestrial sediments, what happened at the 'Early-Mid- (Middle) Pleistocene Transition', dealing with trends that cross phase boundaries, and the current controversial focus on how to subdivide the Holocene and formally define an 'Anthropocene'.

Quaternary vertebrate faunas from Sumba, Indonesia: implications for Wallacean biogeography and evolution

PubMed Central

Crees, Jennifer J.; Hansford, James; Jeffree, Timothy E.; Crumpton, Nick; Kurniawan, Iwan; Setiyabudi, Erick; Paranggarimu, Umbu; Dosseto, Anthony; van den Bergh, Gerrit D.

2017-01-01

Historical patterns of diversity, biogeography and faunal turnover remain poorly understood for Wallacea, the biologically and geologically complex island region between the Asian and Australian continental shelves. A distinctive Quaternary vertebrate fauna containing the small-bodied hominin Homo floresiensis, pygmy Stegodon proboscideans, varanids and giant murids has been described from Flores, but Quaternary faunas are poorly known from most other Lesser Sunda Islands. We report the discovery of extensive new fossil vertebrate collections from Pleistocene and Holocene deposits on Sumba, a large Wallacean island situated less than 50 km south of Flores. A fossil assemblage recovered from a Pleistocene deposit at Lewapaku in the interior highlands of Sumba, which may be close to 1 million years old, contains a series of skeletal elements of a very small Stegodon referable to S. sumbaensis, a tooth attributable to Varanus komodoensis, and fragmentary remains of unidentified giant murids. Holocene cave deposits at Mahaniwa dated to approximately 2000–3500 BP yielded extensive material of two new genera of endemic large-bodied murids, as well as fossils of an extinct frugivorous varanid. This new baseline for reconstructing Wallacean faunal histories reveals that Sumba's Quaternary vertebrate fauna, although phylogenetically distinctive, was comparable in diversity and composition to the Quaternary fauna of Flores, suggesting that similar assemblages may have characterized Quaternary terrestrial ecosystems on many or all of the larger Lesser Sunda Islands. PMID:28855367

Phase Transformation Temperatures and Solute Redistribution in a Quaternary Zirconium Alloy

NASA Astrophysics Data System (ADS)

Cochrane, C.; Daymond, M. R.

2018-05-01

This study investigates the phase stability and redistribution of solute during heating and cooling of a quaternary zirconium alloy, Excel (Zr-3.2Sn-0.8Mo-0.8Nb). Time-of-flight neutron diffraction data are analyzed using a novel Vegard's law-based approach to determine the phase fractions and location of substitutional solute atoms in situ during heating from room temperature up to 1050 °C. It is seen that this alloy exhibits direct nucleation of the β Zr phase from martensite during tempering, and stable retention of the β Zr phase to high temperatures, unlike other two-phase zirconium alloys. The transformation strains resulting from the α \\leftrightarrow β transformation are shown to have a direct impact on the development of microstructure and crystallographic texture.

Quaternary coral reef refugia preserved fish diversity.

PubMed

Pellissier, Loïc; Leprieur, Fabien; Parravicini, Valeriano; Cowman, Peter F; Kulbicki, Michel; Litsios, Glenn; Olsen, Steffen M; Wisz, Mary S; Bellwood, David R; Mouillot, David

2014-05-30

The most prominent pattern in global marine biogeography is the biodiversity peak in the Indo-Australian Archipelago. Yet the processes that underpin this pattern are still actively debated. By reconstructing global marine paleoenvironments over the past 3 million years on the basis of sediment cores, we assessed the extent to which Quaternary climate fluctuations can explain global variation in current reef fish richness. Comparing global historical coral reef habitat availability with the present-day distribution of 6316 reef fish species, we find that distance from stable coral reef habitats during historical periods of habitat loss explains 62% of the variation in fish richness, outweighing present-day environmental factors. Our results highlight the importance of habitat persistence during periods of climate change for preserving marine biodiversity. Copyright © 2014, American Association for the Advancement of Science.

First principles study on Fe based ferromagnetic quaternary Heusler alloys

NASA Astrophysics Data System (ADS)

Amudhavalli, A.; Rajeswarapalanichamy, R.; Iyakutti, K.

2017-11-01

The study of stable half-metallic ferromagnetic materials is important from various fundamental and application points of view in condensed matter Physics. Structural phase stability, electronic structure, mechanical and magnetic properties of Fe-based quaternary Heusler alloys XX‧YZ (X = Co, Ni; X‧ = Fe; Y = Ti; Z = Si, Ge, As) for three different phases namely α, β and γ phases of LiMgPdSn crystal structure have been studied by density functional theory with generalized gradient approximation formulated by Perdew, Burke and Ernzerhof (GGA-PBE) and the Hubbard formalism (GGA-PBE + U). This work aims to identify the ferromagnetic and half-metallic properties of XX‧YZ (X = Co, Ni, X‧ = Fe; Y = Ti; Z = Si, Ge, As) quaternary Heusler alloys. The predicted phase stability shows that α-phase is found to be the lowest energy phase at ambient pressure. A pressure-induced structural phase transition is observed in CoFeTiSi, CoFeTiGe, CoFeTiAs, NiFeTiSi, NiFeTiGe and NiFeTiAs at the pressures of 151.6 GPa, 33.7 GPa, 76.4 GPa, 85.3 GPa, 87.7 GPa and 96.5 GPa respectively. The electronic structure reveals that these materials are half metals at normal pressure whereas metals at high pressure. The investigation of electronic structure and magnetic properties are performed to reveal the underlying mechanism of half metallicity. The spin polarized calculations concede that these quaternary Heusler compounds may exhibit the potential candidate in spintronics application. The magnetic moments for these quaternary Heusler alloys in all the three different phases (α, β and γ) are estimated.

A closer look at the Neogene erosion and accumulation rate increase

NASA Astrophysics Data System (ADS)

Willenbring, J.; von Blanckenburg, F.

2008-12-01

Glacial erosion and Quaternary cold-stage warm-stage climate cycling have been cited as mechanisms to explain observations of increased Neogene marine sedimentation rates. Quantification of long-term glacial erosion rates from cosmogenic radionuclides from large areas mostly covered by cold-based ice during the Quaternary show very low erosion rates over several glacial cycles. In addition, isotope ratio proxies of dissolved metals in seawater, measured in chemical ocean sediments, lack clear evidence for an increase in terrigenous denudation. In particular, the stable isotope 9Be, derived from continental erosion, shows no change in its ratio to meteoric cosmogenic nuclide 10Be, derived from rain over the past 10 My. Radiogenic Pb and Nd isotopes, mainly show a change in the style of denudation from more chemical to more physical processes in the Quaternary. These data are at odds with a suggested increase in marine sedimentation rates during the late Cenozoic. In order to resolve this contradiction we have scrutinized these sedimentation rate calculations from ocean cores to identify whether they might show only apparent increases in the Neogene sections. Potential explanations are that in some cases, measured sediment thicknesses for different time intervals lack corrections for sediment compaction. Compaction of the lower portions of the cores drastically increases the apparent thickness of the more recent (Quaternary) sediment. In addition, sedimentation rates often only appear higher for recent sections in cores due to an artifact of an averaging timescale that decreases up-core. Such an averaging time scale decrease arises from better chronological resolution in recent times (Sadler et al., 1999). Cannibalization of older sediment might add to this effect. Together, these data question a clear, global-scale Quaternary climate-erosion connection that would be unique in Earth's history.

Nano-sized, quaternary titanium(IV) metal-organic frameworks with multidentate ligands.

PubMed

Baranwal, Balram Prasad; Singh, Alok Kumar

2010-12-01

Some mononuclear nano-sized, quaternary titanium(IV) complexes having the general formula [Ti(acac)(OOCR)2(SB)] (where Hacac=acetylacetone, R=C15H31 or C17H35, HSB=Schiff bases) have been synthesized using different multidentate ligands. These were characterized by elemental analyses, molecular weight determinations and spectral (FTIR, 1H NMR and powder XRD) studies. Conductance measurement indicated their non-conducting nature which may behave like insulators. Structural parameters like the values of limiting indices h, k, l, cell constants a, b, c, angles α, β, γ and particle size are calculated from powder XRD data for complex 1 which indicated nano-sized triclinic system in them. Bidentate chelating nature of acetylacetone, carboxylate and Schiff base anions in the complexes was established by their infrared spectra. Molecular weight determinations confirmed mononuclear nature of the complexes. On the basis of physico-chemical studies, coordination number 8 was assigned for titanium(IV) in the complexes. Transmission electron microscopy (TEM) and the selected area electron diffraction (SAED) studies indicated spherical particles with poor crystallinity. Copyright © 2010 Elsevier B.V. All rights reserved.

Black phosphorus-assisted laser desorption ionization mass spectrometry for the determination of low-molecular-weight compounds in biofluids.

PubMed

He, Xiao-Mei; Ding, Jun; Yu, Lei; Hussain, Dilshad; Feng, Yu-Qi

2016-09-01

Quantitative analysis of small molecules by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has been a challenging task due to matrix-derived interferences in low m/z region and poor reproducibility of MS signal response. In this study, we developed an approach by applying black phosphorus (BP) as a matrix-assisted laser desorption ionization (MALDI) matrix for the quantitative analysis of small molecules for the first time. Black phosphorus-assisted laser desorption/ionization mass spectrometry (BP/ALDI-MS) showed clear background and exhibited superior detection sensitivity toward quaternary ammonium compounds compared to carbon-based materials. By combining stable isotope labeling (SIL) strategy with BP/ALDI-MS (SIL-BP/ALDI-MS), a variety of analytes labeled with quaternary ammonium group were sensitively detected. Moreover, the isotope-labeled forms of analytes also served as internal standards, which broadened the analyte coverage of BP/ALDI-MS and improved the reproducibility of MS signals. Based on these advantages, a reliable method for quantitative analysis of aldehydes from complex biological samples (saliva, urine, and serum) was successfully established. Good linearities were obtained for five aldehydes in the range of 0.1-20.0 μM with correlation coefficients (R (2)) larger than 0.9928. The LODs were found to be 20 to 100 nM. Reproducibility of the method was obtained with intra-day and inter-day relative standard deviations (RSDs) less than 10.4 %, and the recoveries in saliva samples ranged from 91.4 to 117.1 %. Taken together, the proposed SIL-BP/ALDI-MS strategy has proved to be a reliable tool for quantitative analysis of aldehydes from complex samples. Graphical Abstract An approach for the determination of small molecules was developed by using black phosphorus (BP) as a matrix-assisted laser desorption ionization (MALDI) matrix.

Evolving in the highlands: the case of the Neotropical Lerma live-bearing Poeciliopsis infans (Woolman, 1894) (Cyprinodontiformes: Poeciliidae) in Central Mexico.

PubMed

Beltrán-López, Rosa Gabriela; Domínguez-Domínguez, Omar; Pérez-Rodríguez, Rodolfo; Piller, Kyle; Doadrio, Ignacio

2018-04-20

Volcanic and tectonic activities in conjunction with Quaternary climate are the main events that shaped the geographical distribution of genetic variation of many lineages. Poeciliopsis infans is the only poeciliid species that was able to colonize the temperate highlands of central Mexico. We inferred the phylogenetic relationships, biogeographic history, and historical demography in the widespread Neotropical species P. infans and correlated this with geological events and the Quaternary glacial-interglacial climate in the highlands of central Mexico, using the mitochondrial genes Cytochrome b and Cytochrome oxidase I and two nuclear loci, Rhodopsin and ribosomal protein S7. Populations of P. infans were recovered in two well-differentiated clades. The maximum genetic distances between the two clades were 3.3% for cytb, and 1.9% for coxI. The divergence of the two clades occurred ca. 2.83 Myr. Ancestral area reconstruction revealed a complex biogeographical history for P. infans. The Bayesian Skyline Plot showed a demographic decline, although more visible for clade A, and more recently showed a population expansion in the last 0.025 Myr. Finally, the habitat suitability modelling showed that during the LIG, clade B had more areas with high probabilities of presence in comparison to clade A, whereas for the LGM, clade A showed more areas with high probabilities of presence in comparisons to clade B. Poeciliopsis infans has had a complex evolutionary and biogeographic history, which, as in other co-distributed freshwater fishes, seems to be linked to the volcanic and tectonic activities during the Pliocene or early Pleistocene. Populations of P. infans distributed in lowlands showed a higher level of genetic diversity than populations distributed in highlands, which could be linked to more stable and higher temperatures in lowland areas. The fluctuations in population size through time are in agreement with the continuous fluctuations of the climate of central Mexico.

Development of an efficient E. coli expression and purification system for a catalytically active, human Cullin3-RINGBox1 protein complex and elucidation of its quaternary structure with Keap1

DOE Office of Scientific and Technical Information (OSTI.GOV)

Small, Evan; Eggler, Aimee; Mesecar, Andrew D., E-mail: amesecar@purdue.edu

2010-10-01

Research highlights: {yields} A novel expression strategy was used to purify Cul3-Rbx1 from E. coli. {yields} The Cul3-Rbx1 complex is fully active and catalyzes ubiquitination of Nrf2 in vitro. {yields} Cul3, Rbx1, and Keap1 form a complex with unique stoichiometry of 1:1:2. -- Abstract: The Cullin3-based E3 ubiquitin ligase complex is thought to play an important role in the cellular response to oxidative stress and xenobiotic assault. While limited biochemical studies of the ligase's role in these complex signaling pathways are beginning to emerge, structural studies are lagging far behind due to the inability to acquire sufficient quantities of full-length,more » highly pure and active Cullin3. Here we describe the design and construction of an optimized expression and purification system for the full-length, human Cullin3-RINGBox 1 (Rbx1) protein complex from Escherichia coli. The dual-expression system is comprised of codon-optimized Cullin3 and Rbx1 genes co-expressed from a single pET-Duet-1 plasmid. Rapid purification of the Cullin3-Rbx1 complex is achieved in two steps via an affinity column followed by size-exclusion chromatography. Approximately 15 mg of highly pure and active Cullin3-Rbx1 protein from 1 L of E. coli culture can be achieved. Analysis of the quaternary structure of the Cullin3-Rbx1 and Cullin3-Rbx1-Keap1 complexes by size-exclusion chromatography and analytical ultracentrifugation indicates a 1:1 stoichiometry for the Cullin3-Rbx1 complex (MW = 111 kDa), and a 1:1:2 stoichiometry for the Cullin3-Rbx1-Keap1 complex (MW = 280 kDa). This latter complex has a novel quaternary structural organization for cullin E3 ligases, and it is fully active based on an in vitro Cullin3-Rbx1-Keap1-Nrf2 ubiquitination activity assay that was developed and optimized in this study.« less

The role of Quaternary environmental change in plant macroevolution: the exception or the rule?

PubMed Central

Willis, Katherine J; Niklas, Karl J

2004-01-01

The Quaternary has been described as an important time for genetic diversification and speciation. This is based on the premise that Quaternary climatic conditions fostered the isolation of populations and, in some instances, allopatric speciation. However, the 'Quaternary Ice-Age speciation model' rests on two key assumptions: (i) that biotic responses to climate change during the Quaternary were significantly different from those of other periods in Earth's history; and (ii) that the mechanisms of isolation during the Quaternary were sufficient in time and space for genetic diversification to foster speciation. These assumptions are addressed by examining the plant fossil record for the Quaternary (in detail) and for the past 410 Myr, which encompasses previous intervals of icehouse Earth. Our examination of the Quaternary record indicates that floristic responses to climate changes during the past 1.8 Myr were complex and that a distinction has to be made between those plants that were able to withstand the extremes of glacial conditions and those that could not. Generation times are also important as are different growth forms (e.g. herbaceous annuals and arborescent perennials), resulting in different responses in terms of genetic divergence rates during isolation. Because of these variations in the duration of isolation of populations and genomic diversification rates, no canonical statement about the predominant floristic response to climatic changes during the Quaternary (i.e. elevated rates of speciation or extinction, or stasis) is currently possible. This is especially true because of a sampling bias in terms of the fossil record of tree species over that of species with non-arborescent growth forms. Nevertheless, based on the available information, it appears that the dominant response of arborescent species during the Quaternary was extinction rather than speciation or stasis. By contrast, our examination of the fossil record of vascular plants for the past 410 Myr indicates that speciation rates often increased during long intervals of icehouse Earth (spanning up to 50 Myr). Therefore, longer periods of icehouse Earth than those occurring during the Quaternary may have isolated plant populations for sufficiently long periods of time to foster genomic diversification and allopatric speciation. Our results highlight the need for more detailed study of the fossil record in terms of finer temporal and spatial resolution than is currently available to examine the significance of intervals of icehouse Earth. It is equally clear that additional and detailed molecular studies of extant populations of Quaternary species are required in order to determine the extent to which these 'relic' species have genomically diversified across their current populations. PMID:15101573

Reconstruction of the Palaeo-environment of the Alluvial Deposits in the Eastern Free State, South Africa

NASA Astrophysics Data System (ADS)

Evans, M. Y.

2009-04-01

Small alluvial fan systems have formed off the hillslopes of the remnant Karoo koppies at Heelbo in the Eastern Free State, South Africa. The landform geometry is a result of complex relationships between climate, lithology, structure and vegetation. This research area, which includes a large mammal mass death site, potentially contains a wealth of palaeo-environmental and specifically palaeoclimatic information. Palaeo-environmental information and proxy records on past climates in southern Africa has traditionally been obtained from a variety of techniques including stable isotope analysis of speleothems, pollen , faunal analyses at archeological sites, animal remains and crater-lake sediments (see references below). However, little information exists in the scientific literature on the use of palaeosols for defining the depositional palaeoenvironments in southern Africa. The aim of this research is to attempt to address the lack of palaeo-environmental information by extracting palaeoclimatic information from the sedimentary processes and the palaeosols at the Heelbo farm that have been extensively exposed through gullying. The sedimentary fans in the area have experienced climatically controlled histories of erosion, sedimentation and pedogenesis. Extreme sedimentation is assumed to have occurred during relatively arid climatic intervals, when decreased vegetation cover provided little surface protection. In contrast pedogenesis occurs during humid intervals when vegetation cover is restored, the land stabilizes and the uppermost gravely sands weather to form soils. A combined approach of both radiocarbon- and luminescence -dating may provide a detailed chronology of these successive hillslope events in order to relate hillslope instability to climatic forcing factors. Preliminary results indicate that at least 3 depositional events are recorded within the large mammal mass death site, which have been confirmed by the radiocarbon dates of 3,610 ±110 in the top section and 4,610 ±30 at the bottom section. References: Klein, R.G., Cruz-Uribe, K., Beaumont, P.B., 1991. Environmental, ecological, and paleoanthropological implications of the Late Pleistocene mammalian fauna from Equus Cave, northern Cape Province, South Africa. Quaternary Research. 36, 94 119. Lee-Thorp, J.A., Beaumont. PB., 1995. Vegetation and seasonality shift during the late Quaternary deduced from 13C/12C ratios of grazers at Equus Cave, South Africa. Quaternary Research. 43, 426 432. Partridge, T.C., Demenocal, P.B., Lorentz, S.A., Paiker, M.J., Vogel, J.C., 1997: Orbital forcing of climate over South Africa: A 200,000-year rainfall record from Pretoria Saltpan, Quaternary Science Reviews, 16, 1125-1133. Partridge, T.C., Kerr, S.J., Metcalfe, S.E., Scott, L., Vogel, J.C., 1993: The Pretoria Saltpan: A 200,000 year South African lacustrine sequence. Palaeogeography, Palaeoclimatology, Palaeoecology, 101, 317-337. Scott, L. and Thackeray, J.F., 1987: Multivariate analysis of late Pleistocene and Holocene pollen spectra from Wonderkrater, Transvaal, South Africa. South African Journal of Science, 83, 93- 98. Talma, A.S. and Vogel, J.C., 1992: Late Quaternary palaeotemperatures derived from a speleotherm from Cango Caves, Cape Province, South Africa, Quaternary Research, 37, 203-213. Vogel, J.C., 1983. Isotopic evidence for past climates and vegetation of southern Africa. Bothalia 14, 391-394.

Cellular Membrane Phospholipids Act as a Depository for Quaternary Amine containing Drugs thus competing with the Acetylcholine / Nicotinic Receptor

PubMed Central

Barbacci, Damon; Jackson, Shelley N.; Muller, Ludovic; Egan, Thomas; Lewis, Ernest K.; Schultz, J. Albert; Woods, Amina S.

2014-01-01

We previously demonstrated that ammonium- or guanidinium- phosphate interactions are key to forming non-covalent complexes (NCXs) through salt bridge formation with G-protein coupled receptors (GPCR), which are immersed in the cell membrane's lipids. The present work highlights MALDI ion mobility coupled to orthogonal time-of-flight mass spectrometry (MALDI IM oTOF MS) as a method to determine qualitative and relative quantitative affinity of drugs to form NCXs with targeted GPCRs' epitopes in a model system using, bis-quaternary amine based drugs, α- and β- subunit epitopes of the nicotinic acetylcholine receptor' (nAChR) and phospholipids. Bis-quaternary amines proved to have a strong affinity for all nAChR epitopes and negatively charged phospholipids, even in the presence of the physiological neurotransmitter acetylcholine. Ion mobility baseline separated isobaric phosphatidyl ethanolamine and a matrix cluster, providing an accurate estimate for phospholipid counts. Overall this technique is a powerful method for screening drugs' interactions with targeted lipids and protein respectively containing quaternary amines and guanidinium moieties. PMID:22506649

Is Quaternary geology ready for the future?

NASA Astrophysics Data System (ADS)

Ritter, Dale F.

1996-07-01

Armed with a better understanding of process and an array of developing dating techniques, Quaternary geology is poised to achieve greater recognition in the general scientific community. This recognition however, will require some thought adjustment. Quaternary geologists will have to convince government, industry and a variety of scientific groups that they possess unique training and expertise that is needed as part of the thrust to fully understand and/or resolve major scientific problems. Therefore, future research and education efforts should not focus on developing a rigidly defined identity within geoscience, but instead should seek ways to be integrated with interdisciplinary teams that will investigate complex environmental and climate change problems. Such a scenaria creates and enermous dilemma for Quaternary geologists because they will derive greater intellectual stimulation from scientists working in discplines other than geology, and their scientific collaboratiors will most likely not be their academic colleagues. This outward expansion of our scientific network will require the development of interdsciplinary research collaboration and/or degree-granting programs at the graduate level. To accomplish such goals, universities must resist "turf protection", and funding agencies muts become more efficient at facilitating interdisciplinary research.

Enantioselective addition of nitromethane to 2-acylpyridine N-oxides. Expanding the generation of quaternary stereocenters with the Henry reaction.

PubMed

Holmquist, Melireth; Blay, Gonzalo; Muñoz, M Carmen; Pedro, José R

2014-02-21

The direct asymmetric Henry reaction with prochiral ketones, leading to tertiary nitroaldols, is an elusive reaction so far limited to a reduced number of reactive substrates such as trifluoromethyl ketones or α-keto carbonyl compounds. Expanding the scope of this important reaction, the direct asymmetric addition of nitromethane to 2-acylpyridine N-oxides catalyzed by a BOX-Cu(II) complex to give the corresponding pyridine-derived tertiary nitroaldols having a quaternary stereogenic center with variable yields and good enantioselectivity, is described.

Mid-infrared multiple quantum well lasers using digitally-grown aluminum indium arsenic antimonide barriers and strained indium arsenic antimonide wells

NASA Astrophysics Data System (ADS)

Vaughn, Leslie G.

2006-04-01

AlxIn(1-x)AsySb(1-y) quaternary alloys have been used in Type I midwave infrared (MWIR) laser structures as barrier materials with InAs and InAsSb quantum wells. However, growth of these alloys has limited the application because of a large miscibility gap. In this research, quaternary films with compositions well into the miscibility gap (0 ≤ x ≤ 0.50) have been grown for the first time by molecular beam epitaxy (MBE) using a digital alloy technique. These films, lattice-matched to GaSb, have been characterized using double crystal X-ray diffraction (DCXRD), transmission electron microscopy (TEM), and photoluminescence (PL). Results indicate uniform, single-phase, and highly crystalline films. Using PL data, the dependence of the quaternary bandgap on composition has been studied and fit to various theoretical models. Combining the quaternary bandgap equation with strain and quantum size effects, the wavelengths for strained InAsSb wells in AlInAsSb quaternary barriers are predicted and compared to measured values generated from PL experiments. The reasonable agreement of these experimental results with the theoretical model supports the assertion that the AlInAsSb/InAsSb material system is Type I and emits in the target wavelength range of 3.3-4.2 mum. PL spectra of AlInAsSb/InAsSb multiple quantum wells exhibit a substantial increase in intensity with increasing quaternary aluminum content. This is presumably due to increasing valence band offset and, therefore, to better hole confinement. A laser with this active region has been fabricated and tested. Under pulsed optical pumping conditions at 50K, the laser emitted light at ˜3.93 mum. Further work has been done using the digital alloy technique to add gallium to the quaternary alloy to produce an AlGaInAsSb quinary alloy lattice-matched to GaSb. This material is of specific interest for mid-infrared lasers because by adding the fifth element, gallium, the range of material properties is extended. There is some indication from PL testing that the addition of the fifth element may contribute to Auger recombination suppression and may lead to higher operating temperatures. DCXRD and TEM of these quinary alloys give results similar to the quaternary alloys. The stable, single-phase growth of these quinary alloys shows promise for improving the performance of MWIR lasers.

Reversible stalling of transcription elongation complexes by high pressure.

PubMed

Erijman, L; Clegg, R M

1998-07-01

We have investigated the effect of high hydrostatic pressure on the stability of RNA polymerase molecules during transcription. RNA polymerase molecules participating in stalled or active ternary transcribing complexes do not dissociate from the template DNA and nascent RNA at pressures up to 180 MPa. A lower limit for the free energy of stabilization of an elongating ternary complex relative to the quaternary structure of the free RNAP molecules is estimated to be 20 kcal/mol. The rate of elongation decreases at high pressure; transcription completely halts at sufficiently high pressure. The overall rate of elongation has an apparent activation volume (DeltaVdouble dagger) of 55-65 ml . mol-1 (at 35 degrees C). The pressure-stalled transcripts are stable and resume elongation at the prepressure rate upon decompression. The efficiency of termination decreases at the rho-independent terminator tR2 after the transcription reaction has been exposed to high pressure. This suggests that high pressure modifies the ternary complex such that termination is affected in a manner different from that of elongation. The solvent and temperature dependence of the pressure-induced inhibition show evidence for major conformational changes in the core polymerase enzyme during RNA synthesis. It is proposed that the inhibition of the elongation phase of the transcription reaction at elevated pressures is related to a reduction of the partial specific volume of the RNA polymerase molecule; under high pressure, the RNA polymerase molecule does not have the necessary structural flexibility required for the protein to translocate.

Concise Synthesis of (-)-Hodgkinsine, (-)-Calycosidine, (-)-Hodgkinsine B, (-)-Quadrigemine C, and (-)-Psycholeine via Convergent and Directed Modular Assembly of Cyclotryptamines.

PubMed

Lindovska, Petra; Movassaghi, Mohammad

2017-12-06

The enantioselective total synthesis of (-)-hodgkinsine, (-)-calycosidine, (-)-hodgkinsine B, (-)-quadrigemine C, and (-)-psycholeine through a diazene-directed assembly of cyclotryptamine fragments is described. Our synthetic strategy enables multiple and directed assembly of intact cyclotryptamine subunits for convergent synthesis of highly complex bis- and tris-diazene intermediates. Photoextrusion of dinitrogen from these intermediates enables completely stereoselective formation of all C3a-C3a' and C3a-C7' carbon-carbon bonds and all the associated quaternary stereogenic centers. In a representative example, photoextrusion of three dinitrogen molecules from an advanced intermediate in a single-step led to completely controlled introduction of four quaternary stereogenic centers and guided the assembly of four cyclotryptamine monomers en route to (-)-quadrigemine C. The synthesis of these complex diazenes was made possible through a new methodology for synthesis of aryl-alkyl diazenes using electronically attenuated hydrazine-nucleophiles for a silver-promoted addition to C3a-bromocyclotryptamines. The application of Rh- and Ir-catalyzed C-H amination reactions in complex settings were used to gain rapid access to C3a- and C7-functionalized cyclotryptamine monomers, respectively, used for diazene synthesis. This convergent and modular assembly of intact cyclotryptamines offers the first solution to access these alkaloids through completely stereoselective union of monomers at challenging linkages and the associated quaternary stereocenters as illustrated in our synthesis of five members of the oligocyclotryptamine family of alkaloids.

Aliphatic long chain quaternary ammonium compounds analysis by ion-pair chromatography coupled with suppressed conductivity and UV detection in lysing reagents for blood cell analysers.

PubMed

Giovannelli, D; Abballe, F

2005-08-26

A method has been developed which allows simultaneous determination of three linear alkyl trimethylammonium salts. Dodecyltrimethylammonium chloride, tetradecyltrimethylammonium bromide and hexadecyltrimethylammonium chloride are widely used as main active ingredients of lysing reagents for blood cell analyzers which perform white blood cells differential determination into two or more sub-populations by impedance analysis. The ion-pair on styrene-divinyl benzene chromatographic phase looks like a suitable, reliable and long term stable tool for separation of such quaternary compounds. The detection based on suppressed conductivity was chosen because of the lack of significance chromophores. A micromembrane suppressor device compatible with high solvent concentration (up to 80%) was used in order to minimize the conductivity background before the detection. In the present work we show how the chemical post column derivatization makes the alkyl chain detectable also by UV direct detection at 210 nm.

Nanosecond Absorption Spectroscopy of Hemoglobin: Elementary Processes in Kinetic Cooperativity

NASA Astrophysics Data System (ADS)

Hofrichter, James; Sommer, Joseph H.; Henry, Eric R.; Eaton, William A.

1983-04-01

A nanosecond absorption spectrometer has been used to measure the optical spectra of hemoglobin between 3 ns and 100 ms after photolysis of the CO complex. The data from a single experiment comprise a surface, defined by the time-ordered set of 50-100 spectra. Singular value decomposition is used to represent the observed spectra in terms of a minimal set of basis spectra and the time course of their amplitudes. Both CO rebinding and conformational changes are found to be multiphasic. Prior to the quaternary structural change, two relaxations are observed that are assigned to geminate recombination followed by a tertiary structural change. These relaxations are interpreted in terms of a kinetic model that points out their potential role in kinetic cooperativity. The rapid escape of CO from the heme pocket compared with the rate of rebinding observed for both R and T quaternary states shows that the quaternary structure controls the overall dissociation rate by changing the rate at which the Fe--CO bond is broken. A comparable description of the control of the overall association rates must await a more complete experimental description of the kinetics of the quaternary T state.

Two-dimensional NMR spectroscopy reveals cation-triggered backbone degradation in polysulfone-based anion exchange membranes

PubMed Central

Arges, Christopher G.; Ramani, Vijay

2013-01-01

Anion exchange membranes (AEMs) find widespread applications as an electrolyte and/or electrode binder in fuel cells, electrodialysis stacks, flow and metal-air batteries, and electrolyzers. AEMs exhibit poor stability in alkaline media; their degradation is induced by the hydroxide ion, a potent nucleophile. We have used 2D NMR techniques to investigate polymer backbone stability (as opposed to cation stability) of the AEM in alkaline media. We report the mechanism behind a peculiar, often-observed phenomenon, wherein a demonstrably stable polysulfone backbone degrades rapidly in alkaline solutions upon derivatization with alkaline stable fixed cation groups. Using COSY and heteronuclear multiple quantum correlation spectroscopy (2D NMR), we unequivocally demonstrate that the added cation group triggers degradation of the polymer backbone in alkaline via quaternary carbon hydrolysis and ether hydrolysis, leading to rapid failure. This finding challenges the existing perception that having a stable cation moiety is sufficient to yield a stable AEM and emphasizes the importance of the often ignored issue of backbone stability. PMID:23335629

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiong, J.-P.; Stehle, T.; Zhang, R.

The structural basis for the divalent cation-dependent binding of heterodimeric alpha beta integrins to their ligands, which contain the prototypical Arg-Gly-Asp sequence, is unknown. Interaction with ligands triggers tertiary and quaternary structural rearrangements in integrins that are needed for cell signaling. Here we report the crystal structure of the extracellular segment of integrin alpha Vbeta 3 in complex with a cyclic peptide presenting the Arg-Gly-Asp sequence. The ligand binds at the major interface between the alpha V and beta 3 subunits and makes extensive contacts with both. Both tertiary and quaternary changes are observed in the presence of ligand. Themore » tertiary rearrangements take place in beta A, the ligand-binding domain of beta 3; in the complex, beta A acquires two cations, one of which contacts the ligand Asp directly and the other stabilizes the ligand-binding surface. Ligand binding induces small changes in the orientation of alpha V relative to beta 3.« less

A Quaternary Mechanism Enables the Complex Biological Functions of Octameric Human UDP-glucose Pyrophosphorylase, a Key Enzyme in Cell Metabolism

PubMed Central

Führing, Jana Indra; Cramer, Johannes Thomas; Schneider, Julia; Baruch, Petra; Gerardy-Schahn, Rita; Fedorov, Roman

2015-01-01

In mammals, UDP-glucose pyrophosphorylase (UGP) is the only enzyme capable of activating glucose-1-phosphate (Glc-1-P) to UDP-glucose (UDP-Glc), a metabolite located at the intersection of virtually all metabolic pathways in the mammalian cell. Despite the essential role of its product, the molecular basis of UGP function is poorly understood. Here we report the crystal structure of human UGP in complex with its product UDP-Glc. Beyond providing first insight into the active site architecture, we describe the substrate binding mode and intermolecular interactions in the octameric enzyme that are crucial to its activity. Importantly, the quaternary mechanism identified for human UGP in this study may be common for oligomeric sugar-activating nucleotidyltransferases. Elucidating such mechanisms is essential for understanding nucleotide sugar metabolism and opens the perspective for the development of drugs that specifically inhibit simpler organized nucleotidyltransferases in pathogens. PMID:25860585

Cooperative Subunit Refolding of a Light-Harvesting Protein through a Self-Chaperone Mechanism.

PubMed

Laos, Alistair J; Dean, Jacob C; Toa, Zi S D; Wilk, Krystyna E; Scholes, Gregory D; Curmi, Paul M G; Thordarson, Pall

2017-07-10

The fold of a protein is encoded by its amino acid sequence, but how complex multimeric proteins fold and assemble into functional quaternary structures remains unclear. Here we show that two structurally different phycobiliproteins refold and reassemble in a cooperative manner from their unfolded polypeptide subunits, without biological chaperones. Refolding was confirmed by ultrafast broadband transient absorption and two-dimensional electronic spectroscopy to probe internal chromophores as a marker of quaternary structure. Our results demonstrate a cooperative, self-chaperone refolding mechanism, whereby the β-subunits independently refold, thereby templating the folding of the α-subunits, which then chaperone the assembly of the native complex, quantitatively returning all coherences. Our results indicate that subunit self-chaperoning is a robust mechanism for heteromeric protein folding and assembly that could also be applied in self-assembled synthetic hierarchical systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Minimization of material inter-diffusion for thermally stable quaternary-capped InAs quantum dot via strain modification

NASA Astrophysics Data System (ADS)

Ghadi, Hemant; Sehara, Navneet; Murkute, Punam; Chakrabarti, Subhananda

2017-05-01

In this study, a theoretical model is developed for investigating the effect of thermal annealing on a single-layer quaternary-capped (In0.21Al0.21Ga0.58As) InAs quantum dot heterostructure (sample A) and compared to a conventional GaAs-capped sample (sample B). Strain, an interfacial property, aids in dot formation; however, it hinders interdiffusion (up to 650 °C), rendering thermal stability to heterostructures. Three diffusing species In/Al/Ga intermix because of the concentration gradient and temperature variation, which is modeled by Fick's law of diffusion. Ground-state energy for both carriers (electron and holes) is calculated by the Schrodinger equation at different annealing temperatures, incorporating strain computed by the concentration-dependent model. Change in activation energy due to strain decreases particle movement, thereby resulting in thermally stable structures at low annealing temperatures. At low temperature, the conduction band near the dot edge slightly decreases, attributed to the comparatively high strain. Calculated results are consistent with the experimental blue-shift i.e. towards lower wavelength of photoluminescence peak on the same sample with increasing annealing temperatures. Cross-sectional transmission microscopy (TEM) images substantiate the existence of dot till 800 °C for sample (A). With increasing annealing temperature, interdiffusion and dot sublimation are observed in XTEM images of samples A and B. Strain calculated from high-resolution X-ray diffraction (HRXRD) peaks and its decline with increasing temperature are in agreement with that calculated by the model. For highlighting the benefits of quaternary capping, InAlGaAs capping is theoretically and experimentally compared to GaAs capping. Concentration-dependent strain energy is calculated at every point and is further used for computing material interdiffusion, band profiles, and photoluminescence peak wavelength, which can provide better insights into strain energy behavior with temperature and help in the better understanding of thermal annealing.

Oxygen Isotopes Archived in Subfossil Chironomids: Advancing a Promising Proxy for Lake Water Isotopes

NASA Astrophysics Data System (ADS)

Lasher, G. E.; Axford, Y.; Blair, N. E.

2017-12-01

Oxygen isotopes measured in subfossil chironomid head capsules (aquatic insect remains) in lake sediments are beginning to offer paleoclimate insights from previously under-studied areas of the world. Since the first published pilot study demonstrated the potential of chironomid δ18O to record lake water δ18O (Wooller et al., 2004), subsequent work has refined our understanding of this proxy: confirming via lab cultures that growth water controls head capsule δ18O (Wang et al., 2009), refining laboratory pretreatment protocols, and further validating the method by demonstrating strong agreement between carbonate and chironomid-derived paleo-isotope records (Verbruggen et al., 2009, 2010, 2011). However, outstanding questions remain, including the seasonality of chironomid growth, possible species-dependent vital effects, and diagenetic effects on the protein-chitin complex that comprise chironomid cuticles. To address some of these questions, we summarize available data from paired modern chironomid-lake water δ18O values from around the world and discuss climatic and environmental factors affecting chironomid isotopic signatures. We also present new data on the resistance of these subfossils to diagenesis and degradation throughout the late Quaternary using Fourier Transform Infrared Spectroscopy (FT-IR) and Pyrolysis Gas Chromatography Mass Spectrometry (Py-GC/MS) of chironomid remains up to >100,000 years old. As chironomids are nearly ubiquitous in lakes globally and, we argue, molecularly stable through glacial and interglacial cycles, this proxy has the potential to greatly expand the spatial and temporal resolution of Quaternary paleo-isotopes and thus climate records. In addition to reviewing and presenting new methodological advances, we also present applications of chironomid δ18O from millennial- to centennial-scale Holocene Greenland lake records.

Quaternary ammonium oxidative demethylation: X-ray crystallographic, resonance Raman, and UV-visible spectroscopic analysis of a Rieske-type demethylase.

PubMed

Daughtry, Kelly D; Xiao, Youli; Stoner-Ma, Deborah; Cho, Eunsun; Orville, Allen M; Liu, Pinghua; Allen, Karen N

2012-02-08

Herein, the structure resulting from in situ turnover in a chemically challenging quaternary ammonium oxidative demethylation reaction was captured via crystallographic analysis and analyzed via single-crystal spectroscopy. Crystal structures were determined for the Rieske-type monooxygenase, stachydrine demethylase, in the unliganded state (at 1.6 Å resolution) and in the product complex (at 2.2 Å resolution). The ligand complex was obtained from enzyme aerobically cocrystallized with the substrate stachydrine (N,N-dimethylproline). The ligand electron density in the complex was interpreted as proline, generated within the active site at 100 K by the absorption of X-ray photon energy and two consecutive demethylation cycles. The oxidation state of the Rieske iron-sulfur cluster was characterized by UV-visible spectroscopy throughout X-ray data collection in conjunction with resonance Raman spectra collected before and after diffraction data. Shifts in the absorption band wavelength and intensity as a function of absorbed X-ray dose demonstrated that the Rieske center was reduced by solvated electrons generated by X-ray photons; the kinetics of the reduction process differed dramatically for the liganded complex compared to unliganded demethylase, which may correspond to the observed turnover in the crystal.

Numerical dating of a Late Quaternary spit-shoreline complex at the northern end of Silver Lake playa, Mojave Desert, California: A comparison of the applicability of radiocarbon, luminescence, terrestrial cosmogenic nuclide, electron spin resonance, U-series and amino acid racemization methods

USGS Publications Warehouse

Owen, L.A.; Bright, Jordon; Finkel, R.C.; Jaiswal, M.K.; Kaufman, D.S.; Mahan, S.; Radtke, U.; Schneider, J.S.; Sharp, W.; Singhvi, A.K.; Warren, C.N.

2007-01-01

A Late Quaternary spit-shoreline complex on the northern shore of Pleistocene Lake Mojave of southeastern California, USA was studied with the goal of comparing accelerator mass spectrometry (AMS) radiocarbon, luminescence, electron spin resonance (ESR), terrestrial cosmogenic radionuclide (TCN) surface exposure, amino acid racemization (AAR) and U-series dating methods. The pattern of ages obtained by the different methods illustrates the complexity of processes acting in the lakeshore environment and highlights the utility of a multi-method approach. TCN surface exposure ages (mostly ???20-30 ka) record the initial erosion of shoreline benches, whereas radiocarbon ages on shells (determined in this and previous studies) within the spit, supported by AAR data, record its construction at fluctuating lake levels from ???16 to 10 ka. Luminescence ages on spit sediment (???6-7 ka) and ESR ages on spit shells (???4 ka) are anomalously young relative to radiocarbon ages of shells within the same deposits. The significance of the surprisingly young luminescence ages is not clear. The younger ESR ages could be a consequence of post-mortem enrichment of U in the shells. High concentrations of detrital thorium in tufa coating spit gravels inhibited the use of single-sample U-series dating. Detailed comparisons such as this provide one of the few means of assessing the accuracy of Quaternary dating techniques. More such comparisons are needed. ?? 2007 Elsevier Ltd and INQUA.

Geophysical techniques applied to urban planning in complex near surface environments. Examples of Zaragoza, NE Spain

NASA Astrophysics Data System (ADS)

Pueyo-Anchuela, Ó.; Casas-Sainz, A. M.; Soriano, M. A.; Pocoví-Juan, A.

Complex geological shallow subsurface environments represent an important handicap in urban and building projects. The geological features of the Central Ebro Basin, with sharp lateral changes in Quaternary deposits, alluvial karst phenomena and anthropic activity can preclude the characterization of future urban areas only from isolated geomechanical tests or from non-correctly dimensioned geophysical techniques. This complexity is here analyzed in two different test fields, (i) one of them linked to flat-bottomed valleys with irregular distribution of Quaternary deposits related to sharp lateral facies changes and irregular preconsolidated substratum position and (ii) a second one with similar complexities in the alluvial deposits and karst activity linked to solution of the underlying evaporite substratum. The results show that different geophysical techniques allow for similar geological models to be obtained in the first case (flat-bottomed valleys), whereas only the application of several geophysical techniques can permit to correctly evaluate the geological model complexities in the second case (alluvial karst). In this second case, the geological and superficial information permit to refine the sensitivity of the applied geophysical techniques to different indicators of karst activity. In both cases 3D models are needed to correctly distinguish alluvial lateral sedimentary changes from superimposed karstic activity.

Reconstruction of western Pacific and Atlantic Ocean Surface Stability during the Miocene to Quaternary based on nannofossil assemblages

NASA Astrophysics Data System (ADS)

Sato, T.; Pratiwi, S. D.; Effendi, R.

2015-12-01

We studied in detail the calcareous nannofossil assemblages of the middle Miocene to Quaternary sequences of ODP Sites 782, 1005, 1006, and 1007 located in western Pacific Ocean and Bahama Bank of Caribbean Sea. Site 1007, 1005, 1006 are situated in the cross section of Bahama Bank from near shore to offshore site. Discoaster species, which is interpreted as lower photic zone species, is increasing the relative number towards the offshore site. This means that the abundant occurrence of Discoaster specimens indicates the well stratified surface water conditions. We also correlated the variability of maximum size of "Reticulofenestra" specimens between Sites 782, 1005, 1006, and 1007 (Fig ). The variability of the maximum size of Reticulofenestra recorded in site 782 is positive correlation with those in Site 1006, 1005, and 1007. As the occurrence of large size Reticulofenestra indicate the oligotrophic and stable sea surface condition, the drastic decreasing of maximum size of Reticulofenestra fond in 2.75Ma, 3.6Ma, 5.4Ma, 9Ma and 13Ma, indicates the collapse of stable and low nutrient sea surface conditions at these ages in both Caribbean Sea and western Pacific Ocean. The events found in the sequences are correlated to closure of Central American seaway, Messinian salinity crisis, intensify the Asian Monsoon, and closure of Indonesian Sea way.

Phase stability, magnetic, electronic, half-metallic and mechanical properties of a new equiatomic quaternary Heusler compound ZrRhTiIn: A first-principles investigation

NASA Astrophysics Data System (ADS)

Wang, Jia-Xing; Chen, Z. B.; Gao, Y. C.

2018-05-01

In this manuscript, we have studied the electronic, magnetic, half-metallic and mechanical properties of a new Zr-based equiatomic quaternary Heusler (EQH) compound, ZrRhTiIn using first-principles calculations. The generalized gradient approximation (GGA) calculation results imply that at its equilibrium lattice constant of 6.70 Å, ZrRhTiIn is a half-metallic material (HMM) with a considerable band gap (Ebg) of 0.530 eV and a spin-filter/half-metallic band-gap (EHM) of 0.080 eV in the minority-spin channel. For ZrRhTiIn, the formation energy of -2.738 eV and the cohesive energy of 21.38 eV indicate that it is a thermodynamically stable material according to theory. The minority-spin EHM arises from the hybridization among Zr-4d, Ti-3d and Rh-4d electrons. The calculated total magnetic moment of ZrRhTiIn is 2 μB, meeting the well-known Slater-Pauling rule Mt = Zt -18. Furthermore, uniform strain and tetragonal strain were applied in this work to examine the magneto-electronic and half-metallic behaviors of the ZrRhTiIn system. Finally, we show that ZrRhTiIn is mechanically stable, ductile and anisotropic.

C(2) symmetric chiral NHC ligand for asymmetric quaternary carbon constructing copper-catalyzed conjugate addition of grignard reagents to 3-substituted cyclohexenones.

PubMed

Matsumoto, Yasumasa; Yamada, Ken-ichi; Tomioka, Kiyoshi

2008-06-20

The asymmetric construction of quaternary carbon centers by conjugate addition of Grignard reagents to 3-methyl- and 3-ethylcyclohexenones was realized in a maximum enantioselectivity of 80% by using a C 2 symmetric chiral N-heterocyclic carbene (NHC)-copper catalyst, generated from (4 S,5 S)-1,3-bis(2-methoxyphenyl)-4,5-diphenyl-4,5-dihydro-1 H-imidazol-3-ium tetrafluoroborate and copper(II) triflate. The stereostructures of the NHC-Au complexes were analyzed by X-ray crystallography, which rationalized the good stereocontrolling ability of N-aryl NHCs.

Host-guest chemistry of dendrimer-drug complexes. 2. Effects of molecular properties of guests and surface functionalities of dendrimers.

PubMed

Hu, Jingjing; Cheng, Yiyun; Wu, Qinglin; Zhao, Libo; Xu, Tongwen

2009-08-06

The host-guest chemistry of dendrimer-drug complexes is investigated by NMR techniques, including (1)H NMR and 2D-NOESY studies. The effects of molecular properties of drug molecules (protonation ability and spatial steric hindrance of charged groups) and surface functionalities of dendrimers (positively charged amine groups and negatively charged carboxylate groups) on the host-guest interactions are discussed. Different interaction mechanisms between dendrimers and drug molecules are proposed on the basis of NMR results. Primary amine- and secondary amine-containing drugs preferentially bind to negatively charged dendrimers by strong electrostatic interactions, whereas tertiary amine and quaternary ammonium-containing drugs have weak binding ability with dendrimers due to relatively low protonation ability of the tertiary amine group and serious steric hindrance of the quaternary ammonium group. Positively charged drugs locate only on the surface of negatively charged dendrimers, whereas negatively charged drugs locate both on the surface and in the interior cavities of positively charged dendrimers. The host-guest chemistry of dendrimer-drug complexes is promising for the development of new drug delivery systems.

Post-glacial redistribution and shifts in productivity of giant kelp forests

PubMed Central

Graham, Michael H.; Kinlan, Brian P.; Grosberg, Richard K.

2010-01-01

Quaternary glacial–interglacial cycles create lasting biogeographic, demographic and genetic effects on ecosystems, yet the ecological effects of ice ages on benthic marine communities are unknown. We analysed long-term datasets to develop a niche-based model of southern Californian giant kelp (Macrocystis pyrifera) forest distribution as a function of oceanography and geomorphology, and synthesized palaeo-oceanographic records to show that late Quaternary climate change probably drove high millennial variability in the distribution and productivity of this foundation species. Our predictions suggest that kelp forest biomass increased up to threefold from the glacial maximum to the mid-Holocene, then rapidly declined by 40–70 per cent to present levels. The peak in kelp forest productivity would have coincided with the earliest coastal archaeological sites in the New World. Similar late Quaternary changes in kelp forest distribution and productivity probably occurred in coastal upwelling systems along active continental margins worldwide, which would have resulted in complex shifts in the relative productivity of terrestrial and marine components of coastal ecosystems. PMID:19846450

Effect of alkali cations on two-dimensional networks of two new quaternary thioarsenates (III) prepared by a facile surfactant-thermal method

NASA Astrophysics Data System (ADS)

Yan, Dongming; Hou, Peipei; Liu, Chang; Chai, Wenxiang; Zheng, Xuerong; Zhang, Luodong; Zhi, Mingjia; Zhou, Chunmei; Liu, Yi

2016-09-01

Two new quaternary thioarsenates(III) NaAg2AsS3·H2O (1) and KAg2AsS3 (2) with high yields have been successfully prepared through a facile surfactant-thermal method. It is interesting that 2 can only be obtained with the aid of ethanediamine (en), which indicates that weak basicity of solvent is beneficial to the growth of 2 compared with 1. Both 1 and 2 feature the similar two-dimensional (2D) layer structures. However, the distortion of the primary honeycomb-like nets in 2 is more severe than that of 1, which demonstrates that Na+ and K+ cations have different structure directing effects on these two thioarsenates(III). Both experimental and theoretical studies confirm 1 and 2 are semiconductors with band gaps in the visible region. Our success in preparing these two quaternary thioarsenates(III) proves that surfactant-thermal technique is a powerful yet facile synthetic method to explore new complex chalcogenides.

Characterizing the Structure and Oligomerization of Major Royal Jelly Protein 1 (MRJP1) by Mass Spectrometry and Complementary Biophysical Tools.

PubMed

Mandacaru, Samuel C; do Vale, Luis H F; Vahidi, Siavash; Xiao, Yiming; Skinner, Owen S; Ricart, Carlos A O; Kelleher, Neil L; de Sousa, Marcelo Valle; Konermann, Lars

2017-03-21

Royal jelly (RJ) triggers the development of female honeybee larvae into queens. This effect has been attributed to the presence of major royal jelly protein 1 (MRJP1) in RJ. MRJP1 isolated from royal jelly is tightly associated with apisimin, a 54-residue α-helical peptide that promotes the noncovalent assembly of MRJP1 into multimers. No high-resolution structural data are available for these complexes, and their binding stoichiometry remains uncertain. We examined MRJP1/apisimin using a range of biophysical techniques. We also investigated the behavior of deglycosylated samples, as well as samples with reduced apisimin content. Our mass spectrometry (MS) data demonstrate that the native complexes predominantly exist in a (MRJP1 4 apisimin 4 ) stoichiometry. Hydrogen/deuterium exchange MS reveals that MRJP1 within these complexes is extensively disordered in the range of residues 20-265. Marginally stable secondary structure (likely antiparallel β-sheet) exists around residues 266-432. These weakly structured regions interchange with conformers that are extensively unfolded, giving rise to bimodal (EX1) isotope distributions. We propose that the native complexes have a "dimer of dimers" quaternary structure in which MRJP1 chains are bridged by apisimin. Specifically, our data suggest that apisimin acts as a linker that forms hydrophobic contacts involving the MRJP1 segment 316 VLFFGLV 322 . Deglycosylation produces large soluble aggregates, highlighting the role of glycans as aggregation inhibitors. Samples with reduced apisimin content form dimeric complexes with a (MRJP1 2 apisimin 1 ) stoichiometry. The information uncovered in this work will help pave the way toward a better understanding of the unique physiological role played by MRJP1 during queen differentiation.

3D Complex: A Structural Classification of Protein Complexes

PubMed Central

Levy, Emmanuel D; Pereira-Leal, Jose B; Chothia, Cyrus; Teichmann, Sarah A

2006-01-01

Most of the proteins in a cell assemble into complexes to carry out their function. It is therefore crucial to understand the physicochemical properties as well as the evolution of interactions between proteins. The Protein Data Bank represents an important source of information for such studies, because more than half of the structures are homo- or heteromeric protein complexes. Here we propose the first hierarchical classification of whole protein complexes of known 3-D structure, based on representing their fundamental structural features as a graph. This classification provides the first overview of all the complexes in the Protein Data Bank and allows nonredundant sets to be derived at different levels of detail. This reveals that between one-half and two-thirds of known structures are multimeric, depending on the level of redundancy accepted. We also analyse the structures in terms of the topological arrangement of their subunits and find that they form a small number of arrangements compared with all theoretically possible ones. This is because most complexes contain four subunits or less, and the large majority are homomeric. In addition, there is a strong tendency for symmetry in complexes, even for heteromeric complexes. Finally, through comparison of Biological Units in the Protein Data Bank with the Protein Quaternary Structure database, we identified many possible errors in quaternary structure assignments. Our classification, available as a database and Web server at http://www.3Dcomplex.org, will be a starting point for future work aimed at understanding the structure and evolution of protein complexes. PMID:17112313

Ancient and modern sites of natural CO2 leakage: Geochemistry and geochronology of Quaternary and modern travertine deposits on the Colorado Plateau, USA, and implications for CO2 sequestration

NASA Astrophysics Data System (ADS)

Priewisch, A.; Crossey, L. J.; Karlstrom, K. E.; McPherson, B. J.; Mozley, P.

2013-12-01

Travertine-precipitating springs and travertine deposits of the Colorado Plateau serve as natural analogues for evaluating potential leakage associated with geologic sequestration of carbon dioxide (CO2). Extensive Quaternary and modern travertine deposits occur along the Jemez lineament and Rio Grande rift in New Mexico and Arizona, and in the Paradox Basin in Utah, along the Little Grand Wash Fault and the Salt Wash Graben. These groundwater discharge deposits are interpreted to be sites of persistent and significant CO2 degassing along faults and above magmatic systems. Analysis of the geochemical and isotopic composition of U-series dated travertine deposits and modern travertine-precipitating waters allows evaluation of the flow paths of CO2-charged waters. Initial results from New Mexico and Arizona travertine deposits show characteristic rare earth element (REE) signatures for individual travertine deposits and yet generally overlap in concentrations of other trace elements such as Al, As, B, Ba, K, and Si. We report stable oxygen and carbon isotopes of the travertines in New Mexico, Arizona, and Utah. Different travertine deposits have different carbon-oxygen isotope variation patterns suggesting that these stable isotopes are tracers that have the ability to identify distinctive groundwater sources within and between spring groups based on the travertine record. Stable isotope analyses of travertine deposits in New Mexico and Arizona overlap substantially between deposits and cluster around -10‰ to -6‰ for δ18O and around 3.5‰ to 6.5‰ for δ13C. Travertine deposits in Utah show a distinctly different range of stable isotope values: δ18O values cluster around -14‰ to -10.5‰ and δ13C around 4.5‰ to 6.5‰. U-series dating of travertine deposits shows episodic travertine formation in New Mexico and Arizona over the last 700,000 years, and travertine accumulation over the last 400,000 years in Utah. We use U-series dating and volumetric analysis of the travertine deposits to estimate the minimum CO2 flux that was necessary to form the deposits and compare it to modern flux measurements in order to assess the extent of former and modern CO2 leakage. In addition, the thickness of dated travertine sections provides information about the longevity of travertine mound or spring systems that may be controlled by, e. g., sealing of faults, alternating wet/ dry paleohydrologic conditions, and/or rates of magmatic CO2 supply to springs. Understanding travertine deposition is important for the assessment of the long-term performance of a potential CO2 sequestration site because travertine deposits give insight into the complexities of CO2 pathways and leakage rates over timescales necessary for CO2 sequestration.

Influence of temperature on nitrogen fate during hydrothermal carbonization of food waste.

PubMed

Wang, Tengfei; Zhai, Yunbo; Zhu, Yun; Peng, Chuan; Xu, Bibo; Wang, Tao; Li, Caiting; Zeng, Guangming

2018-01-01

The influence of temperature (180-260°C) on the fate of nitrogen during hydrothermal carbonization (HTC) of food waste (FW) was assessed. The distribution and evolution of nitrogen in aqueous products and bio-oil, as well as hydrochar, were conducted. Results suggested that elevated temperature enhanced the deamination and the highest ammonium concentration (929.75mg/L) was acquired at 260°C. At temperatures above 220°C, the total N in the hydrochar became stable, whereas the mass percentage of N increased. Amines and heterocyclic-N compounds from protein cracking and Maillard reactions were identified as the main nitrogen-containing compounds in the bio-oil. As to the hydrochar, increasing temperature resulted in condensed nitrogen-containing aromatic heterocycles (e.g. pyridine-N and quaternary-N). In particular, remarkable Maillard reactions at 180°C and the highest temperature at 260°C enhanced nitrogen incorporation (i.e. quaternary-N) into hydrochar. Copyright © 2017 Elsevier Ltd. All rights reserved.

Temperature and pressure dependent structural and thermo-physical properties of quaternary CoVTiAl alloy

NASA Astrophysics Data System (ADS)

Yousuf, Saleem; Gupta, Dinesh C.

2017-09-01

Investigation of band structure and thermo-physical response of new quaternary CoVTiAl Heusler alloy within the frame work of density functional theory has been analyzed. 100% spin polarization with ferromagnetic stable ground state at the optimized lattice parameter of 6.01 Å is predicted for the compound. Slater-Pauling rule for the total magnetic moment of 3 μB and an indirect semiconducting behavior is also seen for the compound. In order to perfectly analyze the thermo-physical response, the lattice thermal conductivity and thermodynamic properties have been calculated. Thermal effects on some macroscopic properties of CoVTiAl are predicted using the quasi-harmonic Debye model, in which the lattice vibrations are taken into account. The variations of the lattice constant, volume expansion coefficient, heat capacities, and Debye temperature with pressure and temperature in the ranges of 0 GPa to 15 GPa and 0 K to 800 K have been obtained.

New Ni-based quaternary disk-shaped catalysts for low-temperature CO2 methanation: Fabrication, characterization, and performance.

PubMed

Moon, Dea Hyun; Lee, Sang Moon; Ahn, Jeong Yoon; Nguyen, Dinh Duc; Kim, Sung Su; Chang, Soon Woong

2018-07-15

Ni-based quaternary disk catalysts were manufactured for low-temperature CO 2 methanation reactions, and the reaction activity was examined with respect to the thermal treatment conditions. By applying varying reduction and combustion treatments, the same catalysts were compared, and the Ni oxidation conditions and physical features were confirmed through X-Ray diffraction, scanning electron microscopy, and energy dispersive X-ray analyses. In addition, oxygen adsorption/desorption changes were measured by temperature-programmed reduction after pre-treating with oxygen and hydrogen. The reduction treatment catalyst showed a conversion of 20% at 280 °C, and the 70% calcined catalyst did not form a NiO crystalloid. The activation of the catalyst increased because of NiO movement on the catalyst surface, which enabled easy transformation to metallic Ni. The prepared catalyst is a highly reactive, yet stable, candidate for practical catalytic CO 2 methanation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Quaternary bedrock erosion and landscape evolution in the Sør Rondane Mountains, East Antarctica: Reevaluating rates and processes

NASA Astrophysics Data System (ADS)

Matsuoka, Norikazu; Thomachot, Céline E.; Oguchi, Chiaki T.; Hatta, Tamao; Abe, Masahiro; Matsuzaki, Hiroyuki

2006-11-01

Rates and processes of rock weathering, soil formation, and mountain erosion during the Quaternary were evaluated in an inland Antarctic cold desert. The fieldwork involved investigations of weathering features and soil profiles for different stages after deglaciation. Laboratory analyses addressed chemistry of rock coatings and soils, as well as 10Be and 26Al exposure ages of the bedrock. Less resistant gneiss bedrock exposed over 1 Ma shows stone pavements underlain by in situ produced silty soils thinner than 40 cm and rich in sulfates, which reflect the active layer thickness, the absence of cryoturbation, and the predominance of salt weathering. During the same exposure period, more resistant granite bedrock has undergone long-lasting cavernous weathering that produces rootless mushroom-like boulders with a strongly Fe-oxidized coating. The red coating protects the upper surface from weathering while very slow microcracking progresses by the growth of sulfates. Geomorphological evidence and cosmogenic exposure ages combine to provide contrasting average erosion rates. No erosion during the Quaternary is suggested by a striated roche moutonnée exposed more than 2 Ma ago. Differential erosion between granite and gneiss suggests a significant lowering rate of desert pavements in excess of 10 m Ma - 1 . The landscape has been (on the whole) stable, but the erosion rate varies spatially according to microclimate, geology, and surface composition.

High-resolution seismic sequence stratigraphy and history of relative sea level changes since the Late Miocene, northern continental margin, South China Sea

NASA Astrophysics Data System (ADS)

Zhong, G.; Wang, L.

2013-12-01

The northern South China Sea (SCS) margin is suggested as one of the ideal sites for documenting the late Cenozoic sea level changes for its characteristics of rapid sedimentation and relatively stable structural subsidence since the Late Miocene. In this study, high-resolution seismic profiles acquired by the Guangzhou Marine Geological Survey, calibrated by well control from the ODP sites 1146 and 1148, were utilized to construct a time-significant sequence stratigraphic framework, from which the history of relative sea level changes since the Late Miocene on the northern SCS margin was derived. Our study area is situated in the middle segment of the margin, between the Hainan Island to the west and the Dongsha Islands to the east. This region is to a certain degree far away from the active structural zones and is suggested as the most stable region in the margin. Totally 4000 km seismic profiles were used, which controls an area of about 6×104 km2. The seismic data have a vertical resolution of 5 to 15 m for the Upper Miocene to Quaternary interval. Three regional seismic sequence boundaries were identified. They subdivide the Late Miocene to Quaternary into three mega-sequences, which correspond to the Quaternary, Pliocene and Late Miocene, respectively by tying to well control. The Late Miocene mega-sequence, including 13 component sequences, is characterized with a basal incised canyon-developed interval overlain by three sets of progradational sequences formed in deep-water slope environments. The Pliocene mega-sequence consists of four sets of progradational sequences. Each sequence set contains one to three component sequences. At least 7 component sequences can be identified. The Quaternary mega-sequence consists of five sets of progradational sequences, in which the lower two constitute a retrogressive sequence set and the upper three a progradational sequence set. At least 9 component sequences can be recognized. Most of the component sequences within the Pliocene and Quaternary mega-sequences occur adjacent to modern shelf margin, and therefore were interpreted as shelf-marginal progradational deltaic sequences. A relative sea level curve since the Late Miocene was compiled by integrating the shift trajectory of onlap points, the stacking pattern of component sequences, and the chronostratigraphic diagrams. The curve contains about 29 cycles of relative sea level changes, showing a much higher resolution than the previous results in the region. These cycles constitute three large relative sea level rise and fall cycles. General trend of sea level variations is rising since the Late Miocene, which is opposite to the global sea level changes and is in accordance with the previous regional researches. This deviation is ascribed to the combined effects of very rapid regional subsidence and relative deficiency of sediment supply. This research was funded by the National Natural Science Foundation of China (Grant Nos. 91028003 and 41076020).

Regulated assembly and disassembly of the yeast telomerase quaternary complex

PubMed Central

Tucey, Timothy M.

2014-01-01

The enzyme telomerase, which elongates chromosome termini, is a critical factor in determining long-term cellular proliferation and tissue renewal. Hence, even small differences in telomerase levels can have substantial consequences for human health. In budding yeast, telomerase consists of the catalytic Est2 protein and two regulatory subunits (Est1 and Est3) in association with the TLC1 RNA, with each of the four subunits essential for in vivo telomerase function. We show here that a hierarchy of assembly and disassembly results in limiting amounts of the quaternary complex late in the cell cycle, following completion of DNA replication. The assembly pathway, which is driven by interaction of the Est3 telomerase subunit with a previously formed Est1–TLC1–Est2 preassembly complex, is highly regulated, involving Est3-binding sites on both Est2 and Est1 as well as an interface on Est3 itself that functions as a toggle switch. Telomerase subsequently disassembles by a mechanistically distinct pathway due to dissociation of the catalytic subunit from the complex in every cell cycle. The balance between the assembly and disassembly pathways, which dictate the levels of the active holoenzyme in the cell, reveals a novel mechanism by which telomerase (and hence telomere homeostasis) is regulated. PMID:25240060

Drainage isolation and climate change-driven population expansion shape the genetic structures of Tuber indicum complex in the Hengduan Mountains region.

PubMed

Feng, Bang; Zhao, Qi; Xu, Jianping; Qin, Jiao; Yang, Zhu L

2016-02-24

The orogenesis of the Qinghai-Tibetan Plateau and the Quaternary climate changes have played key roles in driving the evolution of flora and fauna in Southwest China, but their effects on higher fungi are poorly addressed. In this study, we investigated the phylogeographic pattern of the Tuber indicum species complex, an economically important fungal group distributed in the Hengduan Mountains region. Our data confirmed the existence of two distinct lineages, T. indicum and T. himalayense, within this species complex. Three geographic groups (Groups W, N and C) were revealed within T. indicum, with Group W found in the paleo-Lancang River region, while Groups N and C corresponded to the two banks along the contemporary Jinsha River, suggesting that rivers have acted as barriers for gene flow among populations from different drainages. Historical range expansion resulted from climate changes was inferred in Group C, contributing to the observed gene flow among geographic populations within this group. Although no significant geographic structure was identified in T. himalayense, evidence of drainage isolation for this species was also detected. Our findings demonstrate that both topographic changes and Quaternary climate oscillations have played important roles in driving the genetic structures of the T. indicum species complex.

Quaternary Structure of the Oxaloacetate Decarboxylase Membrane Complex and Mechanistic Relationships to Pyruvate Carboxylases*

PubMed Central

Balsera, Monica; Buey, Ruben M.; Li, Xiao-Dan

2011-01-01

The oxaloacetate decarboxylase primary Na+ pump (OAD) is an essential membrane protein complex that functions in the citrate fermentation pathway of some pathogenic bacteria under anaerobic conditions. OAD contains three different subunits: Oad-α, a biotinylated extrinsic protein that catalyzes the α-ketodecarboxylation of oxaloacetate; Oad-γ, a structural bitopic membrane protein whose cytosolic tail (named as Oad-γ′) binds tightly to Oad-α; and Oad-β, a multispan transmembrane α-helical protein that constitutes the Na+ channel. How OAD is organized structurally at the membrane and what the molecular determinants are that lead to an efficient energy coupling mechanism remain elusive. In the present work, we elucidate the stoichiometry of the native complex as well as the low resolution structure of the peripheral components of OAD (Oad-α and Oad-γ′) by small angle x-ray scattering. Our results point to a quaternary assembly similar to the pyruvate carboxylase complex organization. Herein, we propose a model in which the association in pairs of Oad-α dimers, mediated by Oad-γ, results in the acquisition of a functional oligomeric state at the bacterial membrane. New structural insights for the conformational rearrangements associated with the carboxylbiotin transfer reaction within OAD are provided. PMID:21209096

In vivo biochemical analyses reveal distinct roles of β-importins and eEF1A in tRNA subcellular traffic

PubMed Central

Huang, Hsiao-Yun

2015-01-01

Bidirectional tRNA movement between the nucleus and the cytoplasm serves multiple biological functions. To gain a biochemical understanding of the mechanisms for tRNA subcellular dynamics, we developed in vivo β-importin complex coimmunoprecipitation (co-IP) assays using budding yeast. Our studies provide the first in vivo biochemical evidence that two β-importin family members, Los1 (exportin-t) and Msn5 (exportin-5), serve overlapping but distinct roles in tRNA nuclear export. Los1 assembles complexes with RanGTP and tRNA. Both intron-containing pre-tRNAs and spliced tRNAs, regardless of whether they are aminoacylated, assemble into Los1–RanGTP complexes, documenting that Los1 participates in both primary nuclear export and re-export of tRNAs to the cytoplasm. In contrast, β-importin Msn5 preferentially assembles with RanGTP and spliced, aminoacylated tRNAs, documenting its role in tRNA nuclear re-export. Tef1/2 (the yeast form of translation elongation factor 1α [eEF1A]) aids the specificity of Msn5 for aminoacylated tRNAs to form a quaternary complex consisting of Msn5, RanGTP, aminoacylated tRNA, and Tef1/2. Assembly and/or stability of this quaternary complex requires Tef1/2, thereby facilitating efficient re-export of aminoacylated tRNAs to the cytoplasm. PMID:25838545

Tertiary and quaternary effects in the allosteric regulation of animal hemoglobins.

PubMed

Ronda, Luca; Bruno, Stefano; Bettati, Stefano

2013-09-01

In the last decade, protein allostery has experienced a major resurgence, boosted by the extension of the concept to systems of increasing complexity and by its exploitation for the development of drugs. Expansion of the field into new directions has not diminished the key role of hemoglobin as a test molecule for theory and experimental validation of allosteric models. Indeed, the diffusion of hemoglobins in all kingdoms of life and the variety of functions and of quaternary assemblies based on a common tertiary fold indicate that this superfamily of proteins is ideally suited for investigating the physical and molecular basis of allostery and firmly maintains its role as a main player in the field. This review is an attempt to briefly recollect common and different strategies adopted by metazoan hemoglobins, from monomeric molecules to giant complexes, exploiting homotropic and heterotropic allostery to increase their functional dynamic range. This article is part of a Special Issue entitled: Oxygen Binding and Sensing Proteins. Copyright © 2013 Elsevier B.V. All rights reserved.

Geomorphological expression of a complex structural region: San Andreas Fault through the San Gorgonio Pass, southern California

NASA Astrophysics Data System (ADS)

Kendrick, K. J.; Matti, J. C.

2015-12-01

The San Gorgonio Pass (SGP) region of southern California is a locus of extensive Quaternary deformation surrounding a complex section of the San Andreas Fault (SAF) zone. The geomorphology of the SGP region reflects the complicated history of geologic events in the formation of this structural 'knot'. Critical questions remain in assessing earthquake hazard for this region: What is the likelihood that rupture will propagate through the SGP? If rupture is able to propagate, what pathway will connect the various fault strands? To address these questions, we focus on the geology and geomorphology of the SGP region. We have identified fault-bounded blocks, and focus on three that are developed within crystalline bedrock: the Yucaipa Ridge block (YRB) block, the Kitching Peak block (KPB), and the Pisgah Peak block (PPB). The latter two blocks are positioned south of the YRB, and partially separated from each other by the San Bernardino strand; this strand cannot be mapped at the surface as an active connection between fault strands. Both KPB and PPB are bounded to the south by the San Gorgonio Pass Fault Zone. Morphometric analyses consistently demonstrate distinctions between KPB and PPB, though the bedrock lithologies are the same. Geologic mapping of the region highlights the differences in Quaternary units within the blocks. These geomorphic and geologic distinctions lead to our interpretation that KPB and PPB have experienced markedly different uplift histories that constrain the history of dextral slip on the SAF through SGP. Specifically, although the latest Quaternary geologic setting of SGP raises questions about modern slip transfer through the Pass, the contrasting uplift histories of KPB and PPB strongly suggest that earlier in Quaternary time SGP was not a barrier to slip transfer between the Coachella Valley to the SE and the San Bernardino Basin to the NW.

Linking micro- and macroevolutionary perspectives to evaluate the role of Quaternary sea-level oscillations in island diversification.

PubMed

Papadopoulou, Anna; Knowles, L Lacey

2017-12-01

With shifts in island area, isolation, and cycles of island fusion-fission, the role of Quaternary sea-level oscillations as drivers of diversification is complex and not well understood. Here, we conduct parallel comparisons of population and species divergence between two island areas of equivalent size that have been affected differently by sea-level oscillations, with the aim to understand the micro- and macroevolutionary dynamics associated with sea-level change. Using genome-wide datasets for a clade of seven Amphiacusta ground cricket species endemic to the Puerto Rico Bank (PRB), we found consistently deeper interspecific divergences and higher population differentiation across the unfragmented Western PRB, in comparison to the currently fragmented Eastern PRB that has experienced extreme changes in island area and connectivity during the Quaternary. We evaluate alternative hypotheses related to the microevolutionary processes (population splitting, extinction, and merging) that regulate the frequency of completed speciation across the PRB. Our results suggest that under certain combinations of archipelago characteristics and taxon traits, the repeated changes in island area and connectivity may create an opposite effect to the hypothesized "species pump" action of oscillating sea levels. Our study highlights how a microevolutionary perspective can complement current macroecological work on the Quaternary dynamics of island biodiversity. © 2017 The Author(s). Evolution © 2017 The Society for the Study of Evolution.

Low frequency of broadly neutralizing HIV antibodies during chronic infection even in quaternary epitope targeting antibodies containing large numbers of somatic mutations.

PubMed

Hicar, Mark D; Chen, Xuemin; Kalams, Spyros A; Sojar, Hakimuddin; Landucci, Gary; Forthal, Donald N; Spearman, Paul; Crowe, James E

2016-02-01

Neutralizing antibodies (Abs) are thought to be a critical component of an appropriate HIV vaccine response. It has been proposed that Abs recognizing conformationally dependent quaternary epitopes on the HIV envelope (Env) trimer may be necessary to neutralize diverse HIV strains. A number of recently described broadly neutralizing monoclonal Abs (mAbs) recognize complex and quaternary epitopes. Generally, many such Abs exhibit extensive numbers of somatic mutations and unique structural characteristics. We sought to characterize the native antibody (Ab) response against circulating HIV focusing on such conformational responses, without a prior selection based on neutralization. Using a capture system based on VLPs incorporating cleaved envelope protein, we identified a selection of B cells that produce quaternary epitope targeting Abs (QtAbs). Similar to a number of broadly neutralizing Abs, the Ab genes encoding these QtAbs showed extensive numbers of somatic mutations. However, when expressed as recombinant molecules, these Abs failed to neutralize virus or mediate ADCVI activity. Molecular analysis showed unusually high numbers of mutations in the Ab heavy chain framework 3 region of the variable genes. The analysis suggests that large numbers of somatic mutations occur in Ab genes encoding HIV Abs in chronically infected individuals in a non-directed, stochastic, manner. Copyright © 2015 Elsevier Ltd. All rights reserved.

Do cosmogenic nuclides (10Be, 14C , 21Ne, 26Al) track late Quaternary climate changes on the Altiplano?

NASA Astrophysics Data System (ADS)

Hippe, K.; Kober, F.; Zeilinger, G.; Ivy-Ochs, S.; Kubik, P.; Maden, C.; Wieler, R.

2010-12-01

The high Altiplano plateau is the most prominent element of the Central Andes, separating the Andean Cordilleras between 15° to 22° S. It represents a tectonically quiet, intramontane basin with arid to semi-arid climate, low relief and internal drainage. Throughout the late Quaternary regional climate on the Altiplano repeatedly changed between wet and dry conditions [1]. The influence of climate on the plateau evolution during the Pleistocene/Holocene is unclear, however, as data on erosion processes and rates on the Altiplano are sparse. Here, we present a multiple-nuclide study investigating surface denudation at the eastern Altiplano of Bolivia (16°-17° S) on millennial and longer timescales. The aim is a better understanding of the complex feedback between climate, tectonics and geomorphology on the topographic evolution of the Andes. Catchment-wide denudation (CWD) rates are provided for a 150 km NW-SE transect along the Altiplano edge based on the analyses of cosmogenic 10Be, 26Al, 21Ne and in-situ 14C in river-borne sediment. Single nuclide CWD rates obtained for 10Be, 26Al and 21Ne are similar for all three nuclides and on the order of 3-37 mm/ka. Thus, the calculated denudation rates provide an averaged denudation history dating back at least to the middle Pleistocene. Denudation rates correlate positively with the mean basin hillslope, which is mainly controlled by basin lithology. For most catchments both, the 26Al/10Be ratios and the 21Ne/10Be ratios indicate a complex erosion/exposure history with probably several periods of sediment storage and burial/shielding totalling ~0.5 - 1.2 Ma. Local geomorphology featuring low slopes and low relief, small terraces and local floodplains also suggests that sediment transport might have been periodically ineffective. Concentrations of in-situ produced short-lived 14C are significantly lower than expected from the concentrations of the long-lived and stable cosmogenic nuclides. This would indicate a 30-40 fold increase in denudation rates since ~3000 years, which appears rather unlikely. Hence, the measured in-situ 14C concentrations may actually reflect sediment storage. Partial sediment shielding at ~80-150 cm depth is plausible from field evidence. Due to the fast decay of 14C, such shielding would result in a drop of the 14C concentration from saturation to the measured values already after several 1000 years. Nevertheless, other explanations as incomplete sediment mixing also have to be taken into account. Interestingly, our CWD long-term data agree well with short-term sediment yield data from the Altiplano (5.6-48 mm/ka) [2]. This suggests an overall uniformity in erosional processes and rates throughout the late Quaternary. The agreement between single nuclide denudation rates, despite the complex storage history, also argues for rather long-term steady-state conditions and highlights the insensitivity of long-lived cosmogenic nuclides to low amplitude, short-term variations in climate. References: [1] Plazcek et al. (2006), GSA Bulletin 118, 515-532, [2] Guyot et al. (1992), Lake Titicaca 113-119.

Arctic systems in the Quaternary: Ecological collision, faunal mosaics and the consequences of wobbling climate

USDA-ARS?s Scientific Manuscript database

Climate oscillations and episodic or recurrent processes interact with evolution, ecology and biogeography determining the structure and complex mosaic that is the biosphere. Parasites and parasite-host assemblages, within an expansive environmental matrix determined by climate, are key components...

Late Quaternary glaciation of the Upper Soca River Region (Southern Julian Alps, NW Slovenia)

USGS Publications Warehouse

Bavec, Milos; Tulaczyk, Slawek M.; Mahan, Shannon; Stock, Gregory M.

2004-01-01

Extent of Late Quaternary glaciers in the Upper Soc??a River Region (Southern Julian Alps, SE Europe) has been analyzed using a combination of geological mapping, glaciological modeling, and sediment dating (radiocarbon, U/Th series and Infrared Stimulated Luminescence-IRSL). Field investigations focused mainly on relatively well preserved Quaternary sequences in the Bovec Basin, an intramontane basin located SW of the Mediterranean/Black Sea divide and surrounded by mountain peaks reaching from approximately 2100 up to 2587 m a.s.l. Within the Basin we recognized two Late Quaternary sedimentary assemblages, which consist of the same facies association of diamictons, laminated lacustrine deposits and sorted fluvial sediments. Radiocarbon dating of the upper part of the lake sediments sequence (between 12790??85 and 5885??60 14C years b.p.) indicates that the younger sedimentary assemblage was deposited during the last glacial maximum and through early Holocene (Marine Isotope Stage 21, MIS 2-1). Sediment ages obtained for the older assemblage with U/Th and IRSL techniques (between 154.74??22.88 and 129.93??7.90 ka b.p. for selected samples) have large errors but both methods yield results consistent with deposition during the penultimate glacial-interglacial transition (MIS 6-5). Based on analyses of field data combined with glaciological modeling, we argue that both sediment complexes formed due to high sediment productivity spurred by paraglacial conditions with glaciers present in the uplands around the Bovec Basin but not extending down to the basin floor. Our study shows that the extent and intensity of direct glacial sedimentation by Late Quaternary glaciers in the region was previously significantly overestimated. ?? 2004 Elsevier B.V. All rights reserved.

Formation and shape-control of hierarchical cobalt nanostructures using quaternary ammonium salts in aqueous media

PubMed Central

Deshmukh, Ruchi; Mehra, Anurag

2017-01-01

Aggregation and self-assembly are influenced by molecular interactions. With precise control of molecular interactions, in this study, a wide range of nanostructures ranging from zero-dimensional nanospheres to hierarchical nanoplates and spindles have been successfully synthesized at ambient temperature in aqueous solution. The nanostructures reported here are formed by aggregation of spherical seed particles (monomers) in presence of quaternary ammonium salts. Hydroxide ions and a magnetic moment of the monomers are essential to induce shape anisotropy in the nanostructures. The cobalt nanoplates are studied in detail, and a growth mechanism based on collision, aggregation, and crystal consolidation is proposed based on a electron microscopy studies. The growth mechanism is generalized for rods, spindles, and nearly spherical nanostructures, obtained by varying the cation group in the quaternary ammonium hydroxides. Electron diffraction shows different predominant lattice planes on the edge and on the surface of a nanoplate. The study explains, hereto unaddressed, the temporal evolution of complex magnetic nanostructures. These ferromagnetic nanostructures represent an interesting combination of shape anisotropy and magnetic characteristics. PMID:28326240

Geomorphic characterization of the U.S. Atlantic continental margin

USGS Publications Warehouse

Brothers, Daniel S.; ten Brink, Uri S.; Andrews, Brian D.; Chaytor, Jason D.

2013-01-01

The increasing volume of multibeam bathymetry data collected along continental margins is providing new opportunities to study the feedbacks between sedimentary and oceanographic processes and seafloor morphology. Attempts to develop simple guidelines that describe the relationships between form and process often overlook the importance of inherited physiography in slope depositional systems. Here, we use multibeam bathymetry data and seismic reflection profiles spanning the U.S. Atlantic outer continental shelf, slope and rise from Cape Hatteras to New England to quantify the broad-scale, across-margin morphological variation. Morphometric analyses suggest the margin can be divided into four basic categories that roughly align with Quaternary sedimentary provinces. Within each category, Quaternary sedimentary processes exerted heavy modification of submarine canyons, landslide complexes and the broad-scale morphology of the continental rise, but they appear to have preserved much of the pre-Quaternary, across-margin shape of the continental slope. Without detailed constraints on the substrate structure, first-order morphological categorization the U.S. Atlantic margin does not provide a reliable framework for predicting relationships between form and process.

Four novel antibacterial sesquiterpene-α-amino acid quaternary ammonium hybrids from the mycelium of mushroom Stereum hirsutum.

PubMed

Duan, Yuan-Chang; Feng, Jun; Bai, Na; Li, Guo-Hong; Zhang, Ke-Qin; Zhao, Pei-Ji

2018-05-21

The mushroom Stereum hirsutum is parasitized by Tremella aurantia to form a heterogeneous basidiocarp Jin'er, which has been used as food and folk medicine in Chinese society. In present work, the S. hirsutum was fermented in YMG broth, and four novel mixed terpenes, stereumamides A-D (1-4), which are sesquiterpenes combined with α-amino acids to form quaternary ammonium hybrids, were isolated from the Stereum hirsutum FP-91666 and their structures were elucidated by spectroscopic data analysis. Stereumamides A and D showed antibacterial activity against Escherichia coli, Staphylococcus aureus, and Salmonella typhimurium, with the minimum inhibitory concentration (MIC) values of 12.5-25.0 μg/mL. The stereumamides A-D should be apparently the first example of naturally occurring a quaternary ammonium compound (QAC) conjugated by sesquiterpene with an α-amino acid. QAC is a common antibacterial agent in food industry, which is found in the mycelium of Stereum hirsutum would suggest that the complex basidiocarp is a functional food and veritable folk medicine. Copyright © 2017. Published by Elsevier B.V.

Late Quaternary climate stability and the origins and future of global grass endemism.

PubMed

Sandel, Brody; Monnet, Anne-Christine; Govaerts, Rafaël; Vorontsova, Maria

2017-01-01

Earth's climate is dynamic, with strong glacial-interglacial cycles through the Late Quaternary. These climate changes have had major consequences for the distributions of species through time, and may have produced historical legacies in modern ecological patterns. Unstable regions are expected to contain few endemic species, many species with strong dispersal abilities, and to be susceptible to the establishment of exotic species from relatively stable regions. We test these hypotheses with a global dataset of grass species distributions. We described global patterns of endemism, variation in the potential for rapid population spread, and exotic establishment in grasses. We then examined relationships of these response variables to a suite of predictor variables describing the mean, seasonality and spatial pattern of current climate and the temperature change velocity from the Last Glacial Maximum to the present. Grass endemism is strongly concentrated in regions with historically stable climates. It also depends on the spatial pattern of current climate, with many endemic species in areas with regionally unusual climates. There was no association between the proportion of annual species (representing potential population spread rates) and climate change velocity. Rather, the proportion of annual species depended very strongly on current temperature. Among relatively stable regions (<10 m year -1 ), increasing velocity decreased the proportion of species that were exotic, but this pattern reversed for higher-velocity regions (>10 m year -1 ). Exotic species were most likely to originate from relatively stable regions with climates similar to those found in their exotic range. Long-term climate stability has important influences on global endemism patterns, largely confirming previous work from other groups. Less well recognized is its role in generating patterns of exotic species establishment. This result provides an important historical context for the conjecture that climate change in the near future may promote species invasions. © The Author 2016. Published by Oxford University Press on behalf of the Annals of Botany Company. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Investigation into MIS 11 in the U.S. Great Basin Using Trace Elements and Stable Isotopes from two Lehman Caves Stalagmites

NASA Astrophysics Data System (ADS)

Neary, A.; McGee, D.; Tal, I.; Shakun, J. D.

2015-12-01

Marine Isotope Stage 11 (MIS 11) represents a long interglacial period of high temperatures and muted orbital variability that occurred around 424-374 kya, and is referred to as a 'super-interglacial'. MIS 11 is marked by especially pronounced high latitude warming in the Northern Hemisphere from 410-400 ka and thus presents a natural experiment for investigating the response of Great Basin precipitation to high latitude temperatures.MIS 11 is recorded by stalagmites LC3 and BT1 from Lehman Caves in Great Basin National Park, Nevada. LC3 represents 378-413 ka, while BT1 has a bottom age of 410 ka. Ongoing U-Th dating will refine chronologies from these samples. We will present stable isotope (δ13C and δ18O) and trace element (Mg/Ca and Sr/Ca) data from these stalagmites to study changes in precipitation recorded in them. Previous studies have shown a relationship between Mg/Ca, Sr/Ca, δ13C and prior calcite precipitation, and thus infiltration rates, in the cave system (Cross et al., 2015; Steponaitis et al., 2015). Meanwhile, δ18O has been shown to reflect larger scale atmospheric circulation.We will compare the records to previously published trace element and stable isotope data from more recent interglacials (Lachniet et al., 2014; Cross et al., 2015; Steponaitis et al., 2015) to test whether extensive high-latitude warming during MIS 11 was marked by anomalous precipitation patterns in the Great Basin. As they are coeval, we will also test the reproducibility between the stalagmites.References cited:Cross M., et al. (2015) Great Basin hydrology, paleoclimate, and connections with the North Atlantic: A speleothem stable isotope and trace element record from Lehman Caves, NV. Quaternary Science Reviews, in press.Steponaitis E., et al. (2015) Mid-Holocene drying the U.S. Great Basin recorded in Nevada speleothems. Quaternary Science Reviews, in press.Lachniet M. S., et al. (2014) Orbital control of western North America atmospheric circulation and climate over two glacial cycles. Nature Communications 5, 1-8.

The role of climate and vegetation on woolly mammoth extinction on St. Paul Island, Alaska and megafauna extinction in North America in the late Quaternary

NASA Astrophysics Data System (ADS)

Wang, Y.; Porter, W.; Miller, P. A.; Graham, R. W.; Williams, J. W.

2016-12-01

Estimate of megafauna behaviors dynamically under associated environmental factors is important to understand the mechanisms and causes of the late Quaternary megafaunal extinctions. On St. Paul Island, an isolated remnant of the Bering Land Bridge, a late-surviving population of woolly mammoth (Mammuthus primigenius) persisted until 5,600 cal BP, while 37 out of 54 megafauna species in the continent of North America, all herbivores, went extinct at the end of Pleistocene between 13,800 and 11,500 cal BP. Proposed natural drivers of the extinction events include abrupt temperature changes, food resource loss and freshwater shortage. Here we tested these three hypothesized mechanisms, using a physiological model (Niche Mapper) to estimate individual megafauna behaviors from the perspectives of metabolic rate, individual vegetation and freshwater requirement under simulated climates from Community Climate System Model version 3 (CCSM3), vegetation reconstructions based on dynamic LPJ-GUESS model and woolly mammoth and megafauna species trait data reconstructed based on mammal fossils. Preliminary simulations of woolly mammoth on St. Paul Island point to the importance of net vegetation primary productivity and freshwater availability as limits on the carrying capacity of St. Paul for mammoth populations, with a low carrying capacity in the middle Holocene making this population highly vulnerable to extinction. Results also indicate that the abrupt warming based around 14,000 cal BP in Bering land bridge on CCSM3 simulations causes woolly mammoth extinction, by driving metabolic rate high up beyond the active basic metabolic rate. Analysis suggests a positive relationship between temperature and metabolic rate, and woolly mammoth would go extinct when summer temperature is up to 12 °C or higher. However the temperature reconstructed based on regional proxies is relatively stable compared to CCSM3 simulations, and leads to stable metabolic rate of woolly mammoth and no extinction events. Proposed simulations of megafauna species in North America indicate the role of ice sheets in limiting habitats. This work helps resolve the drivers of extinction for a small island surviving woolly mammoth population and worldwide megafauna extinctions in the late Quaternary.

Shifting Quaternary migration patterns in the Bahamian archipelago: Evidence from the Zamia pumila complex at the northern limits of the Caribbean island biodiversity hotspot.

PubMed

Salas-Leiva, Dayana E; Meerow, Alan W; Calonje, Michael; Francisco-Ortega, Javier; Griffith, M Patrick; Nakamura, Kyoko; Sánchez, Vanessa; Knowles, Lindy; Knowles, David

2017-05-01

The Bahamas archipelago is formed by young, tectonically stable carbonate banks that harbor direct geological evidence of global ice-volume changes. We sought to detect signatures of major changes on gene flow patterns and reconstruct the phylogeographic history of the monophyletic Zamia pumila complex across the Bahamas. Nuclear molecular markers with both high and low mutation rates were used to capture two different time scale signatures and test several gene flow and demographic hypotheses. Single-copy nuclear genes unveiled apparent ancestral admixture on Andros, suggesting a significant role of this island as main hub of diversity of the archipelago. We detected demographic and spatial expansion of the Zamia pumila complex on both paleo-provinces around the Piacenzian (Pliocene)/Gelasian (Pleistocene). Populations evidenced signatures of different migration models that have occurred at two different times. Populations on Long Island ( Z. lucayana ) may either represent a secondary colonization of the Bahamas by Zamia or a rapid and early-divergence event of at least one population on the Bahamas. Despite changes in migration patterns with global climate, expected heterozygosity with both marker systems remains within the range reported for cycads, but with significant levels of increased inbreeding detected by the microsatellites. This finding is likely associated with reduced gene flow between and within paleo-provinces, accompanied by genetic drift, as rising seas enforced isolation. Our study highlights the importance of the maintenance of the predominant direction of genetic exchange and the role of overseas dispersion among the islands during climate oscillations. © 2017 Botanical Society of America.

Late Quaternary palaeoenvironmental reconstruction of sediment drift accumulation in the Malta Graben (central Mediterranean Sea)

NASA Astrophysics Data System (ADS)

Ferraro, Serena; Sulli, Attilio; Di Stefano, Enrico; Giaramita, Luigi; Incarbona, Alessandro; Graham Mortyn, P.; Sprovieri, Mario; Sprovieri, Rodolfo; Tonielli, Renato; Vallefuoco, Mattia; Zizzo, Elisabetta; Tranchida, Giorgio

2018-06-01

The Malta Graben is a deep tectonic depression in the Sicily Channel, bounded by NW-SE normal faults and filled by thick Pliocene-Quaternary deposits. A previous analysis of a giant piston core (LC09) from the Malta Graben had revealed a wide range of sedimentary features (carbonate turbidites, bioturbated mud and scours), although the chronostratigraphic constraint of the stacking pattern has remained elusive. After establishing a reliable chronological framework based on seven radiocarbon dates for a shorter core from the Malta Graben (ANSIC03-735), a down-core analysis of planktonic foraminifer and coccolith abundance, stable isotopes and sediment grain size was carried out. Since the last glacial maximum, palaeoenvironmental conditions (surface fertility and deep chlorophyll maximum during the last glacial and the Younger Dryas; warm and oligotrophic water masses, with a deep nutricline and intense winter mixing during the Holocene) as well as selected calcareous plankton taxa trends and peaks seem to be similar to those reported for other central and western Mediterranean sites, possibly in spite of a unique response of these areas to late Quaternary climatic fluctuations. Four distinct layers, each tens of centimetres thick, are barren of foraminifers but not of coccoliths. Morphobathymetric data as well as new high-resolution and high-penetration seismic profiles show that prolonged contouritic activity has persisted on the western side of the Malta Graben. It is thus likely that layers barren of foraminifers are due to the overflow of fine-grained (clayey) material beyond drift channel dikes.

Late Quaternary palaeoenvironmental reconstruction of sediment drift accumulation in the Malta Graben (central Mediterranean Sea)

NASA Astrophysics Data System (ADS)

Ferraro, Serena; Sulli, Attilio; Di Stefano, Enrico; Giaramita, Luigi; Incarbona, Alessandro; Graham Mortyn, P.; Sprovieri, Mario; Sprovieri, Rodolfo; Tonielli, Renato; Vallefuoco, Mattia; Zizzo, Elisabetta; Tranchida, Giorgio

2018-03-01

The Malta Graben is a deep tectonic depression in the Sicily Channel, bounded by NW-SE normal faults and filled by thick Pliocene-Quaternary deposits. A previous analysis of a giant piston core (LC09) from the Malta Graben had revealed a wide range of sedimentary features (carbonate turbidites, bioturbated mud and scours), although the chronostratigraphic constraint of the stacking pattern has remained elusive. After establishing a reliable chronological framework based on seven radiocarbon dates for a shorter core from the Malta Graben (ANSIC03-735), a down-core analysis of planktonic foraminifer and coccolith abundance, stable isotopes and sediment grain size was carried out. Since the last glacial maximum, palaeoenvironmental conditions (surface fertility and deep chlorophyll maximum during the last glacial and the Younger Dryas; warm and oligotrophic water masses, with a deep nutricline and intense winter mixing during the Holocene) as well as selected calcareous plankton taxa trends and peaks seem to be similar to those reported for other central and western Mediterranean sites, possibly in spite of a unique response of these areas to late Quaternary climatic fluctuations. Four distinct layers, each tens of centimetres thick, are barren of foraminifers but not of coccoliths. Morphobathymetric data as well as new high-resolution and high-penetration seismic profiles show that prolonged contouritic activity has persisted on the western side of the Malta Graben. It is thus likely that layers barren of foraminifers are due to the overflow of fine-grained (clayey) material beyond drift channel dikes.

Development of a new quaternary alloy Ti-25Ta-25Nb-3Sn for biomedical applications

NASA Astrophysics Data System (ADS)

Rangel Seixas, Mauricio; Bortolini, Celso, Jr.; Pereira, Adelvam, Jr.; Nakazato, Roberto Z.; Popat, Ketul C.; Rosifini Alves Claro, Ana Paula

2018-02-01

Metallic biomaterials have been used for biomedical applications, such as cardiovascular, orthopaedics and orthodontics, due to excellent properties. In this study, the mechanical properties and corrosion resistance of new quaternary alloy Ti25Ta25Nb3Sn were evaluated. Alloys were processing in arc melting furnace with argon atmosphere and cold worked by rotary swaging. Alloy microstructure, crystalline phases and mechanical properties such as Young’s modulus, yield strength and tensile strength were evaluated. Corrosion resistance was investigated in fluoride solution by electrochemical polarization and biocompatibility with human dermal fibroblasts were also evaluated. In our study, for quaternary alloy Ti25Ta25Nb3Sn the stabilization of beta phase was maintained. It was observed that the elastic modulus of Ti25Ta25Nb3Sn (65 GPa) was lower than CP Ti (105 GPa) and Ti6Al4V (110 GPa) and slightly higher than Ti25Ta25Nb (55 GPa) alloy. The addition of Sn suppressed the double yielding verified on ternary alloy Ti25Ta25Nb. Electrochemical studies showed that stable passive oxide film was formed on the Ti25Ta25Nb3Sn surface and an increase of HDF adhesion and proliferation on alloy surface, indicating that the alloy is non-cytotoxic may provide a favorable material for biomedical applications. Results obtained showed that Ti25Ta25Nb3Sn alloy is indicated for biomedical applications.

Preparation and testing of quaternized chitosan nanoparticles as gene delivery vehicles.

PubMed

Li, Guang-Feng; Wang, Jing-Cheng; Feng, Xin-Min; Liu, Zhen-Dong; Jiang, Chao-Yong; Yang, Jian-Dong

2015-04-01

The aim of this study was to synthesize a chitosan (CS) derivative, a quaternary ammonium salt crystal called N-2-hydroxypropyl trimethyl ammonium chloride chitosan (HACC), and test a series of HACC and pEGFP-DNA complexes at different weight ratios for their efficiency of gene delivery into human cells. CS was modified with cationic etherifying agent to obtain the CS derivative. Fourier transform infrared spectra were recorded on KBr pellets with a spectrometer. (1)H nuclear magnetic resonance (NMR) spectra of HACC were obtained using a spectrometer. HACC was subsequently used to prepare HACC/DNA complexes at different weight ratios by coacervation method. The resulting particle size and surface charge were assessed by laser light scattering using a zeta potential analyzer. The HACC/DNA complex formation and DNA protection in the nanoparticle complex was investigated by gel mobility shift assay and DNase I protection assay, respectively. The cytotoxicity of HACC and HACC/DNA nanoparticles was evaluated by MTT assay using (mesenchymal stem cell) MSC lines. The nanoscale structure of the particles was obtained by transmission electron microscope (TEM). The FTIR spectrum of HACC showed the characteristic quaternary ammonium group absorption band at 1475 cm(-1), which indicated the presence of quaternary ammonium group. The successful synthesis of HACC was also confirmed by (1)H NMR spectrum. HACC showed good solubility in water and was electropositive. HACC efficiently packed and protected pEGFP-DNA at a weight ratio of 10. With increased weight ratios, the surface charge of the composite particle increased from negative to positive, the average particle size increased, and HACC nanoparticle had a higher carrying efficiency. The nanoparticles released DNA in two distinct phases, and 55 % was released within the first 20 h of solubilization. The nanoparticles under TEM showed circular or oval shapes. The particles exhibited no cytotoxicity against human cells. No significant difference in gene delivery efficiency was detected between HACC/pEGFP-GDNF and liposome/pEGFP-GDNF complexes (33.8 vs. 34 %, P = 0.363). In this study, HACC was successfully synthesized, and HACC/DNA complex assembled efficiently. HACC showed strong DNA binding affinity and high protection of DNA and was non-cytotoxic to human cells. The particles had appropriate nanostructure, mean diameter, and DNA release time. The results suggest that HACC nanoparticles are a novel tool for efficient and safe gene delivery.

Methyl-β-cyclodextrin quaternary ammonium chitosan conjugate: nanoparticles vs macromolecular soluble complex

PubMed Central

Piras, Anna Maria; Fabiano, Angela; Chiellini, Federica; Zambito, Ylenia

2018-01-01

Purpose The present study aimed to compare a novel cyclodextrin–polymer–drug complex in solution with a dispersed supramolecular nanosize system, made of the same complex, for ability to carry dexamethasone (DEX) across excised rat intestine. Results Methyl-β-cyclodextrin-quaternary ammonium chitosan conjugate (QA-Ch-MCD) was obtained by covalent grafting through a 10-atom spacer. The conjugate was characterized by 1H-NMR, resulting in 24.4% w/w of MCD content. Phase solubility profile analysis of the QA-Ch-MCD/DEX complex yielded an association constant of 14037 M−1, vs 4428 M−1 for the plain MCD/DEX complex. Nanoparticle (NP) dispersions resulted from ionotropic gelation of the QA-Ch-MCD/DEX complex by sodium tripolyphosphate, leading to 9.9%±1.4% drug loading efficiency. The mean diameter and zeta potential for NP were 299±32 nm (polydispersity index [PI] 0.049) and 11.5±1.1 mV, respectively. Those for QA-Ch-MCD/DEX were 2.7±0.4 nm (PI 0.048) and 6.7±0.6 mV. QA-Ch-MCD/DEX solutions and corresponding NP dispersions were compared in vitro for water-assisted transport through mucus, DEX permeation through excised rat intestine, and ex vivo mucoadhesivity. The complex showed higher mucoadhesion and lower transport rate through mucus; also, it provided faster drug permeation across excised rat intestine. Conclusion Carrier adhesion to mucus surface has played a most important role in favoring transepithelial permeation. Then, within the concerns of the present study, the use of NP seems not to provide any determinant advantage over using the simpler macromolecular complex. PMID:29731628

In vivo biochemical analyses reveal distinct roles of β-importins and eEF1A in tRNA subcellular traffic.

PubMed

Huang, Hsiao-Yun; Hopper, Anita K

2015-04-01

Bidirectional tRNA movement between the nucleus and the cytoplasm serves multiple biological functions. To gain a biochemical understanding of the mechanisms for tRNA subcellular dynamics, we developed in vivo β-importin complex coimmunoprecipitation (co-IP) assays using budding yeast. Our studies provide the first in vivo biochemical evidence that two β-importin family members, Los1 (exportin-t) and Msn5 (exportin-5), serve overlapping but distinct roles in tRNA nuclear export. Los1 assembles complexes with RanGTP and tRNA. Both intron-containing pre-tRNAs and spliced tRNAs, regardless of whether they are aminoacylated, assemble into Los1-RanGTP complexes, documenting that Los1 participates in both primary nuclear export and re-export of tRNAs to the cytoplasm. In contrast, β-importin Msn5 preferentially assembles with RanGTP and spliced, aminoacylated tRNAs, documenting its role in tRNA nuclear re-export. Tef1/2 (the yeast form of translation elongation factor 1α [eEF1A]) aids the specificity of Msn5 for aminoacylated tRNAs to form a quaternary complex consisting of Msn5, RanGTP, aminoacylated tRNA, and Tef1/2. Assembly and/or stability of this quaternary complex requires Tef1/2, thereby facilitating efficient re-export of aminoacylated tRNAs to the cytoplasm. © 2015 Huang and Hopper; Published by Cold Spring Harbor Laboratory Press.

Millennial-Scale Temperature Change Velocity in the Continental Northern Neotropics

PubMed Central

Correa-Metrio, Alexander; Bush, Mark; Lozano-García, Socorro; Sosa-Nájera, Susana

2013-01-01

Climate has been inherently linked to global diversity patterns, and yet no empirical data are available to put modern climate change into a millennial-scale context. High tropical species diversity has been linked to slow rates of climate change during the Quaternary, an assumption that lacks an empirical foundation. Thus, there is the need for quantifying the velocity at which the bioclimatic space changed during the Quaternary in the tropics. Here we present rates of climate change for the late Pleistocene and Holocene from Mexico and Guatemala. An extensive modern pollen survey and fossil pollen data from two long sedimentary records (30,000 and 86,000 years for highlands and lowlands, respectively) were used to estimate past temperatures. Derived temperature profiles show a parallel long-term trend and a similar cooling during the Last Glacial Maximum in the Guatemalan lowlands and the Mexican highlands. Temperature estimates and digital elevation models were used to calculate the velocity of isotherm displacement (temperature change velocity) for the time period contained in each record. Our analyses showed that temperature change velocities in Mesoamerica during the late Quaternary were at least four times slower than values reported for the last 50 years, but also at least twice as fast as those obtained from recent models. Our data demonstrate that, given extremely high temperature change velocities, species survival must have relied on either microrefugial populations or persistence of suppressed individuals. Contrary to the usual expectation of stable climates being associated with high diversity, our results suggest that Quaternary tropical diversity was probably maintained by centennial-scale oscillatory climatic variability that forestalled competitive exclusion. As humans have simplified modern landscapes, thereby removing potential microrefugia, and climate change is occurring monotonically at a very high velocity, extinction risk for tropical species is higher than at any time in the last 86,000 years. PMID:24312614

Millennial-scale temperature change velocity in the continental northern Neotropics.

PubMed

Correa-Metrio, Alexander; Bush, Mark; Lozano-García, Socorro; Sosa-Nájera, Susana

2013-01-01

Climate has been inherently linked to global diversity patterns, and yet no empirical data are available to put modern climate change into a millennial-scale context. High tropical species diversity has been linked to slow rates of climate change during the Quaternary, an assumption that lacks an empirical foundation. Thus, there is the need for quantifying the velocity at which the bioclimatic space changed during the Quaternary in the tropics. Here we present rates of climate change for the late Pleistocene and Holocene from Mexico and Guatemala. An extensive modern pollen survey and fossil pollen data from two long sedimentary records (30,000 and 86,000 years for highlands and lowlands, respectively) were used to estimate past temperatures. Derived temperature profiles show a parallel long-term trend and a similar cooling during the Last Glacial Maximum in the Guatemalan lowlands and the Mexican highlands. Temperature estimates and digital elevation models were used to calculate the velocity of isotherm displacement (temperature change velocity) for the time period contained in each record. Our analyses showed that temperature change velocities in Mesoamerica during the late Quaternary were at least four times slower than values reported for the last 50 years, but also at least twice as fast as those obtained from recent models. Our data demonstrate that, given extremely high temperature change velocities, species survival must have relied on either microrefugial populations or persistence of suppressed individuals. Contrary to the usual expectation of stable climates being associated with high diversity, our results suggest that Quaternary tropical diversity was probably maintained by centennial-scale oscillatory climatic variability that forestalled competitive exclusion. As humans have simplified modern landscapes, thereby removing potential microrefugia, and climate change is occurring monotonically at a very high velocity, extinction risk for tropical species is higher than at any time in the last 86,000 years.

Functional alteration of a dimeric insecticidal lectin to a monomeric antifungal protein correlated to its oligomeric status.

PubMed

Banerjee, Nilanjana; Sengupta, Subhadipa; Roy, Amit; Ghosh, Prithwi; Das, Kalipada; Das, Sampa

2011-04-07

Allium sativum leaf agglutinin (ASAL) is a 25-kDa homodimeric, insecticidal, mannose binding lectin whose subunits are assembled by the C-terminal exchange process. An attempt was made to convert dimeric ASAL into a monomeric form to correlate the relevance of quaternary association of subunits and their functional specificity. Using SWISS-MODEL program a stable monomer was designed by altering five amino acid residues near the C-terminus of ASAL. By introduction of 5 site-specific mutations (-DNSNN-), a β turn was incorporated between the 11(th) and 12(th) β strands of subunits of ASAL, resulting in a stable monomeric mutant ASAL (mASAL). mASAL was cloned and subsequently purified from a pMAL-c2X system. CD spectroscopic analysis confirmed the conservation of secondary structure in mASAL. Mannose binding assay confirmed that molecular mannose binds efficiently to both mASAL and ASAL. In contrast to ASAL, the hemagglutination activity of purified mASAL against rabbit erythrocytes was lost. An artificial diet bioassay of Lipaphis erysimi with mASAL displayed an insignificant level of insecticidal activity compared to ASAL. Fascinatingly, mASAL exhibited strong antifungal activity against the pathogenic fungi Fusarium oxysporum, Rhizoctonia solani and Alternaria brassicicola in a disc diffusion assay. A propidium iodide uptake assay suggested that the inhibitory activity of mASAL might be associated with the alteration of the membrane permeability of the fungus. Furthermore, a ligand blot assay of the membrane subproteome of R. solani with mASAL detected a glycoprotein receptor having interaction with mASAL. Conversion of ASAL into a stable monomer resulted in antifungal activity. From an evolutionary aspect, these data implied that variable quaternary organization of lectins might be the outcome of defense-related adaptations to diverse situations in plants. Incorporation of mASAL into agronomically-important crops could be an alternative method to protect them from dramatic yield losses from pathogenic fungi in an effective manner.

Mucoadhesive nanoparticles made of thiolated quaternary chitosan crosslinked with hyaluronan.

PubMed

Zambito, Ylenia; Felice, Francesca; Fabiano, Angela; Di Stefano, Rossella; Di Colo, Giacomo

2013-01-30

Mucoadhesive polymeric nanoparticles intended for drug transport across the gastrointestinal mucosa were prepared from quaternary ammonium-chitosan conjugates synthesised from reduced-MW chitosan (32 kDa). Conjugates contained pendant moieties of 2-4 adjacent diethyl-dimethylene-ammonium groups substituted on repeating units (26-55%). Conjugates were thiolated via amide bonds with thioglycolic acid to yield products with thiol content in the 35-87 μmol/g range. Nanoparticles with mean size in the 270-370 nm range and positive zeta-potential (+3.7 to +12.5 mV) resulted from ionotropic gelation of the thiolated conjugates with de-polymerised hyaluronic acid (470 kDa). The nanoparticles were fairly stable in size and thiol content and showed a significant mucoadhesivity, matching and even exceeding that of the constituent polymers. Nanoparticles were internalised by endothelial progenitor cells in direct relation to their surface charge intensity. Nanoparticle uptake significantly improved cell viability and resistance to oxidation. The lyophilised nanoparticles were re-dispersible and could make a manageable formulation for oral use. Copyright © 2012 Elsevier Ltd. All rights reserved.

An operationally flexible fuel cell based on quaternary ammonium-biphosphate ion pairs

DOE PAGES

Lee, Kwan -Soo; Spendelow, Jacob Schatz; Choe, Yoong -Kee; ...

2016-08-22

Here, fuel cells are promising devices for clean power generation in a variety of economically and environmentally significant applications. Low-temperature proton exchange membrane (PEM) fuel cells utilizing Nafion require a high level of hydration, which limits the operating temperature to less than 100°C. In contrast, high-temperature PEM fuel cells utilizing phosphoric acid-doped polybenzimidazole can operate effectively up to 180°C; however, these devices degrade when exposed to water below 140°C. Here we present a different class of PEM fuel cells based on quaternary ammonium-biphosphate ion pairs that can operate under conditions unattainable with existing fuel cell technologies. These fuel cells exhibitmore » stable performance at 80–160°C with a conductivity decay rate more than three orders of magnitude lower than that of a commercial high-temperature PEM fuel cell. By increasing the operational flexibility, this class of fuel cell can simplify the requirements for heat and water management, and potentially reduce the costs associated with the existing fully functional fuel cell systems.« less

Temporal variations in volumetric magma eruption rates of Quaternary volcanoes in Japan

NASA Astrophysics Data System (ADS)

Yamamoto, Takahiro; Kudo, Takashi; Isizuka, Osamu

2018-04-01

Long-term evaluations of hazard and risk related to volcanoes rely on extrapolations from volcano histories, including the uniformity of their eruption rates. We calculated volumetric magma eruption rates, compiled from quantitative eruption histories of 29 Japanese Quaternary volcanoes, and analyzed them with respect to durations spanning 101-105 years. Calculated eruption rates vary greatly (101-10-4 km3 dense-rock equivalent/1000 years) between individual volcanoes. Although large basaltic stratovolcanoes tend to have high eruption rates and relatively constant repose intervals, these cases are not representative of the various types of volcanoes in Japan. At many Japanese volcanoes, eruption rates are not constant through time, but increase, decrease, or fluctuate. Therefore, it is important to predict whether eruption rates will increase or decrease for long-term risk assessment. Several temporal co-variations of eruption rate and magmatic evolution suggest that there are connections between them. In some cases, magma supply rates increased in response to changing magma-generation processes. On the other hand, stable plumbing systems without marked changes in magma composition show decreasing eruption rates through time.[Figure not available: see fulltext.

An operationally flexible fuel cell based on quaternary ammonium-biphosphate ion pairs

NASA Astrophysics Data System (ADS)

Lee, Kwan-Soo; Spendelow, Jacob S.; Choe, Yoong-Kee; Fujimoto, Cy; Kim, Yu Seung

2016-09-01

Fuel cells are promising devices for clean power generation in a variety of economically and environmentally significant applications. Low-temperature proton exchange membrane (PEM) fuel cells utilizing Nafion require a high level of hydration, which limits the operating temperature to less than 100 ∘C. In contrast, high-temperature PEM fuel cells utilizing phosphoric acid-doped polybenzimidazole can operate effectively up to 180 ∘C however, these devices degrade when exposed to water below 140 ∘C. Here we present a different class of PEM fuel cells based on quaternary ammonium-biphosphate ion pairs that can operate under conditions unattainable with existing fuel cell technologies. These fuel cells exhibit stable performance at 80-160 ∘C with a conductivity decay rate more than three orders of magnitude lower than that of a commercial high-temperature PEM fuel cell. By increasing the operational flexibility, this class of fuel cell can simplify the requirements for heat and water management, and potentially reduce the costs associated with the existing fully functional fuel cell systems.

A new quaternary semiconductor compound (Ba2Sb4GeS10): Ab initio study

NASA Astrophysics Data System (ADS)

Ozisik, Havva Bogaz; Ozisik, Haci; Deligoz, Engin

2017-03-01

The newly synthesised Ba2Sb4GeS10 compound is notable because of the interesting features of the quaternary Sb-containing materials. The first principle method has been used to determine the physical properties of this compound. In particular, the electronic structure has been analysed using both conventional GGA-PBE and HSE06 functional. The values of the band gap for PBE and HSE06 calculations were 1.324 and 1.84 eV, respectively. The calculated elastic constants were used to predict polycrystalline mechanical properties. The estimated Vickers hardness (2.7 GPa) values show that Ba2Sb4GeS10 is soft matter. Moreover, the vibrational properties of the compound have been studied. The calculation of the elastic constants and phonon dispersion curves indicates that the Ba2Sb4GeS10 compound is stable both mechanically and dynamically. Furthermore, the minimum thermal conductivity and optical properties, such as dielectric functions and energy loss function, have also been discussed in detail in this paper.

Multicomponent homogeneous alloys and method for making same

DOEpatents

Dutta, Partha S.; Miller, Thomas R.

2003-09-02

The present application discloses a method for preparing a homogeneous ternary or quaternary alloy from a quaternary melt. The method includes providing a family of phase diagrams for the quaternary melt which shows (i) composition/temperature data, (ii) tie lines connecting equilibrium liquid and solid compositions, and (iii) isotherms representing boundaries of a miscibility gap. Based on the family of phase diagrams, a quaternary melt composition and an alloy growth temperature is selected. A quaternary melt having the selected quaternary melt composition is provided and a ternary or quaternary alloy is grown from the quaternary melt at the selected alloy growth temperature. A method for making homogeneous ternary or quaternary alloy from a ternary or quaternary melt is also disclosed, as are homogeneous quaternary single-crystal alloys which are substantially free from crystal defects and which have the formula A.sub.x B.sub.1-x C.sub.y D.sub.1-y, x and y being the same or different and in the range of 0.001 to 0.999.

Filled Nd(sub z) Fe(sub x) Co(sub 4-x) Sb(sub 12-y) Ge(sub y) Skutterudites: Processing and Thermoelectric Properties

NASA Technical Reports Server (NTRS)

Mackey, Jon; Sehirlioglu, Alp; Dynys, Fred

2016-01-01

Skutterudites have proven to be a useful thermoelectric system as a result of their enhanced figure of merit (ZT1), cheap material cost, favorable mechanical properties, and good thermal stability. The majority of skutterudite interest in recent years has been focused on binary skutterudites like CoSb3. Binary skutterudites are often double and triple filled, with a range of elements from the lanthanide series, in order to reduce the lattice component of thermal conductivity. Ternary and quaternary skutterudites, such as Co4Ge6Se6 or Ni4Sb8Sn4, provide additional paths to tune the electronic structure. The thermal conductivity can further be improved in these complex skutterudites by the introduction of fillers. The Nd (sub z) Fe (sub x) Co (sub 4-x) Sb (sub 12-y)Ge (sub y) system has been investigated as a p-type thermoelectric material, and is stable up to 600 degrees Centigrade. The influence of Fe and Ge content, along with filler Nd, was investigated on thermoelectric transport properties. In addition to the chemical influence on properties, some processing details of the system will also be addressed.

Filled Nd(z)Fe(x)Co(4-x)Sb(12-y)Ge(y) Skutterudites: Processing and Thermoelectric Properties

NASA Technical Reports Server (NTRS)

Mackey, Jon; Sehirlioglu, Alp; Dynys, Fred

2016-01-01

Skutterudites have proven to be a useful thermoelectric system as a result of their enhanced figure of merit (ZT1), cheap material cost, favorable mechanical properties, and good thermal stability. The majority of skutterudite interest in recent years has been focused on binary skutterudites like CoSb3. Binary skutterudites are often double and triple filled, with a range of elements from the lanthanide series, in order to reduce the lattice component of thermal conductivity. Ternary and quaternary skutterudites, such as Co4Ge6Se6 or Ni4Sb8Sn4, provide additional paths to tune the electronic structure. The thermal conductivity can further be improved in these complex skutterudites by the introduction of fillers. The Nd(z)Fe(x)Co(4-x)Sb(12-y)Ge(y) system has been investigated as a p-type thermoelectric material, and is stable up to 600 C. The influence of Fe and Ge content, along with filler Nd, was investigated on thermoelectric transport properties. In addition to the chemical influence on properties, some processing details of the system will also be addressed.

Evaluation of the efficiency of continuous wavelet transform as processing and preprocessing algorithm for resolution of overlapped signals in univariate and multivariate regression analyses; an application to ternary and quaternary mixtures

NASA Astrophysics Data System (ADS)

Hegazy, Maha A.; Lotfy, Hayam M.; Mowaka, Shereen; Mohamed, Ekram Hany

2016-07-01

Wavelets have been adapted for a vast number of signal-processing applications due to the amount of information that can be extracted from a signal. In this work, a comparative study on the efficiency of continuous wavelet transform (CWT) as a signal processing tool in univariate regression and a pre-processing tool in multivariate analysis using partial least square (CWT-PLS) was conducted. These were applied to complex spectral signals of ternary and quaternary mixtures. CWT-PLS method succeeded in the simultaneous determination of a quaternary mixture of drotaverine (DRO), caffeine (CAF), paracetamol (PAR) and p-aminophenol (PAP, the major impurity of paracetamol). While, the univariate CWT failed to simultaneously determine the quaternary mixture components and was able to determine only PAR and PAP, the ternary mixtures of DRO, CAF, and PAR and CAF, PAR, and PAP. During the calculations of CWT, different wavelet families were tested. The univariate CWT method was validated according to the ICH guidelines. While for the development of the CWT-PLS model a calibration set was prepared by means of an orthogonal experimental design and their absorption spectra were recorded and processed by CWT. The CWT-PLS model was constructed by regression between the wavelet coefficients and concentration matrices and validation was performed by both cross validation and external validation sets. Both methods were successfully applied for determination of the studied drugs in pharmaceutical formulations.

Comparative analyses of quaternary arrangements in homo-oligomeric proteins in superfamilies: Functional implications.

PubMed

Sudha, Govindarajan; Srinivasan, Narayanaswamy

2016-09-01

A comprehensive analysis of the quaternary features of distantly related homo-oligomeric proteins is the focus of the current study. This study has been performed at the levels of quaternary state, symmetry, and quaternary structure. Quaternary state and quaternary structure refers to the number of subunits and spatial arrangements of subunits, respectively. Using a large dataset of available 3D structures of biologically relevant assemblies, we show that only 53% of the distantly related homo-oligomeric proteins have the same quaternary state. Considering these homologous homo-oligomers with the same quaternary state, conservation of quaternary structures is observed only in 38% of the pairs. In 36% of the pairs of distantly related homo-oligomers with different quaternary states the larger assembly in a pair shows high structural similarity with the entire quaternary structure of the related protein with lower quaternary state and it is referred as "Russian doll effect." The differences in quaternary state and structure have been suggested to contribute to the functional diversity. Detailed investigations show that even though the gross functions of many distantly related homo-oligomers are the same, finer level differences in molecular functions are manifested by differences in quaternary states and structures. Comparison of structures of biological assemblies in distantly and closely related homo-oligomeric proteins throughout the study differentiates the effects of sequence divergence on the quaternary structures and function. Knowledge inferred from this study can provide insights for improved protein structure classification and function prediction of homo-oligomers. Proteins 2016; 84:1190-1202. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

A Simple Question to Think about When Considering the Hemoglobin Function

ERIC Educational Resources Information Center

Ruiz-Larrea, M. Begona

2002-01-01

Hemoglobin is a complex protein formed by various subunits interacting with each other. These noncovalent interactions, quaternary structure, are responsible for hemoglobin functioning as an excellent oxygen transporter, loading up with oxygen in the lungs and delivering it to tissues, where the oxygen pressure is lower. The communications between…

Solubility Limits in Lennard-Jones Mixtures: Effects of Disparate Molecule Geometries.

PubMed

Dyer, Kippi M; Perkyns, John S; Pettitt, B Montgomery

2015-07-23

In order to better understand general effects of the size and energy disparities between macromolecules and solvent molecules in solution, especially for macromolecular constructs self-assembled from smaller molecules, we use the first- and second-order exact bridge diagram extensions of the HNC integral equation theory to investigate single-component, binary, ternary, and quaternary mixtures of Lennard-Jones fluids. For pure fluids, we find that the HNCH3 bridge function integral equation (i.e., exact to third order in density) is necessary to quantitatively predict the pure gas and pure liquid sides of the coexistence region of the phase diagram of the Lennard-Jones fluid. For the mixtures, we find that the HNCH2 bridge function integral equation is sufficient to qualitatively predict solubility in the binary, ternary, and quaternary mixtures, up to the nominal solubility limit. The results, as limiting cases, should be useful to several problems, including accurate phase diagram predictions for complex mixtures, design of self-assembling nanostructures via solvent controls, and the solvent contributions to the conformational behavior of macromolecules in complex fluids.

Paleoseismicity of two historically quiescent faults in Australia: Implications for fault behavior in stable continental regions

USGS Publications Warehouse

Crone, A.J.; De Martini, P. M.; Machette, M.M.; Okumura, K.; Prescott, J.R.

2003-01-01

Paleoseismic studies of two historically aseismic Quaternary faults in Australia confirm that cratonic faults in stable continental regions (SCR) typically have a long-term behavior characterized by episodes of activity separated by quiescent intervals of at least 10,000 and commonly 100,000 years or more. Studies of the approximately 30-km-long Roopena fault in South Australia and the approximately 30-km-long Hyden fault in Western Australia document multiple Quaternary surface-faulting events that are unevenly spaced in time. The episodic clustering of events on cratonic SCR faults may be related to temporal fluctuations of fault-zone fluid pore pressures in a volume of strained crust. The long-term slip rate on cratonic SCR faults is extremely low, so the geomorphic expression of many cratonic SCR faults is subtle, and scarps may be difficult to detect because they are poorly preserved. Both the Roopena and Hyden faults are in areas of limited or no significant seismicity; these and other faults that we have studied indicate that many potentially hazardous SCR faults cannot be recognized solely on the basis of instrumental data or historical earthquakes. Although cratonic SCR faults may appear to be nonhazardous because they have been historically aseismic, those that are favorably oriented for movement in the current stress field can and have produced unexpected damaging earthquakes. Paleoseismic studies of modern and prehistoric SCR faulting events provide the basis for understanding of the long-term behavior of these faults and ultimately contribute to better seismic-hazard assessments.

The RPAP3-Cterminal domain identifies R2TP-like quaternary chaperones.

PubMed

Maurizy, Chloé; Quinternet, Marc; Abel, Yoann; Verheggen, Céline; Santo, Paulo E; Bourguet, Maxime; C F Paiva, Ana; Bragantini, Benoît; Chagot, Marie-Eve; Robert, Marie-Cécile; Abeza, Claire; Fabre, Philippe; Fort, Philippe; Vandermoere, Franck; M F Sousa, Pedro; Rain, Jean-Christophe; Charpentier, Bruno; Cianférani, Sarah; Bandeiras, Tiago M; Pradet-Balade, Bérengère; Manival, Xavier; Bertrand, Edouard

2018-05-29

R2TP is an HSP90 co-chaperone that assembles important macro-molecular machineries. It is composed of an RPAP3-PIH1D1 heterodimer, which binds the two essential AAA+ATPases RUVBL1/RUVBL2. Here, we resolve the structure of the conserved C-terminal domain of RPAP3, and we show that it directly binds RUVBL1/RUVBL2 hexamers. The human genome encodes two other proteins bearing RPAP3-C-terminal-like domains and three containing PIH-like domains. Systematic interaction analyses show that one RPAP3-like protein, SPAG1, binds PIH1D2 and RUVBL1/2 to form an R2TP-like complex termed R2SP. This co-chaperone is enriched in testis and among 68 of the potential clients identified, some are expressed in testis and others are ubiquitous. One substrate is liprin-α2, which organizes large signaling complexes. Remarkably, R2SP is required for liprin-α2 expression and for the assembly of liprin-α2 complexes, indicating that R2SP functions in quaternary protein folding. Effects are stronger at 32 °C, suggesting that R2SP could help compensating the lower temperate of testis.

Deconstructing mammal dispersals and faunal dynamics in SW Europe during the Quaternary

NASA Astrophysics Data System (ADS)

Palombo, Maria Rita

2014-07-01

This research aims to investigate the relationships between climate change and faunal dynamics in south-west Europe, disentangling the asynchronous and diachronous dispersal bioevents of large mammals across geographical and ecological boundaries, analysing biodiversity and its changes through time. The analysis of local versus regional biological dynamics may shed new light on whether turnovers and ecological and evolutionary changes developed because of global climate changes and related phenomena, or because of intrinsic biological factors. The SW European Quaternary fossil record is particularly suitable for studying the role of climate change at local and regional levels because of the complex physiographic and climatic heterogeneity of the study area, the presence of important geographical/ecological barriers and the complex history of invasions of species of varying geographical origin and provenance. The data base consists of taxonomically revised lists of large mammal species from selected SW European local faunal assemblages ranging in age from the Early to the late Middle Pleistocene (middle Villafranchian to early Aurelian European Land Mammal Ages). The new biochronological scheme proposed here allows for the comparison of local turnovers and biodiversity trends, yielding a better understanding of the action of geographical/ecological barriers that either prevented the range of some taxa from reaching some regions or caused delays in the dispersal of a taxon in some territories. The results obtained provide evidence that major environmental perturbations, triggering dispersal events and removing keystone species, modified the structure of the pre-existing mammalian faunas, merging previously independently-evolved taxa into new palaeo-communities. The coupled action of climatic changes and internal biotic dynamics thus caused the Quaternary SW European faunal complexes to significantly restructure. Diachroneity in local turnover across the study area probably relates to differences in local dynamic patterns of competition/coevolution, although different manifestations of global climate changes in different geographic settings would have contributed to the scale of local bioevents.

Gemini Surfactants Based on Bis-Imidazolium Alkoxy Derivatives as Effective Agents for Delivery of Nucleic Acids: A Structural and Spectroscopic Study.

PubMed

Pietralik, Zuzanna; Kołodziejska, Żaneta; Weiss, Marek; Kozak, Maciej

2015-01-01

The success rate of gene therapy depends on the efficient transfection of genetic material into cells. The golden mean between harmlessness and high effectiveness can be provided by synthetic lipid-like molecules that are similar to the components of biological membranes. Cationic gemini surfactants are one such moiety and because of their favourable physicochemical properties (double positive electric charge, reduced toxicity, low values of critical micelle concentration), they show great potential as delivery system components for genetic material in gene therapy. The aim of this study was to investigate the process of the complexation of cationic gemini surfactants with nucleic acids: double-stranded DNA of different sizes (21 bp, ~185 bp, ~20 kbp) and siRNA (21 bp). The tested series of dicationic surfactants consists of bis-imidazolium quaternary salts with varying lengths of hydrophobic side chains (m = 5, 6, 7, 8, 9, 11, 12, 14, 16). On the basis of the data obtained by circular dichroism spectroscopy and electrophoresis, we concluded that the studied gemini surfactants with long side chains effectively bind nucleic acids at low concentrations, which leads to the formation of stable lipoplexes. Images obtained by atomic force microscopy also confirmed the formation of vesicular structures, i.e., complexes between DNA and surfactants. The cytotoxicity of selected surfactants was also tested on HeLa cells. The surfactant toxicity significantly depends on surfactant geometry (the length of hydrophobic chain).

Gemini Surfactants Based on Bis-Imidazolium Alkoxy Derivatives as Effective Agents for Delivery of Nucleic Acids: A Structural and Spectroscopic Study

PubMed Central

Pietralik, Zuzanna; Kołodziejska, Żaneta; Weiss, Marek; Kozak, Maciej

2015-01-01

The success rate of gene therapy depends on the efficient transfection of genetic material into cells. The golden mean between harmlessness and high effectiveness can be provided by synthetic lipid-like molecules that are similar to the components of biological membranes. Cationic gemini surfactants are one such moiety and because of their favourable physicochemical properties (double positive electric charge, reduced toxicity, low values of critical micelle concentration), they show great potential as delivery system components for genetic material in gene therapy. The aim of this study was to investigate the process of the complexation of cationic gemini surfactants with nucleic acids: double-stranded DNA of different sizes (21 bp, ~185 bp, ~20 kbp) and siRNA (21 bp). The tested series of dicationic surfactants consists of bis-imidazolium quaternary salts with varying lengths of hydrophobic side chains (m = 5, 6, 7, 8, 9, 11, 12, 14, 16). On the basis of the data obtained by circular dichroism spectroscopy and electrophoresis, we concluded that the studied gemini surfactants with long side chains effectively bind nucleic acids at low concentrations, which leads to the formation of stable lipoplexes. Images obtained by atomic force microscopy also confirmed the formation of vesicular structures, i.e., complexes between DNA and surfactants. The cytotoxicity of selected surfactants was also tested on HeLa cells. The surfactant toxicity significantly depends on surfactant geometry (the length of hydrophobic chain). PMID:26641889

Geochemical, isotopic (Sr-Nd-Pb) and geochronological (Ar-Ar and U-Pb) constraints on Quaternary bimodal volcanism of the Nigde Volcanic Complex (Central Anatolia, Turkey)

NASA Astrophysics Data System (ADS)

Aydin, F.; Siebel, W.; Uysal, I.; Ersoy, E. Y.; Schmitt, A. K.; Sönmez, M.; Duncan, R.

2012-04-01

The Nigde Volcanic Complex (NVC) is a major Late Neogene-Quaternary volcanic centre within the Cappadocian Volcanic Province of Central Anatolia. The Late Neogene evolution of the NVC generally initiated with the eruption of extensive andesitic-dacitic lavas and pyroclastic flow deposits, and minor basaltic lavas. This stage was followed by a Quaternary bimodal magma suite which forms Na-alkaline/transitional basaltic and high-K calc-alkaline to alkaline silicic volcanic rocks. In this study, we present new geochemical, isotopic (Sr-Nd-Pb) and geochronological (Ar-Ar and U-Pb) data for the bimodal volcanic suite within the NVC. Recent data suggest that the eruption of this suite took place ranges between ~650 and ~220 ka (Middle-Late Pleistocene). Silicic rocks consisting of rhyolite and associated pumice-rich pyroclastic fall out and surge deposits define a narrow range of 143Nd/144Nd isotope ratios (0.5126-0.5127), and show virtually no difference in Pb isotope composition (206Pb/204Pb = 18.84-18.87, 207Pb/204Pb = 15.64-15.67 and 208Pb/204Pb = 38.93-38.99). 87Sr/86Sr isotopic compositions of the silicic (0.704-0.705) and basaltic rocks (0.703-0.705) are rather similar reflecting a common source. The most mafic sample from basaltic rocks related to monogenetic cones is characterized by 87Sr/86Sr = 0.704, 143Nd/144Nd = 0.5127, 206Pb/204Pb = 18.80, 207Pb/204Pb = 15.60 and 208Pb/204Pb = 38.68. These values suggest a moderately depleted signature of the mantle source. The geochronological and geochemical data suggest that NVC silicic and basaltic rocks are genetically closely related to each other. Mantle derived differentiated basaltic melts which experienced low degree of crustal assimilation are suggested to be the parent melt of the rhyolites. Further investigations will focus on the spatial and temporal evolution of Quaternary bimodal magma suite in the NVC and the genetic relation between silicic and basaltic rocks through detailed oxygen isotope analysis and (U-Th)/He zircon geochronology.

Interaction of pulsating and spinning waves in nonadiabatic flame propagation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Booty, M.R.; Margolis, S.B.; Matkowsky, B.J.

1987-12-01

The authors consider nonadiabatic premixed flame propagation in a long cylindrical channel. A steadily propagating planar flame exists for heat losses below a critical value. It is stable provided that the Lewis number and the volumetric heat loss coefficient are sufficiently small. At critical values of these parameters, bifurcated states, corresponding to time-periodic pulsating cellular flames, emanate from the steadily propagating solution. The authors analyze the problem in a neighborhood of a multiple primary bifurcation point. By varying the radius of the channel, they split the multiple bifurcation point and show that various types of stable periodic and quasi-periodic pulsatingmore » flames can arise as secondary, tertiary, and quaternary bifurcations. Their analysis describes several types of spinning and pulsating flame propagation which have been experimentally observed in nonadiabatic flames, and also describes additional quasi-periodic modes of burning which have yet to be documented experimentally.« less

Water-soluble cationic derivatives of indirubin, the active anticancer component from Indigo naturalis.

PubMed

Ginzinger, Werner; Egger, Alexander; Mühlgassner, Gerhard; Arion, Vladimir B; Jakupec, Michael A; Galanski, Markus; Berger, Walter; Keppler, Bernhard K

2012-10-01

To overcome the problem of poor aqueous solubility and bioavailability of indirubin-3-oximes, the compounds were modified by attaching a quaternary ammonium group at the oxime moiety. Exploring the prodrug concept, an oxime ester with acetyl-l-carnitine was prepared, and the rate of its hydrolysis was investigated to assess its suitability for clinical administration. In addition, the cytotoxic potency of new stable oxime ethers with a choline moiety and their influence on the cell cycle were tested in human cancer cell lines. Copyright © 2012 Verlag Helvetica Chimica Acta AG, Zürich.

Electrochemical membrane incinerator

DOEpatents

Johnson, Dennis C.; Houk, Linda L.; Feng, Jianren

2001-03-20

Electrochemical incineration of p-benzoquinone was evaluated as a model for the mineralization of carbon in toxic aromatic compounds. A Ti or Pt anode was coated with a film of the oxides of Ti, Ru, Sn and Sb. This quaternary metal oxide film was stable; elemental analysis of the electrolyzed solution indicated the concentration of these metal ions to be 3 .mu.g/L or less. The anode showed good reactivity for the electrochemical incineration of benzoquinone. The use of a dissolved salt matrix as the so-called "supporting electrolyte" was eliminated in favor of a solid-state electrolyte sandwiched between the anode and cathode.

Multi-approach quantification of denudation rates in the Gulf of Lion source-to-sink system (SE France)

NASA Astrophysics Data System (ADS)

Molliex, S.; Rabineau, M.; Leroux, E.; Bourlès, D. L.; Authemayou, C.; Aslanian, D.; Chauvet, F.; Civet, F.; Jouët, G.

2016-06-01

During the Pliocene and the Quaternary, the Gulf of Lion, the northern passive margin of the Liguro-Provençal basin in the western Mediterranean Sea, received sediments from a 120 000 km2 drainage area constituted by several structural domains. The denudation of mountainous areas, source of this sedimentary supply, results from complex interactions between tectonics, climate, morphology, and rock erodibility. In this study, denudation rates from the present-day and ranging back to the Quaternary and the Pliocene are quantified using four independent methods allowing an investigation over different time scales: 1) compilation of present-day measured sediment fluxes, 2) determination of catchment-scale cosmogenic denudation rates through measurements of in situ-produced 10Be concentrations in sands sampled at the outlet of present-day rivers, 3) estimation of eroded volumes within catchments using a DEM to quantify long-term averaged Quaternary denudation rates, and 4) quantification of sediment volumes deposited within the marine realm of the Gulf of Lion. The results obtained by these four methods are in agreement within the range of uncertainties. The internal part of the Alps exhibits significantly higher denudation rates (∼700 mm ka-1) than those estimated in the other structural domains: 150-250 mm ka-1 in the foreland Alps, ∼100 mm ka-1 in the Pyrenees, and 55-75 mm ka-1 in the Massif Central. The Alpine domain provides at least 80% of the total eroded volume supplied towards the Gulf of Lion. A quantitative geomorphological approach shows that denudation rates are controlled at the first order by catchment morphologies (slope, relief) over different time scales, suggesting glacial conditioning to be the main driver on denudation from the Quaternary to present-day. Throughout the Pliocene-Quaternary, a doubling of denudation rates related to the mid-Pleistocene Revolution (∼0.9 Ma) is highlighted.

High-Throughput Screening Across Quaternary Alloy Composition Space: Oxidation of (AlxFeyNi1-x-y)∼0.8Cr∼0.2.

PubMed

Payne, Matthew A; Miller, James B; Gellman, Andrew J

2016-09-12

Composition spread alloy films (CSAFs) are commonly used as libraries for high-throughput screening of composition-property relationships in multicomponent materials science. Because lateral gradients afford two degrees of freedom, an n-component CSAF can, in principle, contain any composition range falling on a continuous two-dimensional surface through an (n - 1)-dimensional composition space. However, depending on the complexity of the CSAF gradients, characterizing and graphically representing this composition range may not be straightforward when n ≥ 4. The standard approach for combinatorial studies performed using quaternary or higher-order CSAFs has been to use fixed stoichiometric ratios of one or more components to force the composition range to fall on some well-defined plane in the composition space. In this work, we explore the synthesis of quaternary Al-Fe-Ni-Cr CSAFs with a rotatable shadow mask CSAF deposition tool, in which none of the component ratios are fixed. On the basis of the unique gradient geometry produced by the tool, we show that the continuous quaternary composition range of the CSAF can be rigorously represented using a set of two-dimensional "pseudoternary" composition diagrams. We then perform a case study of (AlxFeyNi1-x-y)∼0.8Cr∼0.2 oxidation in dry air at 427 °C to demonstrate how such CSAFs can be used to screen an alloy property across a continuous two-dimensional subspace of a quaternary composition space. We identify a continuous boundary through the (AlxFeyNi1-x-y)∼0.8Cr∼0.2 subspace at which the oxygen uptake into the CSAF between 1 and 16 h oxidation time increases abruptly with decreasing Al content. The results are compared to a previous study of the oxidation of AlxFeyNi1-x-y CSAFs in dry air at 427 °C.

Coral reef complexes at an atypical windward platform margin: Late Quaternary, southeast Florida

USGS Publications Warehouse

Lidz, B.H.

2004-01-01

Major coral reef complexes rim many modern and ancient carbonate platforms. Their role in margin evolution is not fully understood, particularly when they border a margin atypical of the classic model. Classic windward margins are steeply inclined. The windward margin of southeast Florida is distinct with a very low-gradient slope and a shelf edge ringed with 30-m-high Quaternary outlier reefs on a shallow upper-slope terrace. A newly developed synthesis of temporally well-constrained geologic events is used with surface and subsurface seismic-reflection contours to construct morphogenetic models of four discontinuous reef-complex sequences. The models show uneven subsurface topography, upward and landward buildups, and a previously unreported, rapid, Holocene progradation. The terms backstepped reef-complex margin, backfilled prograded margin, and coalesced reef-complex margin are proposed for sections exhibiting suitable signatures in the stratigraphic record. The models have significant implications for interpretation of ancient analogues. The Florida record chronicles four kinds of geologic events. (1) Thirteen transgressions high enough for marine deposition occurred between ca. 325 ka and the present. Six gave rise to stratigraphically successive coral reef complexes between ca. 185 and ca. 77.8 ka. The seventh reef ecosystem is Holocene. (2) Two primary coral reef architectures built the outer shelf and margin, producing respective ridge-and-swale and reef-and-trough geometries of very different scales. (3) Massive outlier reefs developed on an upper-slope terrace between ca. 106.5 and ca. 80 ka and are inferred to contain corals that would date to highstands at ca. 140 and 125 ka. (4) Sea level remained below elevation of the shelf between ca. 77.8 and ca. 9.6 ka. ?? 2004 Geological Society of America.

Coming to Grips with Ambiguity: Ion Mobility-Mass Spectrometry for Protein Quaternary Structure Assignment

NASA Astrophysics Data System (ADS)

Eschweiler, Joseph D.; Frank, Aaron T.; Ruotolo, Brandon T.

2017-10-01

Multiprotein complexes are central to our understanding of cellular biology, as they play critical roles in nearly every biological process. Despite many impressive advances associated with structural characterization techniques, large and highly-dynamic protein complexes are too often refractory to analysis by conventional, high-resolution approaches. To fill this gap, ion mobility-mass spectrometry (IM-MS) methods have emerged as a promising approach for characterizing the structures of challenging assemblies due in large part to the ability of these methods to characterize the composition, connectivity, and topology of large, labile complexes. In this Critical Insight, we present a series of bioinformatics studies aimed at assessing the information content of IM-MS datasets for building models of multiprotein structure. Our computational data highlights the limits of current coarse-graining approaches, and compelled us to develop an improved workflow for multiprotein topology modeling, which we benchmark against a subset of the multiprotein complexes within the PDB. This improved workflow has allowed us to ascertain both the minimal experimental restraint sets required for generation of high-confidence multiprotein topologies, and quantify the ambiguity in models where insufficient IM-MS information is available. We conclude by projecting the future of IM-MS in the context of protein quaternary structure assignment, where we predict that a more complete knowledge of the ultimate information content and ambiguity within such models will undoubtedly lead to applications for a broader array of challenging biomolecular assemblies. [Figure not available: see fulltext.

Structure-Based Characterization of Multiprotein Complexes

PubMed Central

Wiederstein, Markus; Gruber, Markus; Frank, Karl; Melo, Francisco; Sippl, Manfred J.

2014-01-01

Summary Multiprotein complexes govern virtually all cellular processes. Their 3D structures provide important clues to their biological roles, especially through structural correlations among protein molecules and complexes. The detection of such correlations generally requires comprehensive searches in databases of known protein structures by means of appropriate structure-matching techniques. Here, we present a high-speed structure search engine capable of instantly matching large protein oligomers against the complete and up-to-date database of biologically functional assemblies of protein molecules. We use this tool to reveal unseen structural correlations on the level of protein quaternary structure and demonstrate its general usefulness for efficiently exploring complex structural relationships among known protein assemblies. PMID:24954616

Evaluation of the efficiency of continuous wavelet transform as processing and preprocessing algorithm for resolution of overlapped signals in univariate and multivariate regression analyses; an application to ternary and quaternary mixtures.

PubMed

Hegazy, Maha A; Lotfy, Hayam M; Mowaka, Shereen; Mohamed, Ekram Hany

2016-07-05

Wavelets have been adapted for a vast number of signal-processing applications due to the amount of information that can be extracted from a signal. In this work, a comparative study on the efficiency of continuous wavelet transform (CWT) as a signal processing tool in univariate regression and a pre-processing tool in multivariate analysis using partial least square (CWT-PLS) was conducted. These were applied to complex spectral signals of ternary and quaternary mixtures. CWT-PLS method succeeded in the simultaneous determination of a quaternary mixture of drotaverine (DRO), caffeine (CAF), paracetamol (PAR) and p-aminophenol (PAP, the major impurity of paracetamol). While, the univariate CWT failed to simultaneously determine the quaternary mixture components and was able to determine only PAR and PAP, the ternary mixtures of DRO, CAF, and PAR and CAF, PAR, and PAP. During the calculations of CWT, different wavelet families were tested. The univariate CWT method was validated according to the ICH guidelines. While for the development of the CWT-PLS model a calibration set was prepared by means of an orthogonal experimental design and their absorption spectra were recorded and processed by CWT. The CWT-PLS model was constructed by regression between the wavelet coefficients and concentration matrices and validation was performed by both cross validation and external validation sets. Both methods were successfully applied for determination of the studied drugs in pharmaceutical formulations. Copyright © 2016 Elsevier B.V. All rights reserved.

Quaternary of Himalaya

NASA Astrophysics Data System (ADS)

Srivastava, Pradeep; Singh, Vimal

2017-05-01

Tectonically active Himalayan mountains evolves via feedbacks from deep earth and surface processes; the complex interaction of various processes results into the landscape which is dynamic both at longer and shorter time scales. The extreme hydrological events that possibly ride over a long term climate cycle bring the changes in the landscape that impact human societies more closely. These events in the Himalaya frequently cause huge damage to economy and human lives. The geologist community under the umbrella of Himalaya-Karakorum-Tibet (HKT) workshop in its 30th edition convened a special session and deliberated on the subject. This special issue "Quaternary of Himalaya" is an outcome of papers presented and discussion held during this session; it consists of 18 papers in three sub-themes (i) Extreme Events in Himalaya (ii) Paleoglaciation in Himalaya and (iii) Expressions of climate and neotectonics in Himalaya.

Physiological temperatures reduce dimerization of dengue and Zika virus recombinant envelope proteins.

PubMed

Kudlacek, Stephan T; Premkumar, Lakshmanane; Metz, Stefan W; Tripathy, Ashutosh; Bobkov, Andrey A; Payne, Alexander Matthew; Graham, Stephen; Brackbill, James A; Miley, Michael J; de Silva, Aravinda M; Kuhlman, Brian

2018-06-08

The spread of dengue (DENV) and Zika virus (ZIKV) is a major public health concern. The primary target of antibodies that neutralize DENV and ZIKV is the envelope (E) glycoprotein, and there is interest in using soluble recombinant E (sRecE) proteins as subunit vaccines. However, the most potent neutralizing antibodies against DENV and ZIKV recognize epitopes on the virion surface that span two or more E proteins. Therefore, to create effective DENV and ZIKV vaccines, presentation of these quaternary epitopes may be necessary. The sRecE proteins from DENV and ZIKV crystallize as native-like dimers, but studies in solution suggest that these dimers are marginally stable. To better understand the challenges associated with creating stable sRecE dimers, we characterized the thermostability of sRecE proteins from ZIKV and three DENV serotypes, DENV2-4. All four proteins irreversibly unfolded at moderate temperatures (46-53 °C). At 23 °C and low micromolar concentrations, DENV2 and ZIKV were primarily dimeric, and DENV3-4 were primarily monomeric, whereas at 37 °C, all four proteins were predominantly monomeric. We further show that the dissociation constant for DENV2 dimerization is very temperature-sensitive, ranging from <1 μm at 25 °C to 50 μm at 41 °C, due to a large exothermic enthalpy of binding of -79 kcal/mol. We also found that quaternary epitope antibody binding to DENV2-4 and ZIKV sRecE is reduced at 37 °C. Our observation of reduced sRecE dimerization at physiological temperature highlights the need for stabilizing the dimer as part of its development as a subunit vaccine. © 2018 Kudlacek et al.

An ab initio study on the structural, electronic and mechanical properties of quaternary full-Heusler alloys FeMnCrSn and FeMnCrSb

NASA Astrophysics Data System (ADS)

Erkişi, Aytaç

2018-06-01

The quaternary full Heusler alloys FeMnCrSn and FeMnCrSb, which have face-centred cubic (FCC) crystal structure and conform to ? space group with 216 space number, have been investigated using Generalised Gradient Approximation (GGA) in the Density Functional Theory (DFT) as implemented in VASP (Vienna Ab initio Simulation Package) software. These alloys are considered in ferromagnetic (FM) order. After the investigation of structural stability of these alloys, their mechanical and thermal properties and also electronic band structures have been examined. The calculated spin-polarised electronic band structures and total electronic density of states (DOS) within GGA approximation show that these alloys can exhibit both metallic and half-metallic characters in different structural phases. The calculated formation enthalpies and the plotted energy-volume graphs show that Type-III phase is most stable structural phase for these materials. Also, FeMnCrSb alloy in Type-I/Type-III phases and FeMnCrSn alloy in Type-III phase show half-metallic behaviour with integer total magnetic moments almost 2 and 1 μB per formula unit, respectively, since there are band gaps observed in spin-down states, whereas they have metallic behaviour in majority bands. Other structural phases of both systems are also metallic. Moreover, the calculated elastic constants and the estimated anisotropy shear factors indicate that these materials are stable mechanically in all of three phases except FeMnCrSn in Type-I phase that does not satisfy Born stability criteria in this phase and have high anisotropic behaviour.

Effect of High Pressure and Temperature on Structural, Thermodynamic and Thermoelectric Properties of Quaternary CoFeCrAl Alloy

NASA Astrophysics Data System (ADS)

Bhat, Tahir Mohiuddin; Gupta, Dinesh C.

2018-03-01

Employing first-principles based on density functional theory we have investigated the structural, magneto-electronic, thermoelectric and thermodynamic properties of quaternary Heusler alloy CoFeCrAl. Electronic band structure displays that CoFeCrAl is an indirect band gap semiconductor in spin-down state with the band gap value of 0.65 eV. Elastic constants reveal CoFeCrAl is a mechanically stable structure having a Debye temperature of 648 K along with a high melting temperature (2130 K). The thermoelectric properties in the temperature range 50-800 K have been calculated. CoFeCrAl possesses a high Seebeck coefficient of - 46 μV/K at room temperature along with the huge power factor of ˜ 4.8 (1012 μW cm-1 K-2 s-1) which maximizes the figure-of-merit up to ˜ 0.75 at 800 K temperature and suggesting CoFeCrAl as potential thermoelectric material. The effect of high pressure and high temperature on the thermal expansion, Grüneisen parameter and heat capacity were also studied by using the quasi-harmonic Debye model.

Paleomagnetic investigation of late Quaternary sediments of south San Francisco Bay, California

USGS Publications Warehouse

Hillhouse, John W.

1977-01-01

Paleomagnetic inclinations of the Late Quaternary sediments of South San Francisco Bay were determined from bore hole samples collected near Dumbarton Bridge. The sediments consist of estuarine muds and nonmarine sand deposits, floored by bedrock of the Mesozoic Franciscan Formation. - Beneath Dumbarton Bridge the entire sedimentary fill is normally polarized; therefore, the fill postdates the Brunhes-Matayama polarity reversal (700,000 y. B.P.). Magnetic time lines such as the Mono Lake excursion (24,000 y. B.P.) and the reversed Blake event (110,000 y B.P.) were not found in this bore hole. In addition to Holocene and modern deposits of San Francisco Bay, an older estuarine unit occurs in the stratigraphic section. The older unit was deposited during a period of high sea level, tentatively correlated with the Sangamon interglacial period. Because evidence of the Blake event is not present in the older estuarine unit, the proposed age of this unit could not be confirmed. Although the Holocene estuarine deposits of South San Francisco Bay carry stable remanent magnetization, a reliable record of geomagnetic secular variation could not be recovered because the water-saturated sdiment was deformed by drilling.

Cationic gemini surfactants with cleavable spacer: chemical hydrolysis, biodegradation, and toxicity.

PubMed

Tehrani-Bagha, A R; Holmberg, K; van Ginkel, C G; Kean, M

2015-07-01

The paper describes synthesis and characterization of a new type of cationic gemini surfactant, which has dodecyl tails and a spacer that contains an ester bond. The nomenclature used to describe the structure is 12Q2OCO1Q12, with Q being a quaternary ammonium group and the numbers indicating the number of methylene or methyl groups. Due to the close proximity to the two quaternary ammonium groups, the ester bond is very stable on the acid side and very labile already at slightly alkaline conditions. The hydrolysis products are two single chain surfactants (i.e. 12Q2OH and 12Q1COOH) which are less surface active than the intact gemini surfactant. 12Q2OCO1Q12 was found to be readily biodegradable, i.e. it gave more than 60% biodegradation after 28 days. This is interesting because similar gemini surfactants but with ester bonds in the tails instead of the spacer, have previously been found not to be readily biodegradable. The gemini surfactant was found to be toxic to aquatic organisms (ErC50 value of 0.27 mg/l), although less toxic than the two hydrolysis products. Copyright © 2014 Elsevier Inc. All rights reserved.

One-pot Diels–Alder cycloaddition/gold(I)-catalyzed 6-endo-dig cyclization for the synthesis of the complex bicyclo[3.3.1]alkenone framework

PubMed Central

Sow, Boubacar; Bellavance, Gabriel; Barabé, Francis

2011-01-01

Summary The rapid synthesis of bicyclo[m.n.1]alkanone cores possessing quaternary carbon centers adjacent to a bridged ketone represents a significant synthetic challenge. This type of architectural feature is embedded in various complex biologically active compounds such as hyperforin and garsubellin A. Herein, we report a highly diastereoselective one-pot Diels–Alder reaction/Au(I)-catalyzed carbocyclization to generate bicyclo[3.3.1]alkanones in yields ranging from 48–93%. PMID:21915201

A novel route to recognizing quaternary ammonium cations using electrospray mass spectrometry.

PubMed

Shackman, Holly M; Ding, Wei; Bolgar, Mark S

2015-01-01

Characterizing and elucidating structures is a commonplace and necessary activity in the pharmaceutical industry with mass spectrometry and NMR being the primary tools for analysis. Although many functional groups are readily identifiable, quaternary ammonium cations have proven to be difficult to unequivocally identify using these techniques. Due to the lack of an N-H bond, quaternary ammonium groups can only be detected in the (1)H NMR spectra by weak signals generated from long-range (14)N-H coupling, which by themselves are inconclusive evidence of a quaternary ammonium functional group. Due to their low intensity, these signals are frequently not detected. Additionally, ions cannot be differentiated in a mass spectrum as an M(+) or [M + H](+) ion without prior knowledge of the compound's structure. In order to utilize mass spectrometry as a tool for determining this functionality, ion cluster formation of quaternary ammonium cations and non-quaternary amines was studied using electrospray ionization. Several mobile phase modifiers were compared; however, the addition of small amounts of trifluoroacetic acid proved superior in producing characteristic and intense [M +2TFA](-) clusters for compounds containing quaternary ammonium cations when using negative electrospray. By fragmenting this characteristic ion using CID, nearly all compounds studied could be unambiguously identified as containing a quaternary ammonium cation or a non-quaternary amine attributable to the presence (non-quaternary amine) or absence (quaternary ammonium cation) of the resulting [2TFA + H](-) ion in the product spectra. This method of analysis provides a rapid, novel, and reliable technique for indicating the presence of quaternary ammonium cations in order to aid in structural elucidation.

Epiguruk: a late Quaternary environmental record from northwestern Alaska

USGS Publications Warehouse

Hamilton, T.D.; Ashley, G.M.

1993-01-01

Epiguruk, a prominent bluff along the Kobuk River in northwestern Alaska, exposes a rich depositional record of Quaternary eolian and fluvial sand, with associated loess, paleosols, and periglacial features. Three major complexes of alluvial and eolian deposits are separated by two conspicuous organic-rich paleosols which formed during cool-moist interstadial intervals. Sediments between the two paleosols include eolian, channel, and floodplain deposits that formed during alluviation of the Kobuk River to a height of about 12m above the present level. The youngest depositional complex, which overlies the upper paleosol, is divisible into late Wisconsinan and Holocene components and into fluvial-channel, flood-plain, eolian-dune, sand-sheet, loess, and pond facies. Eolian sand from the active Kobuk sand sea overloaded the river during late Wisconsinan time, causing it to alluviate to about 13m above its modern level. The Holocene record reflects erosion and deposition by a small southern Tributary to the Kobuk River, downcutting by the Kobuk River toward its modern level, and subsequent erosion across a meander belt nearly 8km wide. 66 radiocarbon ages, many from rooted shrubs, provide a firm chronology for the past 35 k.y. at Epiguruk. -from Authors

A phylogeographic study of the endemic rodent Eliurus carletoni (Rodentia: Nesomyinae) in an ecological transition zone of Northern Madagascar.

PubMed

Rakotoarisoa, Jean-Eric; Raheriarisena, Martin; Goodman, Steven M

2013-01-01

We conducted a mitochondrial phylogeographic study of the endemic dry forest rodent Eliurus carletoni (Rodentia: Nesomyinae) in an ecological transition zone of northern Madagascar (Loky-Manambato) and 2 surrounding regions (Ankarana and Analamerana). The main goal was to assess the evolutionary consequences on this taxon of the complex landscape features and Quaternary ecological vicissitudes. Three haplogroups were identified from the 215 specimens obtained from 15 populations. High levels of genetic diversity and significant genetic differentiation among populations were observed. The different geographical subdivisions of the study area by regions, by river catchment zones, and the physical distance between populations are not correlated with genetic patterns. In contrast, population structure is mostly explained by the geographic distribution of the samples among existing forest blocks. E. carletoni experienced a genetic bottleneck between 18 750 and 7500 years BP, which correlates with periods when moister climates existed on the island. Overall, our data suggest that the complex genetic patterns of E. carletoni can be explained by Quaternary climatic vicissitudes that resulted in habitat fluctuations between dry and humid forests, as well as subsequent human-induced fragmentation of forest habitat.

Quaternary structure of a G-protein-coupled receptor heterotetramer in complex with Gi and Gs.

PubMed

Navarro, Gemma; Cordomí, Arnau; Zelman-Femiak, Monika; Brugarolas, Marc; Moreno, Estefania; Aguinaga, David; Perez-Benito, Laura; Cortés, Antoni; Casadó, Vicent; Mallol, Josefa; Canela, Enric I; Lluís, Carme; Pardo, Leonardo; García-Sáez, Ana J; McCormick, Peter J; Franco, Rafael

2016-04-05

G-protein-coupled receptors (GPCRs), in the form of monomers or homodimers that bind heterotrimeric G proteins, are fundamental in the transfer of extracellular stimuli to intracellular signaling pathways. Different GPCRs may also interact to form heteromers that are novel signaling units. Despite the exponential growth in the number of solved GPCR crystal structures, the structural properties of heteromers remain unknown. We used single-particle tracking experiments in cells expressing functional adenosine A1-A2A receptors fused to fluorescent proteins to show the loss of Brownian movement of the A1 receptor in the presence of the A2A receptor, and a preponderance of cell surface 2:2 receptor heteromers (dimer of dimers). Using computer modeling, aided by bioluminescence resonance energy transfer assays to monitor receptor homomerization and heteromerization and G-protein coupling, we predict the interacting interfaces and propose a quaternary structure of the GPCR tetramer in complex with two G proteins. The combination of results points to a molecular architecture formed by a rhombus-shaped heterotetramer, which is bound to two different interacting heterotrimeric G proteins (Gi and Gs). These novel results constitute an important advance in understanding the molecular intricacies involved in GPCR function.

Sol-Gel-Synthesis of Nanoscopic Complex Metal Fluorides

PubMed Central

Rehmer, Alexander; Scheurell, Kerstin; Scholz, Gudrun; Kemnitz, Erhard

2017-01-01

The fluorolytic sol-gel synthesis for binary metal fluorides (AlF3, CaF2, MgF2) has been extended to ternary and quaternary alkaline earth metal fluorides (CaAlF5, Ca2AlF7, LiMgAlF6). The formation and crystallization of nanoscopic ternary CaAlF5 and Ca2AlF7 sols in ethanol were studied by 19F liquid and solid state NMR (nuclear magnetic resonance) spectroscopy, as well as transmission electron microscopy (TEM). The crystalline phases of the annealed CaAlF5, Ca2AlF7, and LiMgAlF6 xerogels between 500 and 700 °C could be determined by X-ray powder diffraction (XRD) and 19F solid state NMR spectroscopy. The thermal behavior of un-annealed nanoscopic ternary and quaternary metal fluoride xerogels was ascertained by thermal analysis (TG/DTA). The obtained crystalline phases of CaAlF5 and Ca2AlF7 derived from non-aqueous sol-gel process were compared to crystalline phases from the literature. The corresponding nanoscopic complex metal fluoride could provide a new approach in ceramic and luminescence applications. PMID:29099086

Preliminary maps of Quaternary deposits and liquefaction susceptibility, nine-county San Francisco Bay region, California: a digital database

USGS Publications Warehouse

Knudsen, Keith L.; Sowers, Janet M.; Witter, Robert C.; Wentworth, Carl M.; Helley, Edward J.; Nicholson, Robert S.; Wright, Heather M.; Brown, Katherine H.

2000-01-01

This report presents a preliminary map and database of Quaternary deposits and liquefaction susceptibility for the nine-county San Francisco Bay region, together with a digital compendium of ground effects associated with past earthquakes in the region. The report consists of (1) a spatial database of fivedata layers (Quaternary deposits, quadrangle index, and three ground effects layers) and two text layers (a labels and leaders layer for Quaternary deposits and for ground effects), (2) two small-scale colored maps (Quaternary deposits and liquefaction susceptibility), (3) a text describing the Quaternary map, liquefaction interpretation, and the ground effects compendium, and (4) the databse description pamphlet. The nine counties surrounding San Francisco Bay straddle the San Andreas fault system, which exposes the region to serious earthquake hazard (Working Group on California Earthquake Probabilities, 1999). Much of the land adjacent to the Bay and the major rivers and streams is underlain by unconsolidated deposits that are particularly vulnerable to earthquake shaking and liquefaction of water-saturated granular sediment. This new map provides a modern and regionally consistent treatment of Quaternary surficial deposits that builds on the pioneering mapping of Helley and Lajoie (Helley and others, 1979) and such intervening work as Atwater (1982), Helley and others (1994), and Helley and Graymer (1997a and b). Like these earlier studies, the current mapping uses geomorphic expression, pedogenic soils, and inferred depositional environments to define and distinguish the map units. In contrast to the twelve map units of Helley and Lajoie, however, this new map uses a complex stratigraphy of some forty units, which permits a more realistic portrayal of the Quaternary depositional system. The two colored maps provide a regional summary of the new mapping at a scale of 1:275,000, a scale that is sufficient to show the general distribution and relationships of the map units but cannot distinguish the more detailed elements that are present in the database. The report is the product of years of cooperative work by the USGS National Earthquake Hazards Reduction Program (NEHRP) and National Cooperative Geologic Mapping Program, William Lettis and & Associates, Inc. (WLA) and, more recently, by the California Division of Mines and Geology as well. An earlier version was submitted to the Geological Survey by WLA as a final report for a NEHRP grant (Knudsen and others, 2000). The mapping has been carried out by WLA geologists under contract to the NEHRP Earthquake Program (Grants #14-08-0001-G2129, 1434-94-G-2499, 1434-HQ-97-GR-03121, and 99-HQ-GR-0095) and with other limited support from the County of Napa, and recently also by the California Division of Mines and Geology. The current map consists of this new mapping and revisions of previous USGS mapping.

Quaternary and Geomorphology.

ERIC Educational Resources Information Center

Andrews, J. T.; Graf, W. L.

1983-01-01

Highlights conferences and meetings of organizations involved with quaternary geology and geomorphology, including International Union of Quaternary Research Conference held in Moscow. The impetus of a revision of "The Quaternary of the United States" resulted from this conference. Includes activities/aims of "Friends of the…

Reconstruction of the Late Quaternary Glaciation of the Macha Khola valley (Gorkha Himal, Nepal) using relative and absolute ( 14C, 10Be, dendrochronology) dating techniques

NASA Astrophysics Data System (ADS)

Zech, W.; Glaser, B.; Abramowski, U.; Dittmar, C.; Kubik, P. W.

2003-11-01

Late Quaternary glacier fluctuations in the Macha Khola valley (Gorkha Himal, Nepal) were reconstructed using relative and absolute dating techniques. Our results indicate that younger moraine complexes were left by Late Holocene (<1.7 cal. ka BP), mid-Holocene (ca 3 cal. ka BP), and Lateglacial (ca 13 cal. ka BP) ice advances. Older Late Quaternary glacier advances occurred during Marine Oxygen Isotope Stages (MIS) 2 and 3-4. No relics of Middle or Early Pleistocene glaciations could be found. During MIS 3-4, glaciers advanced down to an altitude of at least 2150 m a.s.l., corresponding to an ELA depression of approximately 1300 m. At about 3500 m a.s.l., the MIS 2 Macha Khola glacier reached almost the thickness of the former MIS 3-4 glacier and retreated some time before 17.9 cal. ka BP. The Lateglacial glacier advanced again several times to altitudes between 2450 and 3400 m a.s.l. The mid-Holocene glaciers extended much farther down-valley than the Late Holocene ones. Dendrochronological data of Abies spectabilis suggested several periods of unfavourable growth conditions especially at the beginning of the 19th (1820) and 20th (1905) centuries.

Ice-sheet dynamics through the Quaternary on the mid-Norwegian continental margin inferred from 3D seismic data.

PubMed

Montelli, A; Dowdeswell, J A; Ottesen, D; Johansen, S E

2017-02-01

Reconstructing the evolution of ice sheets is critical to our understanding of the global environmental system, but most detailed palaeo-glaciological reconstructions have hitherto focused on the very recent history of ice sheets. Here, we present a three-dimensional (3D) reconstruction of the changing nature of ice-sheet derived sedimentary architecture through the Quaternary Ice Age of almost 3 Ma. An extensive geophysical record documents a marine-terminating, calving Fennoscandian Ice Sheet (FIS) margin present periodically on the mid-Norwegian shelf since the beginning of the Quaternary. Spatial and temporal variability of the FIS is illustrated by the gradual development of fast-flowing ice streams and associated intensification of focused glacial erosion and sedimentation since that time. Buried subglacial landforms reveal a complex and dynamic ice sheet, with converging palaeo-ice streams and several flow-switching events that may reflect major changes in topography and basal thermal regime. Lack of major subglacial meltwater channels suggests a largely distributed drainage system beneath the marine-terminating part of the FIS. This palaeo-environmental examination of the FIS provides a useful framework for ice-sheet modelling and shows that fragmentary preservation of buried surfaces and variability of ice-sheet dynamics should be taken into account when reconstructing glacial history from spatially limited datasets.

A simple route to alloyed quaternary nanocrystals Ag-In-Zn-S with shape and size control.

PubMed

Gabka, Grzegorz; Bujak, Piotr; Giedyk, Kamila; Ostrowski, Andrzej; Malinowska, Karolina; Herbich, Jerzy; Golec, Barbara; Wielgus, Ireneusz; Pron, Adam

2014-05-19

A convenient method of the preparation of alloyed quaternary Ag-In-Zn-S nanocrystals is elaborated, in which a multicomponent mixture of simple and commercially available precursors, namely, silver nitrate, indium(III) chloride, zinc stearate, 1-dodecanethiol, and sulfur, is used with 1-octadecene as a solvent. The formation of quaternary nanocrystals necessitates the use of an auxiliary sulfur precursor, namely, elemental sulfur dissolved in oleylamine, in addition to 1-dodecanethiol. Without this additional precursor binary ZnS nanocrystals are formed. The optimum reaction temperature of 180 °C was also established. In these conditions shape, size, and composition of the resulting nanocrystals can be adjusted in a controlled manner by changing the molar ratio of the precursors in the reaction mixture. For low zinc stearate contents anisotropic rodlike (ca.3 nm x 10 nm) and In-rich nanocrystals are obtained. This is caused by a significantly higher reactivity of the indium precursor as compared to the zinc one. With increasing zinc precursor content the reactivities of both precursors become more balanced, and the resulting nanocrystals are smaller (1.5-4.0 nm) and become Zn-rich as evidenced by transmission electron microscopy, X-ray diffraction, and energy-dispersive spectrometry investigations. Simultaneous increases in the zinc and sulfur precursor content result in an enlargement of nanocrystals (2.5 to 5.0 nm) and further increase in the molar ZnS content (up to 0.76). The prepared nanoparticles show stable photoluminescence with the quantum yield up to 37% for In and Zn-rich nanocrystals. Their hydrodynamic diameter in toluene dispersion, determined by dynamic light scattering, is roughly twice larger than the diameter of their inorganic core.

Structural analysis of a 3-deoxy-D-arabino-heptulosonate 7-phosphate synthase with an N-terminal chorismate mutase-like regulatory domain

DOE Office of Scientific and Technical Information (OSTI.GOV)

Light, Samuel H.; Halavaty, Andrei S.; Minasov, George

2012-06-27

3-Deoxy-D-arabino-heptulosonate 7-phosphate synthase (DAHPS) catalyzes the first step in the biosynthesis of a number of aromatic metabolites. Likely because this reaction is situated at a pivotal biosynthetic gateway, several DAHPS classes distinguished by distinct mechanisms of allosteric regulation have independently evolved. One class of DAHPSs contains a regulatory domain with sequence homology to chorismate mutase - an enzyme further downstream of DAHPS that catalyzes the first committed step in tyrosine/phenylalanine biosynthesis - and is inhibited by chorismate mutase substrate (chorismate) and product (prephenate). Described in this work, structures of the Listeria monocytogenes chorismate/prephenate regulated DAHPS in complex with Mn{sup 2+}more » and Mn{sup 2+} + phosphoenolpyruvate reveal an unusual quaternary architecture: DAHPS domains assemble as a tetramer, from either side of which chorismate mutase-like (CML) regulatory domains asymmetrically emerge to form a pair of dimers. This domain organization suggests that chorismate/prephenate binding promotes a stable interaction between the discrete regulatory and catalytic domains and supports a mechanism of allosteric inhibition similar to tyrosine/phenylalanine control of a related DAHPS class. We argue that the structural similarity of chorismate mutase enzyme and CML regulatory domain provides a unique opportunity for the design of a multitarget antibacterial.« less

Quaternary re-arrangement analysed by spectral enhancement: the interaction of a sporulation repressor with its antagonist.

PubMed

Scott, D J; Leejeerajumnean, S; Brannigan, J A; Lewis, R J; Wilkinson, A J; Hoggett, J G

1999-11-12

The protein/protein interaction between SinI and SinR has been studied by analytical ultracentrifugation and gel electrophoresis in an attempt to understand how these proteins contribute to developmental control of sporulation in Bacillus subtilis. SinR was found to be tetrameric, while SinI was found to exist as monomers and dimers in a rapidly reversible equilibrium. Labelling of SinR by incorporating the tryptophan analogue 7-azatryptophan (7AW) into the protein in place of tryptophan shifts the UV absorbance spectrum, thus allowing selective monitoring of 7AWSinR at 315 nm using the UV absorption optics of the analytical ultracentrifuge. Selective monitoring of SinR in mixtures of SinR and SinI enables the binding and stoichiometry of the interaction to be investigated quantitatively and unambiguously. We demonstrate that the oligomeric forms of SinR and SinI re-arrange to form a tight 1:1 SinR:SinI complex, with no stable intermediate species. A fragment of SinR, SinR(1-69), which contains only the DNA-binding domain, was found to be monomeric, showing that the protein appears not to oligomerise in a similar manner to the Cro repressor, a protein with which it shares a marked structural similarity. Copyright 1999 Academic Press.

Structure-based characterization of multiprotein complexes.

PubMed

Wiederstein, Markus; Gruber, Markus; Frank, Karl; Melo, Francisco; Sippl, Manfred J

2014-07-08

Multiprotein complexes govern virtually all cellular processes. Their 3D structures provide important clues to their biological roles, especially through structural correlations among protein molecules and complexes. The detection of such correlations generally requires comprehensive searches in databases of known protein structures by means of appropriate structure-matching techniques. Here, we present a high-speed structure search engine capable of instantly matching large protein oligomers against the complete and up-to-date database of biologically functional assemblies of protein molecules. We use this tool to reveal unseen structural correlations on the level of protein quaternary structure and demonstrate its general usefulness for efficiently exploring complex structural relationships among known protein assemblies. Copyright © 2014 The Authors. Published by Elsevier Inc. All rights reserved.

Aluminum electroplating on steel from a fused bromide electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prabhat K. Tripathy; Laura A. Wurth; Eric J. Dufek

A quaternary bromide bath (LiBr–KBr–CsBr–AlBr3) was used to electro-coat aluminum on steel substrates. The electrolytewas prepared by the addition of AlBr3 into the eutectic LiBr–KBr–CsBr melt. A smooth, thick, adherent and shiny aluminum coating could be obtained with 80 wt.% AlBr3 in the ternary melt. The SEM photographs of the coated surfaces suggest the formation of thick and dense coatings with good aluminum coverage. Both salt immersion and open circuit potential measurement suggested that the coatings did display a good corrosionresistance behavior. Annealing of the coated surfaces, prior to corrosion tests, suggested the robustness of the metallic aluminum coating inmore » preventing the corrosion of the steel surfaces. Studies also indicated that the quaternary bromide plating bath can potentially provide a better aluminumcoating on both ferrous and non-ferrous metals, including complex surfaces/geometries.« less

Aluminium Electroplating on Steel from a Fused Bromide Electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prabhat Tripathy; Laura Wurth; Eric Dufek

A quaternary bromide bath (LiBr-KBr-CsBr-AlBr3) was used to electro-coat aluminium on steel substrates. The electrolyte was prepared by the addition of AlBr3 into the eutectic LiBr-KBr-CsBr melt. A smooth, thick, adherent and shiny aluminium coating could be obtained with 80 wt.% AlBr3 in the ternary melt. The SEM photographs of the coated surfaces suggest the formation of thick and dense coatings with good aluminium coverage. Both salt immersion and open circuit potential measurement suggest that the coatings did display good corrosion-resistance behavior. Annealing of the coated surfaces, prior to corrosion tests, suggested the robustness of the metallic aluminium coating inmore » preventing the corrosion of the steel surfaces. Studies also indicated that the quaternary bromide plating bath can potentially provide a better aluminium coating on both ferrous and non-ferrous metals, including complex surfaces/geometries.« less

Quaternary Sea-ice history in the Arctic Ocean based on a new Ostracode sea-ice proxy

USGS Publications Warehouse

Cronin, T. M.; Gemery, L.; Briggs, W.M.; Jakobsson, M.; Polyak, L.; Brouwers, E.M.

2010-01-01

Paleo-sea-ice history in the Arctic Ocean was reconstructed using the sea-ice dwelling ostracode Acetabulastoma arcticum from late Quaternary sediments from the Mendeleyev, Lomonosov, and Gakkel Ridges, the Morris Jesup Rise and the Yermak Plateau. Results suggest intermittently high levels of perennial sea ice in the central Arctic Ocean during Marine Isotope Stage (MIS) 3 (25-45 ka), minimal sea ice during the last deglacial (16-11 ka) and early Holocene thermal maximum (11-5 ka) and increasing sea ice during the mid-to-late Holocene (5-0 ka). Sediment core records from the Iceland and Rockall Plateaus show that perennial sea ice existed in these regions only during glacial intervals MIS 2, 4, and 6. These results show that sea ice exhibits complex temporal and spatial variability during different climatic regimes and that the development of modern perennial sea ice may be a relatively recent phenomenon. ?? 2010.

Ligand-Induced Asymmetry in Histidine Sensor Kinase Complex Regulates Quorum Sensing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Neiditch,M.; Federle, M.; Pompeani, A.

2006-01-01

Bacteria sense their environment using receptors of the histidine sensor kinase family, but how kinase activity is regulated by ligand binding is not well understood. Autoinducer-2 (AI-2), a secreted signaling molecule originally identified in studies of the marine bacterium Vibrio harveyi, regulates quorum-sensing responses and allows communication between different bacterial species. AI-2 signal transduction in V. harveyi requires the integral membrane receptor LuxPQ, comprised of periplasmic binding protein (LuxP) and histidine sensor kinase (LuxQ) subunits. Combined X-ray crystallographic and functional studies show that AI-2 binding causes a major conformational change within LuxP, which in turn stabilizes a quaternary arrangement inmore » which two LuxPQ monomers are asymmetrically associated. We propose that formation of this asymmetric quaternary structure is responsible for repressing the kinase activity of both LuxQ subunits and triggering the transition of V. harveyi into quorum-sensing mode.« less

21 CFR 172.165 - Quaternary ammonium chloride combination.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Quaternary ammonium chloride combination. 172.165... HUMAN CONSUMPTION Food Preservatives § 172.165 Quaternary ammonium chloride combination. The food additive, quaternary ammonium chloride combination, may be safely used in food in accordance with the...

Tertiary and Quaternary tectonic faulting in southernmost Illinois

USGS Publications Warehouse

Nelson, W.J.; Denny, F.B.; Devera, J.A.; Follmer, L.R.; Masters, J.M.

1997-01-01

Tertiary and/or Quaternary tectonic faulting is documented in three areas of southernmost Illinois: the Fluorspar Area Fault Complex (FAFC) in Pope and Massac Counties, the Ste. Genevieve Fault Zone (SGFZ) in Alexander and Union Counties, and the Commerce Fault Zone (CFZ) in Alexander County. In the FAFC, faults that strike NE and NNE displace Mounds Gravel (late Miocene to early Pleistocene) and, locally, the Metropolis terrace gravel (Pleistocene; pre-Woodfordian). No Woodfordian or younger deposits are deformed. Faults typically outline narrow, linear grabens that formed under tension with a component of strike slip. North-south to NW-trending vertical faults near the southeast end of the SGFZ displace Eocene sediments. Again, faults outline narrow grabens and show indications of strike slip. Deformed Quaternary sediments have not been observed. The CFZ, which trends northeast, displaces Mounds Gravel in Illinois and units as young as Peoria Silt (Woodfordian) in Missouri. Quaternary movement has been interpreted as right-lateral strike-slip. The CFZ coincides with a subtle gravity and magnetic lineament and seems to reflect a major feature in the basement. Surface expression in Illinois is subtle, but mafic and ultramafic intrusions, hydrothermal alteration and small faults align with the Commerce geophysical lineament. Earthquake foci in Missouri and Illinois lie on or close to the CFZ; some focal mechanisms fit the fault trend. Among these structures, only the CFZ exhibits slip that conforms to the current stress field (principal compressive stress axis E-W to ENE-WSW). Possibly, the stress field changed during Neogene time. Alternatively, high fluid pressures or local stress concentrations may have induced slip on less favorably oriented fractures. Tighter constraints are needed on timing, magnitude, and direction of Neogene displacement. ?? 1997 Elsevier Science B.V.

Quaternary evolution of the Fennoscandian Ice Sheet from 3D seismic data

NASA Astrophysics Data System (ADS)

Montelli, A.; Dowdeswell, J. A.; Ottesen, D.; Johansen, S. E.

2016-12-01

The Quaternary seismic stratigraphy and architecture of the mid-Norwegian continental shelf and slope are investigated using extensive grids of marine 2D and 3D seismic reflection data that cover more than 100,000 km2 of the continental margin. At least 26 distinct regional palaeo-surfaces have been interpreted within the stratigraphy of the Quaternary Naust Formation on the mid-Norwegian margin. Multiple assemblages of buried glacigenic landforms are preserved within the Naust Formation across most of the study area, facilitating detailed palaeo-glaciological reconstructions. We document a marine-terminating, calving Fennoscandian Ice Sheet (FIS) margin present periodically on the Norwegian shelf since at least the beginning of the Quaternary. Elongate, streamlined landforms interpreted as mega-scale glacial lineations (MSGLs) have been found within the upper part of the Naust sequence N ( 1.9-1.6 Ma), sugesting the development of fast-flowing ice streams since that time. Shifts in the location of depocentres and direction of features indicative of fast ice-flow suggest that several reorganisations in the FIS drainage have occurred since 1.5 Ma. Subglacial landforms reveal a complex and dynamic ice sheet, with converging palaeo-ice streams and several flow-switching events that may reflect major changes in topography and internal ice-sheet structure. Lack of subglacial meltwater channels suggests a largely distributed, low-volume meltwater system that drained the FIS through permeable subglacial till without leaving much erosional evidence. This regional palaeo-environmental examination of the FIS provides a useful framework for ice-sheet modelling and shows that fragmentary preservation of buried surfaces and variability of ice-sheet dynamics should be taken into account when reconstructing glacial history from spatially limited datasets.

Understanding the paleo environment in the Danish North Sea using 2D and 3D seismic analyses

NASA Astrophysics Data System (ADS)

Prins, Lasse K.; Clausen, Ole R.; Andresen, Katrine J.

2017-04-01

This study presents the first detailed and integrated mapping of buried Quaternary valleys, river systems and iceberg scourings from the Danish North Sea region. The mapped features coincide spatially but have very different characteristics and incision levels which allow us to constrain their relative timing and differentiate their environment of formation (subglacial, proglacial and marine). The results of the study bring new critical information regarding the paleoenvironment of the North Sea Basin during the latest Quaternary deglaciation period and our analysis provide a well-tested workflow for utilizing 2D and 3D seismic data in relation to paleogeographical reconstructions. Our analysis is based on interpretation of conventional 3D seismic and high-resolution sparker data from the Southern Danish Central Graben. The project forms part of the portfolio for the 'Danish Hydrocarbon Research and Technology Centre' and aims at building a high-resolution 3D geological-geotechnical model of the shallow subsurface by using geophysical data combined with geological and geotechnical data from shallow borings. One of the objectives is to map potential geohazards for offshore installations such as buried valleys and constrain their geotechnical properties. The central North Sea is known to have been covered by glaciers several times during the Quaternary with climate changing between arctic and boreal. Marine conditions periodically prevailed and large river systems mainly from central Europe dominated during periods of subaerial exposure. Hence, many buried erosional incisions, primarily tunnel valleys but also river systems, can be observed within the upper 200-400 meters of the Quaternary succession throughout the central North Sea region. A high-resolution mapping of the infill of the tunnel valleys and river systems have however not previously been presented. Our analysis shows that within the study area at least four generations of tunnel valley formation and river system incisions can be mapped. The tunnel valleys have a strong NE-SW orientation and are typically characterized by an irregular base. The fluvial river systems which are the youngest, are smaller, typically with an anastomosing appearance. They generally have an NW-SE strike perpendicular to the older tunnel valleys. Clear sedimentary structures can be recognized on the high-resolution 2D seismic data indicating a complex history of cut and fill. In general, the study area displays a very heterogenic sedimentation pattern with varying valley types and significant lateral variations within the same valleys revealing a subtle interplay between incision and infilling. In some areas we furthermore see a distinct control of the river system morphology by deeper salt structures adding to the complexity of controlling factors for the rivers and tunnel valleys in the study area. The results of the study provide valuable information on the evolution of the Quaternary ice-sheets and drainage patterns and hence exemplify the use of seismic data for Quaternary paleo-environmental studies. With the good control on the distribution and infill of buried valleys and river systems, the study furthermore provides the first constrain to a detailed 3D model of different litho-facies based on seismic facies analysis combined with information from shallow borings.

The preparation of new perfluoro ether fluids exhibiting excellent thermal-oxidative stabilities

NASA Technical Reports Server (NTRS)

Jones, William R., Jr.; Bierschenk, Thomas R.; Juhlke, Timothy J.; Kawa, Hajima; Lagow, Richard J.

1988-01-01

A series of low molecular weight perfluoroalkyl ethers (PFAEs) were synthesized by direct fluorination. Viscosity-temperature properties and oxidation stabilities were determined. Viscosity-temperature correlations indicated that increases in branching and increases in the size of the branching substituent caused a deterioration in viscometric properties (i.e., an increase in ASTM slope). In addition, increasing the ratio of carbon to oxygen in these compounds also increased the ASTM slope. Preliminary oxidation stability measurements indicated that highly branched PFAE fluids (i.e., those containing quaternary carbons) may be less stable than either those containing a single trifluoromethyl pendant group or those containing no branching at all.

The preparation of new perfluoroether fluids exhibiting excellent thermal-oxidative stabilities

NASA Technical Reports Server (NTRS)

Jones, W. R., Jr.; Bierschenk, T. R.; Juhlke, T. J.; Kawa, H.; Lagow, R. J.

1986-01-01

A series of low molecular weight perfluoroalkylethers (PFAE) were synthesized by direct fluorination. Viscosity-temperature properties and oxidation stabilities were determined. Viscosity-temperature correlations indicated that increases in branching and increases in the size of the branching substituent caused a deterioration in viscometric properties (i.e., an increase in ASTM slope). In addition, increasing the ratio of carbon to oxygen in these compounds also increased the ASTM slope. Preliminary oxidation stability tests indicated that highly branched PFAE fluids. (i.e., those containing quaternary carbons) may be less stable than either those containing a single trifluoromethyl pendant group or those containing no branching at all.

Quaternary prevention: reviewing the concept.

PubMed

Martins, Carlos; Godycki-Cwirko, Maciek; Heleno, Bruno; Brodersen, John

2018-12-01

According to the Wonca International Dictionary for General/Family Practice Quaternary Prevention is defined as: 'Action taken to identify patient at risk of overmedicalization, to protect him from new medical invasion, and to suggest to him interventions, which are ethically acceptable.' The concept of quaternary prevention was initially proposed by Marc Jamoulle and the targets were mainly patients with illness but without a disease. The purpose of this opinion article is to open the debate around a new possible definition and a new conceptual model of quaternary prevention based on the belief that quaternary prevention should be present in physicians' minds for every intervention they suggest to a patient. The debate around quaternary prevention is vital in the context of contemporary medicine and has expanded worldwide. The human being may suffer harm from medical interventions from conception, during their childhood, during their entire healthy lifetime as well as during a self-limited disease, a chronic disease, or a terminal disease. The current definition of quaternary prevention has limitations because it excludes patients and medical interventions where a quaternary prevention perspective would be needed and useful to protect patients from harm. In this context, a new definition and conceptual model of quaternary prevention is proposed. In this new proposal, quaternary prevention is defined as an 'action taken to protect individuals (persons/patients) from medical interventions that are likely to cause more harm than good.'

Compound Specific and Enantioselective Stable Isotope Analysis as Tools To Monitor Transformation of Hexachlorocyclohexane (HCH) in a Complex Aquifer System.

PubMed

Liu, Yaqing; Bashir, Safdar; Stollberg, Reiner; Trabitzsch, Ralf; Weiß, Holger; Paschke, Heidrun; Nijenhuis, Ivonne; Richnow, Hans-Hermann

2017-08-15

Technical hexachlorocyclohexane (HCH) mixtures and Lindane (γ-HCH) have been produced in Bitterfeld-Wolfen, Germany, for about 30 years until 1982. In the vicinity of the former dump sites and production facilities, large plumes of HCHs persist within two aquifer systems. We studied the natural attenuation of HCH in these groundwater systems through a combination of enantiomeric and carbon isotope fractionation to characterize the degradation of α-HCH in the areas downstream of a former disposal and production site in Bitterfeld-Wolfen. The concentration and isotope composition of α-HCH from the Quaternary and Tertiary aquifers were analyzed. The carbon isotope compositions were compared to the source signal of waste deposits for the dumpsite and highly contaminated areas. The average value of δ 13 C at dumpsite was -29.7 ± 0.3 ‰ and -29.0 ± 0.1 ‰ for (-) and (+)α-HCH, respectively, while those for the β-, γ-, δ-HCH isomers were -29.0 ± 0.3 ‰, -29.5 ± 0.4 ‰, and -28.2 ± 0.2 ‰, respectively. In the plume, the enantiomer fraction shifted up to 0.35, from 0.50 at source area to 0.15 (well T1), and was found accompanied by a carbon isotope enrichment of 5 ‰ and 2.9 ‰ for (-) and (+)α-HCH, respectively. The established model for interpreting isotope and enantiomer fractionation patterns showed potential for analyzing the degradation process at a field site with a complex history with respect to contamination and fluctuating geochemical conditions.

Noncovalent Complexation of Monoamine Neurotransmitters and Related Ammonium Ions by Tetramethoxy Tetraglucosylcalix[4]arene

NASA Astrophysics Data System (ADS)

Torvinen, Mika; Kalenius, Elina; Sansone, Francesco; Casnati, Alessandro; Jänis, Janne

2012-02-01

The noncovalent complexation of monoamine neurotransmitters and related ammonium and quaternary ammonium ions by a conformationally flexible tetramethoxy glucosylcalix[4]arene was studied by electrospray ionization Fourier transform ion cyclotron resonance (ESI-FTICR) mass spectrometry. The glucosylcalixarene exhibited highest binding affinity towards serotonin, norepinephrine, epinephrine, and dopamine. Structural properties of the guests, such as the number, location, and type of hydrogen bonding groups, length of the alkyl spacer between the ammonium head-group and the aromatic ring structure, and the degree of nitrogen substitution affected the complexation. Competition experiments and guest-exchange reactions indicated that the hydroxyl groups of guests participate in intermolecular hydrogen bonding with the glucocalixarene.

Quaternary prevention: reviewing the concept

PubMed Central

Martins, Carlos; Godycki-Cwirko, Maciek; Heleno, Bruno; Brodersen, John

2018-01-01

Abstract Background: According to the Wonca International Dictionary for General/Family Practice Quaternary Prevention is defined as: ‘Action taken to identify patient at risk of overmedicalization, to protect him from new medical invasion, and to suggest to him interventions, which are ethically acceptable.’ The concept of quaternary prevention was initially proposed by Marc Jamoulle and the targets were mainly patients with illness but without a disease. Objectives: The purpose of this opinion article is to open the debate around a new possible definition and a new conceptual model of quaternary prevention based on the belief that quaternary prevention should be present in physicians’ minds for every intervention they suggest to a patient. Discussion: The debate around quaternary prevention is vital in the context of contemporary medicine and has expanded worldwide. The human being may suffer harm from medical interventions from conception, during their childhood, during their entire healthy lifetime as well as during a self-limited disease, a chronic disease, or a terminal disease. The current definition of quaternary prevention has limitations because it excludes patients and medical interventions where a quaternary prevention perspective would be needed and useful to protect patients from harm. In this context, a new definition and conceptual model of quaternary prevention is proposed. Conclusion: In this new proposal, quaternary prevention is defined as an ‘action taken to protect individuals (persons/patients) from medical interventions that are likely to cause more harm than good.’ PMID:29384397

Geological and climatic changes in quaternary shaped the evolutionary history of Calibrachoa heterophylla, an endemic South-Atlantic species of petunia

PubMed Central

2013-01-01

Background The glacial and interglacial cycles that characterized the Quaternary greatly affected the distribution and genetic diversity of plants. In the Neotropics, few phylogeographic studies have focused on coastal species outside of the Atlantic Rainforest. Climatic and sea level changes during the Quaternary played an important role in the evolutionary history of many organisms found in coastal regions. To contribute to a better understanding of plant evolution in this environment in Southern South America, we focused on Calibrachoa heterophylla (Solanaceae), an endemic and vulnerable wild petunia species from the South Atlantic Coastal Plain (SACP). Results We assessed DNA sequences from two cpDNA intergenic spacers and analyzed them using a phylogeographic approach. The present phylogeographic study reveals the influence of complex geologic and climatic events on patterns of genetic diversification. The results indicate that C. heterophylla originated inland and subsequently colonized the SACP; the data show that the inland haplogroup is more ancient than the coastal one and that the inland was not affected by sea level changes in the Quaternary. The major diversification of C. heterophylla that occurred after 0.4 Myr was linked to sea level oscillations in the Quaternary, and any diversification that occurred before this time was obscured by marine transgressions that occurred before the coastal sand barrier’s formation. Results of the Bayesian skyline plot showed a recent population expansion detected in C. heterophylla seems to be related to an increase in temperature and humidity that occurred at the beginning of the Holocene. Conclusions The geographic clades have been formed when the coastal plain was deeply dissected by paleochannels and these correlate very well with the distributional limits of the clades. The four major sea transgressions formed a series of four sand barriers parallel to the coast that progressively increased the availability of coastal areas after the regressions and that may have promoted the geographic structuring of genetic diversity observed today. The recent population expansion for the entire species may be linked with the event of marine regression after the most recent sea transgression at ~5 kya. PMID:23987105

Late Quaternary Faulting along the San Juan de los Planes Fault Zone, Baja California Sur, Mexico

NASA Astrophysics Data System (ADS)

Busch, M. M.; Coyan, J. A.; Arrowsmith, J.; Maloney, S. J.; Gutierrez, G.; Umhoefer, P. J.

2007-12-01

As a result of continued distributed deformation in the Gulf Extensional Province along an oblique-divergent plate margin, active normal faulting is well manifest in southeastern Baja California. By characterizing normal-fault related deformation along the San Juan de los Planes fault zone (SJPFZ) southwest of La Paz, Baja California Sur we contribute to understanding the patterns and rates of faulting along the southwest gulf-margin fault system. The geometry, history, and rate of faulting provide constraints on the relative significance of gulf-margin deformation as compared to axial system deformation. The SJPFZ is a major north-trending structure in the southern Baja margin along which we focused our field efforts. These investigations included: a detailed strip map of the active fault zone, including delineation of active scarp traces and geomorphic surfaces on the hanging wall and footwall; fault scarp profiles; analysis of bedrock structures to better understand how the pattern and rate of strain varied during the development of this fault zone; and a gravity survey across the San Juan de los Planes basin to determine basin geometry and fault behavior. The map covers a N-S swath from the Gulf of California in the north to San Antonio in the south, an area ~45km long and ~1-4km wide. Bedrock along the SJPFZ varies from Cretaceous Las Cruces Granite in the north to Cretaceous Buena Mujer Tonalite in the south and is scarred by shear zones and brittle faults. The active scarp-forming fault juxtaposes bedrock in the footwall against Late Quaternary sandstone-conglomerate. This ~20m wide zone is highly fractured bedrock infused with carbonate. The northern ~12km of the SJPFZ, trending 200°, preserves discontinuous scarps 1-2km long and 1-3m high in Quaternary units. The scarps are separated by stretches of bedrock embayed by hundreds of meters-wide tongues of Quaternary sandstone-conglomerate, implying low Quaternary slip rate. Further south, ~2 km north of the Los Planes highway, the fault steps to the right 2km with no overlap. The fault is inactive until ~3km south of the Los Planes highway where scarp heights in the Quaternary sediments rise to ~3-11m for ~11km with an average trend of 160°, implying increasing slip rate. The fault then steps left 2km with no overlap, trending 145°. Scarp heights range from 3-6m in the step. The southernmost 9km of the fault zone, trending 200°, is marked by discontinuous scarps and embayed bedrock, reflecting diminished fault activity. The footwall landscape in this area is characterized by a broad, gently-sloping, low-relief pediment surface with thin Quaternary cover, disrupted by inselberg-like hills. The young scarp-forming fault appears to have reactivated older faults to rupture this pediment, reflecting the episodic nature of slip along this fault zone. Preliminary OSL ages of the youngest faulted deposit imply a Late Pleistocene-Holocene slip rate of 0.1-1mm/yr. The SJPFZ is thus characterized by reactivation of pre-existing faults to rupture a pre-existing low relief erosional landscape. Whereas the entire region might have experienced the quiescent period that allowed for development of the low- relief, stable surface along the SJPFZ, we speculate that while the SJPFZ was dormant, other faults within the gulf-margin system were actively accommodating strain.

Publications - MP 141 | Alaska Division of Geological & Geophysical Surveys

Science.gov Websites

DGGS MP 141 Publication Details Title: Quaternary faults and folds in Alaska: A digital database Combellick, R.A., 2012, Quaternary faults and folds in Alaska: A digital database, in Koehler, R.D Quaternary faults, scale 1:3,700,000 (63.0 M) Digital Geospatial Data Digital Geospatial Data Quaternary

Generation of stable cell line by using chitosan as gene delivery system.

PubMed

Şalva, Emine; Turan, Suna Özbaş; Ekentok, Ceyda; Akbuğa, Jülide

2016-08-01

Establishing stable cell lines are useful tools to study the function of various genes and silence or induce the expression of a gene of interest. Nonviral gene transfer is generally preferred to generate stable cell lines in the manufacturing of recombinant proteins. In this study, we aimed to establish stable recombinant HEK-293 cell lines by transfection of chitosan complexes preparing with pDNA which contain LacZ and GFP genes. Chitosan which is a cationic polymer was used as gene delivery system. Stable HEK-293 cell lines were established by transfection of cells with complexes which were prepared with chitosan and pVitro-2 plasmid vector that contains neomycin drug resistance gene, beta gal and GFP genes. The transfection efficiency was shown with GFP expression in the cells using fluorescence microscopy. Beta gal protein expression in stable cells was examined by beta-galactosidase assay as enzymatically and X-gal staining method as histochemically. Full complexation was shown in the above of 1/1 ratio in the chitosan/pDNA complexes. The highest beta-galactosidase activity was obtained with transfection of chitosan complexes. Beta gal gene expression was 15.17 ng/ml in the stable cells generated by chitosan complexes. In addition, intensive blue color was observed depending on beta gal protein expression in the stable cell line with X-gal staining. We established a stable HEK-293 cell line that can be used for recombinant protein production or gene expression studies by transfecting the gene of interest.

Nitrogen isotopes from terrestrial organic matter as a new paleoclimatic proxy for pre-quaternary time

NASA Astrophysics Data System (ADS)

Tramoy, romain; Schnyder, johann; thuy Nguyen Tu, thanh; Yans, johan; Storme, jean yves; Sebilo, mathieu; Derenne, sylvie; Jacob, jérémy; Baudin, françois

2014-05-01

Marine and lacustrine sedimentary organic matter is often dominated by algal-bacterial production. Its nitrogen isotopic composition (δ15Norg) is frequently used to reconstruct biogeochemical processes involved in the nitrogen cycle, such as N utilization by organisms (e.g. Altabet et al., 1995), denitrification and diagenesis processes (e.g. Altabet et al., 1995; Sebilo et al., 2003; Gälman et al., 2009) or to evidence N sources variability (e.g. Hodell and Schelske, 1998; Vreca and Muri, 2006) . However, all these parameters and processes make N isotopic signals in marine and lacustrine environments often very complex to interpret. After pioneer studies, Mariotti et al. (1981), Austin and Vitousek (1998), Amundson et al. (2003), Swap et al. (2004), and Liu and Wang (2008) have shown that the δ15Norg of modern or quaternary terrestrial plants seem to be positively correlated with temperature and negatively correlated with precipitations. Therefore, δ15Norg of terrestrial OM might be a better record for paleoclimatic studies than δ15Norg of sedimentary OM dominated by algal-bacterial production. Recently, promising organic nitrogen isotopic data (δ15Norg) have been published on lignites from the Dieppe-Hampshire Basin (Paleocene-Eocene transition, Normandy (Storme et al., 2012). Authors suggest that the δ15Norg recorded local paleoclimatic and paleoenvironmental conditions. Following these results, the aim of this work is to test the use of stable nitrogen isotopes in terrestrial OM as a new paleoclimatic marker for pre-quaternary geological series. Does δ15Norg constitute a valuable tool to reconstruct past climates? What are the limits in the use of this proxy and possible methodological bias related to organic sources or diagenetic processes? To address these questions, δ15Norg must be measured in samples from periods associated with large and well documented climate change. We therefore selected a Liassic continental sedimentary succession from Taskomirsay, Kazakhstan. This succession is rich in dispersed OM and wood fragments allowing accurate N isotopes measurements. Preliminary results on δ13Corg and palynology suggest that the Pliensbachian/Toarcian transition is recorded at the top of the sedimentary succession. This transition has been studied for a long time since it is characterized by one of the most important global environmental and climatic change of the Phanerozoic time ( Jenkyns, 1988; Hermoso et al., 2012). We are therefore testing the paleoclimatic "proxy" potential of δ15Norg for this time interval by comparing the δ15Norg signal with other indicators more classically used for paleoclimate studies. We have also investigated the influence of differences in organic sources and of early diagenesis on the δ15Norg variations.

Paleo-fluid flow in folded, poorly lithified Quaternary sediments revealed by diagenetic concretions developed during the growth of Quattro Castella Anticline (Northern Apennines, Italy)

NASA Astrophysics Data System (ADS)

Pizzati, Mattia; Balsamo, Fabrizio; Iacumin, Paola; Swennen, Rudy; Storti, Fabrizio

2017-04-01

Diagenetic concretions and mineral masses may provide a useful tool to better understand paleo-fluid flows in transforming porous media. Moreover, the selective cementation responsible of diagenetic alterations formation, plays a key role in diminishing sediments porosity and permeability and hence reservoir quality. In compressive settings of a fold-and-thrust-belt, the presence of deep or blind thrusts could lead to the generation of folds which may influence syn-kinematic sedimentation, deep fluids migration and shallow fluid flow pattern. In this contribution we present a multidisciplinary field and laboratory study on carbonate concretions developed in Quaternary poorly lithified, shallow marine syn-kinematic sediments of the Quattro Castella Anticline in Northern Apennines (Italy). The study site is located along the Enza River, where shallow marine to continental sediments are exposed along the forelimb of the fold nucleated during Late Miocene and still active today. Field mapping was aimed to link bedding attitude of syn-kinematic sediments with the geometry, arrangement, shape and size of concretionary bodies. The studied concretions are both tabular (i.e. parallel to sediment bedding) and elongate single or coalescent concretionary bodies (i.e. plunging at different angle to bedding dip throughout the stratigraphic section). Concretions dimensions range from a few centimeters in single elongate concretions, up to a few meters in tabular and coalescent ones. In situ permeability measurements and laboratory grain size analyses were performed along the studied section to constrain the petrophysical properties of sediments hosting carbonate concretions. Carbon and oxygen stable isotopes analyses on carbonate concretions (performed both on hand specimens and also on thin sections), together with petrographic and cathodoluminescence observations, were used to better constrain the diagenetic environment in which calcite precipitation occurred. Our results indicate that the growing anticline promoted the development of a local topographic and hydraulic gradient which induced cement precipitation in the form of carbonate concretions in syn-kinematic sediments. Such diagenetic alterations can be a good marker to reconstruct the paleo-fluid flow history in structurally complex siliciclastic reservoirs.

Systematics and evolution of the Meriones shawii/grandis complex (Rodentia, Gerbillinae) during the Late Quaternary in northwestern Africa: Exploring the role of environmental and anthropogenic changes

NASA Astrophysics Data System (ADS)

Stoetzel, Emmanuelle; Cornette, Raphaël; Lalis, Aude; Nicolas, Violaine; Cucchi, Thomas; Denys, Christiane

2017-05-01

Rodents of the Meriones shawii/grandis complex have been attested to in North Africa since the Middle Pleistocene and are abundant in archaeological sites. Today, they are widely spread and represent a major pest to local human populations. This complex, therefore, represents an accurate model for investigating the roles of climate change and human impact in shaping Quaternary faunal diversity and distribution. Many gray areas still exist regarding the systematics, ecology and geographical distribution of this complex, for both present and past populations. The purpose of this study is to compare modern genotyped and fossil Meriones specimens in order to 1) clarify the current systematics and distribution of the Meriones populations of the shawii/grandis complex, 2) document the taxonomic diversity in fossil Meriones from northwestern Africa, and 3) track their phenotypic and biogeographic evolution through time. To answer these questions we used geometric morphometrics on skulls (landmarks) and first upper molars (landmarks and sliding landmarks). We evidenced the existence of two morpho-groups within the M. shawii/grandis complex, with a clear geographic pattern (M. grandis in Morocco vs. M. shawii in Algeria and Tunisia). Currently only one morpho-group, attributed to M. grandis, seems to exist in Morocco, with a small overlap with M. shawii in the most eastern part of the country. However, according to fossil data, M. shawii was also present in Atlantic Morocco during the Late Pleistocene. We have also highlighted the impact of Holocene climate change and habitat anthropization on this arid adapted group. During the Middle Holocene, a major climatic event (last interglacial optimum) seems to have induced a demographic collapse in Moroccan populations and the disappearance of the shawii clade from Morocco (except in the most eastern areas). Both species then re-expanded, benefitting from the increasing aridity and the new ecological niche driven by agriculture dispersal from the Neolithic onwards.

13C NMR and XPS characterization of anion adsorbent with quaternary ammonium groups prepared from rice straw, corn stalk and sugarcane bagasse

NASA Astrophysics Data System (ADS)

Cao, Wei; Wang, Zhenqian; Zeng, Qingling; Shen, Chunhua

2016-12-01

Despite amino groups modified crop straw has been intensively studied as new and low-cost adsorbent for removal of anionic species from water, there is still a lack of clear characterization for amino groups, especially quaternary ammonium groups in the surface of crop straw. In this study, we used 13C NMR and XPS technologies to characterize adsorbents with quaternary ammonium groups prepared from rice straw, corn stalk and sugarcane bagasse. 13C NMR spectra clearly showed the presence of quaternary ammonium groups in lignocelluloses structure of modified crop straw. The increase of nitrogen observed in XPS survey spectra also indicated the existence of quaternary ammonium group in the surface of the adsorbents. The curve fitting of high-resolution XPS N1s and C1s spectra were conducted to probe the composition of nitrogen and carbon contained groups, respectively. The results showed the proportion of quaternary ammonium group significantly increased in the prepared adsorbent's surface that was dominated by methyl/methylene, hydroxyl, quaternary ammonium, ether and carbonyl groups. This study proved that 13C NMR and XPS could be successfully utilized for characterization of quaternary ammonium modified crop straw adsorbents.

Resolving Phase Ambiguities In OQPSK

NASA Technical Reports Server (NTRS)

Nguyen, Tien M.

1991-01-01

Improved design for modulator and demodulator in offset-quaternary-phase-key-shifting (OQPSK) communication system enables receiver to resolve ambiguity in estimated phase of received signal. Features include unique-code-word modulation and detection and digital implementation of Costas loop in carrier-recovery subsystem. Enchances performance of carrier-recovery subsystem, reduces complexity of receiver by removing redundant circuits from previous design, and eliminates dependence of timing in receiver upon parallel-to-serial-conversion clock.

Quaternary history of the Kiseiba Oasis region, southern Egypt

NASA Astrophysics Data System (ADS)

Maxwell, Ted A.; Haynes, C. Vance; Nicoll, Kathleen; Johnston, Andrew K.; Grant, John A.; Kilani, Ali

2017-12-01

Kiseiba Oasis and depression are located in southern Egypt between the Selima Sand Sheet to the west and the Nile to the east, an important area that hosted Late Cenozoic drainage, Middle Pleistocene lakes, and numerous Paleolithic and Neolithic cultural sites. A synthesis of orbital data, field surveying and near-surface stratigraphy provides new insights into the Quaternary history of this region. Shuttle Imaging Radar data show a complex of fluvial channels that are due to stringers of surficial fluvial lag, subsurface fluvial deposits, and areas of deep alluvium. Three topographic surfaces are described: 1) the Atmur El-Kibeish, above 230 m elevation, which displays a linear pattern of light radar returns, possibly formed from northeast drainage; 2) the Acheulean Surface, at 200 m elevation, that has dark radar patterns resulting from thick alluvium bounded by pebble sand and calcrete strata, and 3) the Kiseiba Surface, below 190 m, that has a complex series of surface and subsurface fluvial and aeolian sediments. Initial drainage from the Early through Middle Pleistocene was to the northeast, which may have lasted through the Last Interglacial. Later reworking of sediments during the Last Glacial Maximum and the Holocene resulted in topographic inversion, with any subsequent local drainage on the Kiseiba Surface to the southwest, towards the Kiseiba Scarp.

(Model) Peatlands in late Quaternary interglacials

NASA Astrophysics Data System (ADS)

Kleinen, Thomas; Brovkin, Victor

2016-04-01

Peatlands have accumulated a substantial amount of carbon, roughly 600 PgC, during the Holocene. Prior to the Holocene, there is relatively little direct evidence of peatlands, though coal deposits bear witness to a long history of peat-forming ecosystems going back to the Carboniferous. We therefore need to rely on models to investigate peatlands in times prior to the Holocene. We have developed a dynamical model of wetland extent and peat accumulation, integrated in the coupled climate carbon cycle model of intermediate complexity CLIMBER2-LPJ, in order to mechanistically model interglacial carbon cycle dynamics. This model consists of the climate model of intermediate complexity CLIMBER2 and the dynamic global vegetation model LPJ, which we have extended with modules to determine peatland extent and carbon accumulation. The model compares reasonably well to Holocene peat data. We have used this model to investigate the dynamics of atmospheric CO2 in the Holocene and two other late Quaternary interglacials, namely the Eemian, which is interesting due to its warmth, and Marine Isotope Stage 11 (MIS11), which is the longest interglacial during the last 500ka. We will also present model results of peatland extent and carbon accumulation for these interglacials. We will discuss model shortcomings and knowledge gaps currently preventing an application of the model to full glacial-interglacial cycles.

Deformation of the Western Caribbean: Insights from Block and Geodynamic Models of Geodetic, Seismic and Geologic Data

NASA Astrophysics Data System (ADS)

La Femina, P. C.; Geirsson, H.; Kobayashi, D.

2012-12-01

Cocos - Caribbean convergence along the Middle America Trench, including subduction of the Cocos Ridge and seamount domain, and Nazca - Caribbean oblique convergence along the South Panama Deformed Belt have resulted in complex plate boundary zone deformation since Miocene - Pliocene time. Plate boundary evolution and upper plate deformation in the western Caribbean is well studied and indicates, 1) Quaternary migration of the volcanic arc toward the back-arc northwest of the Cocos Ridge; 2) Pleistocene to present northwestward motion of the Central American Fore Arc (CAFA); 3) Quaternary to present deformation within the Central Costa Rica Deformed Belt; 4) Miocene-Pliocene cessation of volcanism and uplift of the Cordillera de Talamanca inboard the ridge; 5) Quaternary to present shortening across the fore-arc Fila Costeña fold and thrust belt and back-arc North Panama Deformed Belt (NPDB); 6) Quaternary to present outer fore-arc uplift above the seamount domain (Nicoya Peninsula), and above (Osa Peninsula) and flanking (Burica Peninsula) the ridge; and 7) Quaternary to present faulting along the Sona-Azuero and Canal Discontinuity fault systems. We investigate the dynamic effects of Cocos and Nazca convergence along the entire Central American margin, and the implications on western Caribbean plate boundary evolution with a new GPS derived three-dimensional (horizontal and vertical) velocity field and kinematic block and geodynamic models. Specifically, we test the hypotheses that the Cocos Ridge is the main driver for upper plate deformation and that there is an independent Panama block. Our model results provide new Euler vectors for the CAFA and Panama block, rates of relative plate and block motions in the region, and constraints on interseismic coupling along the Middle America Trench and other major block bounding fault systems. These results are compared to existing geophysical and geologic data for the region and add insights into the rates of deformation across the regions listed above. We demonstrate that Cocos Ridge collision drives northwest-directed motion of the CAFA and the northeast-directed motion of the Panama region. The Panama region is driven into the Caribbean across the NPDB and into the Choco and North Andes blocks of northwestern South America, which are also converging with the Panama region, pushing it toward the west-northwest. Motion of the Panama region can be fit by an Euler vector suggesting that it is a rigid block, however, this is not in agreement with Quaternary faulting across the isthmus.

Quaternary tephrochronology and deposition in the subsurface Sacramento-San Joaquin Delta, California, U.S.A.

USGS Publications Warehouse

Maier, Katherine L.; Gatti, Emma; Wan, Elmira; Ponti, Daniel J.; Pagenkopp, Mark; Starratt, Scott W.; Olson, Holly A.; Tinsley, John

2015-01-01

We document characteristics of tephra, including facies and geochemistry, from 27 subsurface sites in the Sacramento-San Joaquin Delta, California, to obtain stratigraphic constraints in a complex setting. Analyzed discrete tephra deposits are correlative with: 1) an unnamed tephra from the Carlotta Formation near Ferndale, California, herein informally named the ash of Wildcat Grade (<~1.450 - >~0.780 Ma), 2) the Rockland ash bed (~0.575 Ma), 3) the Loleta ash bed (~0.390 Ma), and 4) a middle Pleistocene tephra resembling volcanic ash deposits at Tulelake, California, and Pringle Falls, Bend, and Summer Lake, Oregon, herein informally named the dacitic ash of Hood (<~0.211 to >~0.180 Ma, correlated age). All four tephra are derived from Cascades volcanic sources. The Rockland ash bed erupted from the southern Cascades near Lassen Peak, California, and occurs in deposits up to >7 m thick as observed in core samples taken from ~40 m depth below land surface. Tephra facies and tephra age constraints suggest rapid tephra deposition within fluvial channel and overbank settings, likely related to flood events shortly following the volcanic eruption. Such rapidly deposited tephra are important chronostratigraphic markers that suggest varying sediment accumulation rates (~0.07-0.29 m/1000 yr) in Quaternary deposits below the modern Sacramento-San Joaquin Delta. This study provides the first steps in developing a subsurface Quaternary stratigraphic framework necessary for future hazard assessment.

Shallow groundwater investigation using time-domain electromagnetic (TEM) method at Itay El-Baroud, Nile Delta, Egypt

NASA Astrophysics Data System (ADS)

Shaaban, H.; El-Qady, G.; Al-Sayed, E.; Ghazala, H.; Taha, A. I.

2016-12-01

The Nile Delta is one of the oldest known ancient delta, largest and most important depositional complex in the Mediterranean sedimentary basin. Furthermore, it is a unique site in Egypt that is suitable for accumulation and preservation of the Quaternary sediments. In this work we applied time-domain electromagnetic (TEM) method to investigate the Quaternary sediments sequence as well as detecting the groundwater aquifer in the area of study. A suite of 232 TEM sounding at 43 stations were carried out using a ;SIROTEM MK-3; time-domain electromagnetic system. A simple coincident loop configuration, in which the same loop transmits and receives signals, was employed with loop side length of 25 m. The 1-D modeling technique was applied to estimate the depth and the apparent resistivity of the interpreted geoelectrical data. Based on the interpretation of the acquired geophysical data, four geoelectric cross-sections were constructed. These sections show that the Upper Quaternary sequence consists of three geoelectric layers. The Holocene Nile mud is separated into two layers: the agricultural root zone (Layer 1) and thick water saturated mud (Layer 2). The Upper Pleistocene sandy aquifer (Layer 3) is very complicated non-linear boundary. This aquifer is the most important unit since it is considered as the main water bearing unit in the study area.

Within-plate Cenozoic Volcanism and Mantle Sources Within The Western-central Mediterranean Area

NASA Astrophysics Data System (ADS)

Beccaluva, L.; Bianchini, G.; Bonadiman, C.; Coltorti, M.; Siena, F.

An integrated study of anorogenic basic magmas and entrained mantle xenoliths rep- resents a promising approach for a comprehension of the magmatogenic events occur- ring within the lithospheric mantle in the western-central Mediterranean area. In this contribution we review the geochemical characteristics of mafic lavas and associated peridotite xenoliths from three anorogenic volcanic districts: Pliocene-Quaternary vol- canism of Sardinia; Pliocene-Quaternary volcanism of the Iblean area (eastern Sicily); Paleocene-Oligocene Veneto Volcanic Province. Investigations have been focused on 1) petrological features of parental magmas, which may contribute to infer the com- positional characteristics of mantle sources and to constrain the modes of partial melt- ing; 2) modelling the depletion events and metasomatic enrichments in mantle xeno- liths of the three volcanic districts, as well as the nature of their causative agents. Petrological features and Sr-Nd-Pb isotopic data, both of lava and xenoliths, indicate that DM+HIMU components distinguish the lithospheric mantle sections of Iblean and Veneto Volcanic Provinces. On the other hand, lavas and xenoliths from Sardinia display a significant different isotopic signature characterised by DM+EM1. Similar geochemical fingerprints, i.e. the significant presence of EM components are gener- ally recorded by mafic lavas and mantle xenoliths from the European Plate, whereas they are not observed in the stable African lithospheric domain.

Partial and Complete Wetting in Ultralow Interfacial Tension Multiphase Blends with Polylactide.

PubMed

Zolali, Ali M; Favis, Basil D

2016-12-15

The control of phase structuring in multiphase blends of polylactide (PLA) with other polymers is a viable approach to promote its broader implementation. In this article, ternary and quaternary blends of PLA with poly(butylene succinate) (PBS), poly(butylene adipate-co-terephthalate) (PBAT), and poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV) are prepared by melt blending. The interfacial tensions between components are measured using three different techniques, and a Fourier transform infrared imaging technique is developed for the purpose of unambiguous phase identification. A tricontinuous complete wetting behavior is observed for the ternary 33PLA/33PBS/33PBAT blend before and after quiescent annealing, which correlates closely with spreading theory analysis. In the quaternary PLA/PBS/PBAT/PHBV blend, a concentration-dependent wetting behavior is found. At 10 vol % PBAT, self-assembled partially wet droplets of PBAT are observed at the interface of PBS and PHBV, and they remain stable after quiescent annealing as predicted by spreading theory. In contrast, at 25 vol % PBAT, a quadruple continuous system is observed after mixing, which only transforms to partially wet PBAT droplets after subsequent annealing. These results clearly indicate the potential of composition control during the mixing of multiphase systems to result in a complete change of spreading behavior.

Palynological evidence for a southward shift of the North Atlantic Current at 2.6 Ma during the intensification of late Cenozoic Northern Hemisphere glaciation

NASA Astrophysics Data System (ADS)

Hennissen, Jan A. I.; Head, Martin J.; De Schepper, Stijn; Groeneveld, Jeroen

2014-06-01

The position of the North Atlantic Current (NAC) during the intensification of Northern Hemisphere glaciation (iNHG) has been evaluated using dinoflagellate cyst assemblages and foraminiferal geochemistry from a 260 kyr interval straddling the base of the Quaternary System from two sites: eastern North Atlantic Deep Sea Drilling Project Site 610 in the path of the present NAC and central North Atlantic Integrated Ocean Drilling Program Site U1313 in the subtropical gyre. Stable isotope and foraminiferal Mg/Ca analyses confirm cooling near the marine isotope stage (MIS) G7-G6 transition (2.74 Ma). However, a continued dominance of the dinoflagellate cyst Operculodinium centrocarpum sensu Wall and Dale (1966) indicates an active NAC in the eastern North Atlantic for a further 140 kyr. At MIS 104 ( 2.60 Ma), a profound dinoflagellate cyst assemblage turnover indicates NAC shutdown in the eastern North Atlantic, implying elevated atmospheric pressure over the Arctic and a resulting shift in the westerlies that would have driven the NAC. These findings challenge recent suggestions that there was no significant southward shift of the NAC or the Arctic Front during iNHG, and reveal a fundamental climatic reorganization near the base of the Quaternary.

Simultaneous determination of phosphatidylcholine-derived quaternary ammonium compounds by a LC-MS/MS method in human blood plasma, serum and urine samples.

PubMed

Steuer, Christian; Schütz, Philipp; Bernasconi, Luca; Huber, Andreas R

2016-01-01

The determination of circulating trimethylamine-N-oxide (TMAO), choline, betaine, l-carnitine and O-acetyl-l-carnitine concentration in different human matrices is of great clinical interest. Recent results highlighted the prognostic value of TMAO and quaternary ammonium containing metabolites in the field of cardiovascular and kidney diseases. Herein, we report a method for the rapid and simultaneous measurement of closely related phosphatidylcholine-derived metabolites in three different biological matrices by stable isotope dilution assay. Plasma, serum and urine samples were simply deproteinized and separated by HILIC-chromatography. Detection and quantification were performed using LC-MS/MS with electrospray ionization in positive mode. For accuracy and precision, full calibration was performed covering more than the full reference range. Assay performance metrics include intra- and interday imprecision were below 10% for all analytes. To exclude matrix effects standard addition methods were applied for all matrices. It was shown that calibration standards and quality control prepared in water can be used instead of matrix-matched calibration and controls. The LC/MS/MS-based assay described in this article may improve future clinical studies evaluating TMAO and related substances as prognostic markers for cardiovascular risk and all-cause mortality in different patient populations. Copyright © 2015 Elsevier B.V. All rights reserved.

QuEChERS-based purification method coupled to ultrahigh performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) to determine six quaternary ammonium compounds (QACs) in dairy products.

PubMed

Xian, Yanping; Dong, Hao; Wu, Yuluan; Guo, Xindong; Hou, Xiangchang; Wang, Bin

2016-12-01

QuEChERS-based purification coupled with UPLC-MS/MS method, was developed for six quaternary ammonium compounds (QACs) determination in dairy products. Powder samples were firstly dispersed by water. Protein in liquid milk was precipitated and sample solution was extracted by acetonitrile. QuEChERS-based purification was used to purify the solution. QACs were finally separated by HILIC column and detected in MRM mode of MS/MS under ESI(+). The stable isotope benzyl-2,3,4,5,6-d5-dimethyltetradecylammonium bromide (C14-BAC-d5) was used as an internal standard. This method was validated in terms of linearity, sensitivity, precision, accuracy. Linear relations were favorable for QACs over the selected concentration ranges of 0.2-50μg/L, with correlation coefficients greater than 0.999. The limits of detection (LODs) were in the range of 0.4-14.5μg/kg. Recoveries were between 91.2% and 115% with RSDs of 2.8-7.5% for intra-day precision and 3.7-6.7% for inter-day precision. This validated method was successfully applied to determine the QACs concentrations in dairy products. Copyright © 2016 Elsevier Ltd. All rights reserved.

Resistance to quaternary ammonium compounds in food-related bacteria.

PubMed

Sidhu, Maan Singh; Sørum, Henning; Holck, Askild

2002-01-01

Microbial resistance to antimicrobial agents continues to be a major problem. The frequent use and misuse of disinfectants based on quaternary ammonium compounds (QACs) in food-processing industries have imposed a selective pressure and may contribute to the emergence of disinfectant-resistant microorganisms. A total number of 1,325 Gram-negative isolates (Escherichia coli, other coliforms Vibrio spp., and Aeromonas spp.) and 500 Enterococcus spp. from food and food-processing industries and fish farming were screened for natural resistance to the QAC-based disinfectant benzalkonium chloride (BC). Of the 1,825 isolates, 16 strains, mainly from meat retail shops, showed low-level resistance to BC. None of the Enterococcus spp. from broiler, cattle, and pigs, the antibiotic-resistant E. coli from pig intestine and fish pathogens Vibrio spp. and Aeromonas spp. from the Norwegian fish farming industry were resistant to BC. The BC-resistant strains were examined for susceptibility to 15 different antibiotics, disinfectants, and dyes. No systematic cross-resistance between BC and any of the other antimicrobial agents tested was detected. Stable enhanced resistance in Enterobacter cloacae isolates was demonstrated by step-wise adaptation in increasing concentrations of BC. In conclusion, BC resistance among food-associated Gram-negative bacteria and Enterococcus spp. is not frequent, but resistance may develop to user concentrations after exposure to sublethal concentrations of BC.

Comparison of GPS and Quaternary slip rates: Insights from a new Quaternary fault database for Central Asia

NASA Astrophysics Data System (ADS)

Mohadjer, Solmaz; Ehlers, Todd; Bendick, Rebecca; Mutz, Sebastian

2016-04-01

Previous studies related to the kinematics of deformation within the India-Asia collision zone have relied on slip rate data for major active faults to test kinematic models that explain the deformation of the region. The slip rate data, however, are generally disputed for many of the first-order faults in the region (e.g., Altyn Tagh and Karakorum faults). Several studies have also challenged the common assumption that geodetic slip rates are representative of Quaternary slip rates. What has received little attention is the degree to which geodetic slip rates relate to Quaternary slip rates for active faults in the India-Asia collision zone. In this study, we utilize slip rate data from a new Quaternary fault database for Central Asia to determine the overall relationship between Quaternary and GPS-derived slip rates for 18 faults. The preliminary analysis investigating this relationship uses weighted least squares and a re-sampling analysis to test the sensitivity of this relationship to different data point attributes (e.g., faults associated with data points and dating methods used for estimating Quaternary slip rates). The resulting sample subsets of data points yield a maximum possible Pearson correlation coefficient of ~0.6, suggesting moderate correlation between Quaternary and GPS-derived slip rates for some faults (e.g., Kunlun and Longmen Shan faults). Faults with poorly correlated Quaternary and GPS-derived slip rates were identified and dating methods used for the Quaternary slip rates were examined. Results indicate that a poor correlation between Quaternary and GPS-derived slip rates exist for the Karakorum and Chaman faults. Large differences between Quaternary and GPS slip rates for these faults appear to be connected to qualitative dating of landforms used in the estimation of the Quaternary slip rates and errors in the geomorphic and structural reconstruction of offset landforms (e.g., offset terrace riser reconstructions for Altyn Tagh fault). Other factors such as a low density in the GPS network (e.g., GPS rate based on data from a single station for the Karakorum fault) appear to also contribute to the mismatch observed between the slip rates. Taken together, these results suggest that GPS-derived slip rates are often (but not always) representative of Quaternary slip rates and that the dating methods and sampling approaches used to identify transients in a fault slip rate history should be heavily scrutinized before interpreting the seismic hazards for a region.

Investigating Western Dead Sea spring systems and their origin by application of hydrogeochemical patterns

NASA Astrophysics Data System (ADS)

Wilske, Cornelia; Siebert, Christian; Geyer, Stefan; Rödiger, Tino; Merkel, Broder

2013-04-01

One of the ecologic and touristic hot spots along the western Dead Sea shore is the spring system of Ein Feshkha (Enot Zukim), which suffers from a changing environment. Its feeding Cretaceous aquifers are hosted in the western Graben flank of the Jordan-Dead Sea Rift. However, the origin of water and the ratio of influence of the unconsolidated Quaternary Graben fill is a controversial issue. The aim of the study is to combine hydrogeochemical information of the spring waters and the potential source aquifers to characterize and differentiate the groundwater origins, groundwater flow paths and eventually groundwater mixtures. Within this case study, which is embedded in the SMART II project (Sustainable Management of Available Water Resources of the Lower Jordan Valley), the investigation area extends in the Judean Mountains from the vicinity of Ramallah down to Hebron and ends along the north-western shoreline of the Dead Sea. The Cretaceous limestone aquifers of Turonian/Upper Cenomanian and Albian age are widely separated by a clayey aquiclude. That so called Judea Group is underlaid by the Kurnub sandstone aquifer. Mainly due to the development of the Rift, the entire area is intensely folded and crossed by faults. Groundwater recharge takes place in the uplands and the groundwater flow gradient is oriented towards the Valley, where it transgresses into the Quaternary Graben fill. Our hypothesis is that Ein Feshkha springs are fed by groundwater originating in general in the mountain range, which also takes a detour through the Graben fill in the north of the Dead Sea. Groundwater from these aquifers emerges along the coast of the Dead Sea through springs. The methodological approach is to use geogenic and anthropogenic hydrochemical parameters like major- and trace elements, stable isotopes like δ2H, δ18O or δ87Sr and heavy metals. Sampling campaigns were and will be carried out quarterly within one hydrological year to uncover possible seasonal variations. Samples are taken from the different aquifers over the whole investigation area. The first results represent the variability of the groundwater chemistry in terms of their TDS contents and their stable isotope signatures. The measured stable isotope ratios of Strontium, which refer to the geological background, show a differentiation between the groundwater of the main Judean aquifers. In combination with stable isotopes the composition of major- and trace elements including heavy metals improve the aquifer differentiation against the background of changes in geological formations.

Structure and Location of the Regulatory β Subunits in the (αβγδ)4 Phosphorylase Kinase Complex* ♦

PubMed Central

Nadeau, Owen W.; Lane, Laura A.; Xu, Dong; Sage, Jessica; Priddy, Timothy S.; Artigues, Antonio; Villar, Maria T.; Yang, Qing; Robinson, Carol V.; Zhang, Yang; Carlson, Gerald M.

2012-01-01

Phosphorylase kinase (PhK) is a hexadecameric (αβγδ)4 complex that regulates glycogenolysis in skeletal muscle. Activity of the catalytic γ subunit is regulated by allosteric activators targeting the regulatory α, β, and δ subunits. Three-dimensional EM reconstructions of PhK show it to be two large (αβγδ)2 lobes joined with D2 symmetry through interconnecting bridges. The subunit composition of these bridges was unknown, although indirect evidence suggested the β subunits may be involved in their formation. We have used biochemical, biophysical, and computational approaches to not only address the quaternary structure of the β subunits within the PhK complex, i.e. whether they compose the bridges, but also their secondary and tertiary structures. The secondary structure of β was determined to be predominantly helical by comparing the CD spectrum of an αγδ subcomplex with that of the native (αβγδ)4 complex. An atomic model displaying tertiary structure for the entire β subunit was constructed using chemical cross-linking, MS, threading, and ab initio approaches. Nearly all this model is covered by two templates corresponding to glycosyl hydrolase 15 family members and the A subunit of protein phosphatase 2A. Regarding the quaternary structure of the β subunits, they were directly determined to compose the four interconnecting bridges in the (αβγδ)4 kinase core, because a β4 subcomplex was observed through both chemical cross-linking and top-down MS of PhK. The predicted model of the β subunit was docked within the bridges of a cryoelectron microscopic density envelope of PhK utilizing known surface features of the subunit. PMID:22969083

A History of Repeated Failures: Stratigraphy of the Currituck and Cape Fear Slide Complexes on the Central U.S. Atlantic Margin

NASA Astrophysics Data System (ADS)

Hill, J. C.; Brothers, D. S.; Ten Brink, U. S.

2016-12-01

The Currituck and Cape Fear Slide complexes, offshore of North Carolina, are two of the largest (>150 km3) submarine slope failure provinces on the U.S. Atlantic margin. Detailed stratigraphy of these slides and the surrounding regions is derived from a combination of high-resolution sparker multichannel seismic (MCS) data collected by the USGS in 2012, airgun MCS collected as part of the NSF GeoPRISMs Community Seismic Experiment in 2014 & legacy industry airgun MCS data collected in 1970s and 80s. Both the Currituck and Cape Fear Slide complexes are located in regions with high sediment input that resulted in the development of a broad, low gradient (<6°) margin with thick slope sediment accumulation since at least the Miocene. Bedding parallel failure planes highlight the influence of subsurface stratigraphy here. Differential compaction across buried scarps and other erosional surfaces found in proximity to many of the headwalls may have contributed to excess pore pressure in these zones, setting the stage for repeated failures. Within the Currituck Slide complex, there appear to be several buried mass transport deposits (MTDs) within both the Quaternary and Pliocene sections that may be related to buried scarps found beneath both the upper and lower headwalls. At the Cape Fear Slide, the Quaternary section upslope of a large salt diapir displays evidence of possible downslope creep folding within strata that downlap onto a possible buried failure plane. While submarine slope failure along this portion of the margin has long been linked with hydrate dissociation and/or salt tectonics, features that are pervasive along the margin, our new stratigraphic analyses suggest that antecedent margin physiography and sediment loading may be critical factors in determining the locations of large-scale slope failures.

Cathodic electrocatalyst layer for electrochemical generation of hydrogen peroxide

NASA Technical Reports Server (NTRS)

Tennakoon, Charles L. K. (Inventor); Singh, Waheguru Pal (Inventor); Rhodes, Christopher P. (Inventor); Anderson, Kelvin C. (Inventor)

2011-01-01

A cathodic gas diffusion electrode for the electrochemical production of aqueous hydrogen peroxide solutions. The cathodic gas diffusion electrode comprises an electrically conductive gas diffusion substrate and a cathodic electrocatalyst layer supported on the gas diffusion substrate. A novel cathodic electrocatalyst layer comprises a cathodic electrocatalyst, a substantially water-insoluble quaternary ammonium compound, a fluorocarbon polymer hydrophobic agent and binder, and a perfluoronated sulphonic acid polymer. An electrochemical cell using the novel cathodic electrocatalyst layer has been shown to produce an aqueous solution having between 8 and 14 weight percent hydrogen peroxide. Furthermore, such electrochemical cells have shown stable production of hydrogen peroxide solutions over 1000 hours of operation including numerous system shutdowns.

Mechanism of the Intramolecular Claisen Condensation Reaction Catalyzed by MenB, a Crotonase Superfamily Member†

PubMed Central

Li, Huei-Jiun; Li, Xiaokai; Liu, Nina; Zhang, Huaning; Truglio, James J.; Mishra, Shambhavi; Kisker, Caroline; Garcia-Diaz, Miguel; Tonge, Peter J.

2014-01-01

MenB, the 1,4-dihydroxy-2-naphthoyl-CoA synthase from the bacterial menaquinone biosynthesis pathway, catalyzes an intramolecular Claisen condensation (Dieckmann reaction) in which the electrophile is an unactivated carboxylic acid. Mechanistic studies on this crotonase family member have been hindered by partial active site disorder in existing MenB X-ray structures. In the current work the 2.0 Å structure of O-succinylbenzoyl-aminoCoA (OSB-NCoA) bound to the MenB from Escherichia coli provides important insight into the catalytic mechanism by revealing the position of all active site residues. This has been accomplished by the use of a stable analogue of the O-succinylbenzoyl-CoA (OSB-CoA) substrate in which the CoA thiol has been replaced by an amine. The resulting OSB-NCoA is stable and the X-ray structure of this molecule bound to MenB reveals the structure of the enzyme-substrate complex poised for carbon-carbon bond formation. The structural data support a mechanism in which two conserved active site Tyr residues, Y97 and Y258, participate directly in the intramolecular transfer of the substrate α-proton to the benzylic carboxylate of the substrate, leading to protonation of the electrophile and formation of the required carbanion. Y97 and Y258 are also ideally positioned to function as the second oxyanion hole required for stabilization of the tetrahedral intermediate formed during carbon-carbon bond formation. In contrast, D163, which is structurally homologous to the acid-base catalyst E144 in crotonase, is not directly involved in carbanion formation and may instead play a structural role by stabilizing the loop that carries Y97. When similar studies were performed on the MenB from Mycobacterium tuberculosis, a twisted hexamer was unexpectedly observed, demonstrating the flexibility of the interfacial loops that are involved in the generation of the novel tertiary and quaternary structures found in the crotonase superfamily. This work reinforces the utility of using a stable substrate analogue as a mechanistic probe in which only one atom has been altered leading to a decrease in α-proton acidity. PMID:21830810

Mechanism of the intramolecular Claisen condensation reaction catalyzed by MenB, a crotonase superfamily member.

PubMed

Li, Huei-Jiun; Li, Xiaokai; Liu, Nina; Zhang, Huaning; Truglio, James J; Mishra, Shambhavi; Kisker, Caroline; Garcia-Diaz, Miguel; Tonge, Peter J

2011-11-08

MenB, the 1,4-dihydroxy-2-naphthoyl-CoA synthase from the bacterial menaquinone biosynthesis pathway, catalyzes an intramolecular Claisen condensation (Dieckmann reaction) in which the electrophile is an unactivated carboxylic acid. Mechanistic studies on this crotonase family member have been hindered by partial active site disorder in existing MenB X-ray structures. In the current work the 2.0 Å structure of O-succinylbenzoyl-aminoCoA (OSB-NCoA) bound to the MenB from Escherichia coli provides important insight into the catalytic mechanism by revealing the position of all active site residues. This has been accomplished by the use of a stable analogue of the O-succinylbenzoyl-CoA (OSB-CoA) substrate in which the CoA thiol has been replaced by an amine. The resulting OSB-NCoA is stable, and the X-ray structure of this molecule bound to MenB reveals the structure of the enzyme-substrate complex poised for carbon-carbon bond formation. The structural data support a mechanism in which two conserved active site Tyr residues, Y97 and Y258, participate directly in the intramolecular transfer of the substrate α-proton to the benzylic carboxylate of the substrate, leading to protonation of the electrophile and formation of the required carbanion. Y97 and Y258 are also ideally positioned to function as the second oxyanion hole required for stabilization of the tetrahedral intermediate formed during carbon-carbon bond formation. In contrast, D163, which is structurally homologous to the acid-base catalyst E144 in crotonase (enoyl-CoA hydratase), is not directly involved in carbanion formation and may instead play a structural role by stabilizing the loop that carries Y97. When similar studies were performed on the MenB from Mycobacterium tuberculosis, a twisted hexamer was unexpectedly observed, demonstrating the flexibility of the interfacial loops that are involved in the generation of the novel tertiary and quaternary structures found in the crotonase superfamily. This work reinforces the utility of using a stable substrate analogue as a mechanistic probe in which only one atom has been altered leading to a decrease in α-proton acidity.

Deep reaching versus vertically restricted Quaternary normal faults: Implications on seismic potential assessment in tectonically active regions: Lessons from the middle Aterno valley fault system, central Italy

NASA Astrophysics Data System (ADS)

Falcucci, E.; Gori, S.; Moro, M.; Fubelli, G.; Saroli, M.; Chiarabba, C.; Galadini, F.

2015-05-01

We investigate the Middle Aterno Valley fault system (MAVF), a poorly investigated seismic gap in the central Apennines, adjacent to the 2009 L'Aquila earthquake epicentral area. Geological and paleoseismological analyses revealed that the MAVF evolved through hanging wall splay nucleation, its main segment moving at 0.23-0.34 mm/year since the Middle Pleistocene; the penultimate activation event occurred between 5388-5310 B.C. and 1934-1744 B.C., the last event after 2036-1768 B.C. and just before 1st-2nd century AD. These data define hard linkage (sensu Walsh and Watterson, 1991; Peacock et al., 2000; Walsh et al., 2003, and references therein) with the contiguous Subequana Valley fault segment, able to rupture in large magnitude earthquakes (up to 6.8), that did not rupture since about two millennia. By the joint analysis of geological observations and seismological data acquired during to the 2009 seismic sequence, we derive a picture of the complex structural framework of the area comprised between the MAVF, the Paganica fault (the 2009 earthquake causative fault) and the Gran Sasso Range. This sector is affected by a dense array of few-km long, closely and regularly spaced Quaternary normal fault strands, that are considered as branches of the MAVF northern segment. Our analysis reveals that these structures are downdip confined by a decollement represented by to the presently inactive thrust sheet above the Gran Sasso front limiting their seismogenic potential. Our study highlights the advantage of combining Quaternary geological field analysis with high resolution seismological data to fully unravel the structural setting of regions where subsequent tectonic phases took place and where structural interference plays a key role in influencing the seismotectonic context; this has also inevitably implications for accurately assessing seismic hazard of such structurally complex regions.

Formation of Stable Cationic Lipid/DNA Complexes for Gene Transfer

NASA Astrophysics Data System (ADS)

Hofland, Hans E. J.; Shephard, Lee; Sullivan, Sean M.

1996-07-01

Stable cationic lipid/DNA complexes were formed by solubilizing cationic liposomes with 1% octylglucoside and complexing a DNA plasmid with the lipid in the presence of detergent. Removal of the detergent by dialysis yielded a lipid/DNA suspension that was able to transfect tissue culture cells up to 90 days after formation with no loss in activity. Similar levels of gene transfer were obtained by mixing the cationic lipid in a liposome form with DNA just prior to cell addition. However, expression was completely lost 24 hr after mixing. The transfection efficiency of the stable complex in 15% fetal calf serum was 30% of that obtained in the absence of serum, whereas the transient complex was completely inactivated with 2% fetal calf serum. A 90-day stability study comparing various storage conditions showed that the stable complex could be stored frozen or as a suspension at 4 degrees C with no loss in transfection efficiency. Centrifugation of the stable complex produced a pellet that contained approximately 90% of the DNA and 10% of the lipid. Transfection of cells with the resuspended pellet and the supernatant showed that the majority of the transfection activity was in the pellet and all the toxicity was in the supernatant. Formation of a stable cationic lipid/DNA complex has produced a transfection vehicle that can be stored indefinitely, can be concentrated with no loss in transfection efficiency, and the toxicity levels can be greatly reduced when the active complex is isolated from the uncomplexed lipid.

Excellently guarded materials against UV and oxygen in the surfactant molecular complex crystal matrix

NASA Astrophysics Data System (ADS)

Ichikawa, Haruyo; Iimura, Nahoko; Hirata, Hirotaka

2000-07-01

Crystalline surfactant molecular complexes (SCMs) generated between quaternary ammonium cationic surfactants such as CTAB and various additives disclose their excellent protective properties from UV light and oxygen to complex additive materials, which are occluded in the complex crystal matrix. The effects of UV and oxygen were followed by the absorption decay of additive chromophores in comparing that of naked additive specimens with that of those in the complexed state. From the decay profiles, the rate constants and the half-life times were estimated under the assumptions in which the photo and oxidation processes were dominated in accordance with the first-ordered reaction. The results afford us promising prospects in extending the shelf-life of every material, above all medicinal drug, with the consequence that these obtained values evidently demonstrate the remarkably suppressed rate and extremely elongated half-life times.

Long term landscape evolution within central Apennines (Italy): Marsica and Peligna region morphotectonics and surface processes

NASA Astrophysics Data System (ADS)

Miccadei, E.; Piacentini, T.; Berti, C.

2010-12-01

The relief features of the Apennines have been developed in a complex geomorphological and geological setting from Neogene to Quaternary. Growth of topography has been driven by active tectonics (thrust-related crustal shortening and high-angle normal faulting related to crustal extension), regional rock uplift, and surface processes, starting from Late Miocene(?) - Early Pliocene. At present a high-relief landscape is dominated by morphostructures including high-standing, resistant Mesozoic and early Tertiary carbonates ridges (i.e. thrust ridges, faulted homocline ridges) and intervening, erodible Tertiary siliciclastics valleys (i.e. fault line valleys) and Quaternary continental deposits filled basins (i.e. tectonic valleys, tectonic basins). This study tries to identify paleo-uplands that may be linked to paleo-base levels and aims at the reconstruction of ancient landscapes since the incipient phases of morphogenesis. It analyzes the role of tectonics and morphogenic processes in the long term temporal scale landscape evolution (i.e. Mio?-Pliocene to Quaternary). It is focused on the marsicano-peligna region, located along the main drainage divide between Adriatic side and Tyrrhenian side of Central Apennines, one of the highest average elevation area of the whole chain. The work incorporates GIS-based geomorphologic field mapping of morphostructures and Quaternary continental deposits, and plano-altimetric analysis and morphometry (DEM-, map-based) of the drainage network (i.e. patterns, hypsometry, knick points, Ks). Field mapping give clues on the definition of paleo-landscapes related to different paleo-morpho-climatic environments (i.e. karst, glacial, slope, fluvial). Geomorphological evidence of tectonics and their cross-cutting relationships with morphostructures, continental deposits and faults, provide clues on the deciphering of the reciprocal relationship of antecedence of the paleo-landscapes and on the timing of morphotectonics. Morphotectonic features are related to Neogene thrusts, reactivated or displaced by complex kinematic strike slip and followed by extensional tectonic features (present surface evidence given by fault line scarps, fault line valleys, fault scarps, fault slopes, wind gaps, etc.). Geomorphic evidence of faults is provided also by morphometry of the drainage network: highest long slope of the main streams (knick points and Ks) are located where the streams cut across or run along recent faults. Correlation of tectonic elements, paleosurfaces, Quaternary continental deposits, by means of morphotectonic cross sections, lead to the identification, in the marsicano-peligna region, of areas in which morphotectonics acted in the same period, becoming younger moving from the West to the East. In conclusion, recognition of different morphotectonic features, identification of different paleo-landscapes, and reconstruction of their migration history, contribute to define the main phases of syn and post orogenic, Apennine chain landscape evolution: it results from the link of alternating morphotectonics and surface processes, due to migrating fault activity, rock uplift processes and alternating karst, glacial, slope, fluvial processes.

Century scale climatic rhythms in the equatorial Indian Ocean during the late Quaternary: Faunal and geochemical proxies from the Maldivian Archipelago

NASA Astrophysics Data System (ADS)

Sarkar, S.; Gupta, A. K.

2012-04-01

The equatorial Indian Ocean is swept by the Indian Ocean equatorial westerlies (IEW) which are strong during monsoon transitions in April-May and October-November, driving Eastward Equatorial Current (EEC) in the upper ocean. This study is based on the biogenic sediments from Ocean Drilling Program (ODP) Hole 716A, recovered beneath the narrow equatorial track (7 Degree North to 7 Degree South) along which the IEW prevail. We analyzed 300 Kyr record of benthic and planktic foraminifera, pteropods combined with stable isotope values measured on planktic foraminifer Globigerinoides ruber from 451 core samples to understand paleoceanographic and paleoclimatic changes in the equatorial Indian Ocean during the late Quaternary (~450 - 150 Kyrs). Factor and cluster analyses of the 53 highest-ranked benthic foraminiferal species enabled to identify five biofacies, indicating varied nature of deep-sea environments during the late Quaternary, with a major shift across the middle Brunhes epoch (across Marine Isotope Stage 9 and 8). Biofacies Robulus nicobarensis - Trifarina reussi (Rn-Tr), Uvigerina porrecta - Reussella simplex (Upo-Rs) and Cymbaloporetta squammosa - Bolivinita sp. (Cs-Bsp) document high organic flux with low oxygen paleoenvironment dominating before the mid-Brunhes event, similar to Globigerina bulloides population, while benthic foraminiferal biofacies Hoeglundina elegans - Miliolinella subrotunda (He-Ms) and Uvigerina peregrina - Quinqueloculina seminulum (Upe-Qs) record high seasonality in food supply with well-oxygenated deep water after ~300 Kyr. These changes are also visible in planktic foraminifera and pteropod record. In the present day, the strength of the IEW is inversely related to the Indian Ocean Dipole (IOD). The IEW weakened across MIS 9/8 during which time the IOD strengthened, causing heavy rains and floods over the equatorial East Africa and deficient rainfall over Australasia. The proxy response changed from low to high frequency cycles across the mid-Brunhes event with a shift towards stronger precessional signal. The weakening of the IEW was coupled with the strengthening of the IOD and was related to changes in the West Pacific Warm Pool-Southern Oscillation. This study establishes a link between long-term IOD dynamics and climate of the Indian Ocean region in the paleo record and captured IOD-IEW-driven changes from the late Quaternary marine biogenic sediments of the equatorial Indian Ocean.

Structural basis of respiratory syncytial virus neutralization by motavizumab

DOE Office of Scientific and Technical Information (OSTI.GOV)

McLellan, Jason S.; Chen, Man; Kim, Albert

2010-04-13

Motavizumab is {approx}tenfold more potent than its predecessor, palivizumab (Synagis), the FDA-approved monoclonal antibody used to prevent respiratory syncytial virus (RSV) infection. The structure of motavizumab in complex with a 24-residue peptide corresponding to its epitope on the RSV fusion (F) glycoprotein reveals the structural basis for this greater potency. Modeling suggests that motavizumab recognizes a different quaternary configuration of the F glycoprotein than that observed in a homologous structure.

Uncompetitive Inhibition of Yeast Alcohol Dehydrogenase by Diacetoxyscirpenol.

DTIC Science & Technology

1986-10-01

PREFACE The work described in this report was authorized under Project No. 1L161102A71A, Research in Chemical & Biological Defense, Biotechnology . This...Epoxytrichothecenes are the major components of the Fusarium myco- toxins identified as the causative agents for the epidemic outbreak of the alimentary ...The quaternary complex may have the structure such as NAD ~A EtOH ADS 14 LITERATURE CITED 1. Joffe, A.Z. Alimentary Toxic Aleukia. In Microbial Toxins

PRN 88-2: Clustering of Quaternary Ammonium Compounds

EPA Pesticide Factsheets

This Notice announces that EPA has clustered the Quaternary Ammonium Compounds into four groups for the purpose of testing chemicals to build a database that will support continued registration of the entire family of quaternary ammonium compounds

A Test of the Biogenicity Criteria Established for Microfossils and Stromatolites on Quaternary Tufa and Speleothem Materials Formed in the "Twilight Zone" at Caerwys, UK.

PubMed

Brasier, A T; Rogerson, M R; Mercedes-Martin, R; Vonhof, H B; Reijmer, J J G

2015-10-01

The ability to distinguish the features of a chemical sedimentary rock that can only be attributed to biology is a challenge relevant to both geobiology and astrobiology. This study aimed to test criteria for recognizing petrographically the biogenicity of microbially influenced fabrics and fossil microbes in complex Quaternary stalactitic carbonate rocks from Caerwys, UK. We found that the presence of carbonaceous microfossils, fabrics produced by the calcification of microbial filaments, and the asymmetrical development of tufa fabrics due to the more rapid growth of microbially influenced laminations could be recognized as biogenic features. Petrographic evidence also indicates that the development of "speleothem-like" laminae was related to episodes of growth interrupted by intervals of nondeposition and erosion. The lack of any biogenic characteristics in these laminae is consistent with their development as a result of variation in the physicochemical parameters that drive calcite precipitation from meteoric waters in such environmental settings.

Identifying drivers of biodiversity change from fossil long-lived lakes: lessons for risk and resilience of todays long-lived lake biota.

NASA Astrophysics Data System (ADS)

Wesselingh, Frank

2015-04-01

Several fossil long-lived lake systems exist that have a very good spatiotemporal geological and faunal record enabling us to study timeseries of biodiversity change. These complexes, such as the Miocene Pannonian and Quaternary Pontocaspian systems of Europe, Quaternary Lake Biwa in Japan and the Miocene Pebas System in South America enable us to assess the impact of environmental stability and pertubation on component processes of turnover, e.g. migration, speciation and extinction/ extirpation. Also, the temporal dimensions of such processes can be clarified and compared to the nature and rates of current turnover in long-lived lake systems. Our studies suggest that we are currently witnessing dramatic biodiversity loss caused mostly by habitat degradation and destruction in smaller lakes and invasives in larger lakes that may exceed the potential of endemic lake biota to recover. Long-live lakes should serve as an excellent illustration of the magnitude of the current anthropogenic-induced biodiversity crisis.

Assembly-directed antivirals differentially bind quasiequivalent pockets to modify hepatitis B virus capsid tertiary and quaternary structure.

PubMed

Katen, Sarah P; Tan, Zhenning; Chirapu, Srinivas Reddy; Finn, M G; Zlotnick, Adam

2013-08-06

Hepatitis B virus (HBV) is a major cause of liver disease. Assembly of the HBV capsid is a critical step in virus production and an attractive target for new antiviral therapies. We determined the structure of HBV capsid in complex with AT-130, a member of the phenylpropenamide family of assembly effectors. AT-130 causes tertiary and quaternary structural changes but does not disrupt capsid structure. AT-130 binds a hydrophobic pocket that also accommodates the previously characterized heteroaryldihydropyrimidine compounds but favors a unique quasiequivalent location on the capsid surface. Thus, this pocket is a promiscuous drug-binding site and a likely target for different assembly effectors with a broad range of mechanisms of activity. That AT-130 successfully decreases virus production by increasing capsid assembly rate without disrupting capsid structure delineates a paradigm in antiviral design, that disrupting reaction timing is a viable strategy for assembly effectors of HBV and other viruses. Copyright © 2013 Elsevier Ltd. All rights reserved.

Study of efficacy of reactivator HI 6 in reactivation of immobilized acetylcholinesterase, inhibited by organophosphorus chemical warfare agents of the "G" series.

PubMed

Hoskovcová, Monika; Halámek, Emil; Kobliha, Zbynĕk

2009-01-01

Reactivation with bis quaternary aldoxime HI-6, chemical formula 1-(2-hydroxyamino-methylpyridinium)-3-(4-carbamoylpyridinium)-2-oxapropane dichloride of immobilized enzyme acetylcholinesterase inhibited by nerve agent type "G" was studied. This aldoxime is effective in reactivation of sarin-inhibited acetylcholinesterase. Substantially lower reactivation potency was observed with cyclosarin-inhibited enzyme and almost no effect was found for that acetylcholinesterase is the enzyme complex. HI 6 is completely ineffective towards the soman-inhibited enzyme: After a 2-minute inhibition of the enzyme with soman no ability to define reactivator the inhibited enzymes and complexes.

Scaffold Diversity Synthesis Delivers Complex, Structurally, and Functionally Distinct Tetracyclic Benzopyrones

PubMed Central

Sankar, Muthukumar G.; Roy, Sayantani; Tran, Tuyen Thi Ngoc; Wittstein, Kathrin; Bauer, Jonathan O.; Strohmann, Carsten; Ziegler, Slava

2018-01-01

Abstract Complexity‐generating chemical transformations that afford novel molecular scaffolds enriched in sp 3 character are highly desired. Here, we present a highly stereoselective scaffold diversity synthesis approach that utilizes cascade double‐annulation reactions of diverse pairs of zwitterionic and non‐zwitterionic partners with 3‐formylchromones to generate highly complex tetracyclic benzopyrones. Each pair of annulation partners adds to the common chroman‐4‐one scaffold to build two new rings, supporting up to four contiguous chiral centers that include an all‐carbon quaternary center. Differently ring‐fused benzopyrones display different biological activities, thus demonstrating their immense potential in medicinal chemistry and chemical biology research. PMID:29721402

Subsurface and petroleum geology of the southwestern Santa Clara Valley ("Silicon Valley"), California

USGS Publications Warehouse

Stanley, Richard G.; Jachens, Robert C.; Lillis, Paul G.; McLaughlin, Robert J.; Kvenvolden, Keith A.; Hostettler, Frances D.; McDougall, Kristin A.; Magoon, Leslie B.

2002-01-01

Gravity anomalies, historical records of exploratory oil wells and oil seeps, new organic-geochemical results, and new stratigraphic and structural data indicate the presence of a concealed, oil-bearing sedimentary basin beneath a highly urbanized part of the Santa Clara Valley, Calif. A conspicuous isostatic-gravity low that extends about 35 km from Palo Alto southeastward to near Los Gatos reflects an asymmetric, northwest-trending sedimentary basin comprising low-density strata, principally of Miocene age, that rest on higher-density rocks of Mesozoic and Paleogene(?) age. Both gravity and well data show that the low-density rocks thin gradually to the northeast over a distance of about 10 km. The thickest (approx 4 km thick) accumulation of low-density material occurs along the basin's steep southwestern margin, which may be controlled by buried, northeast-dipping normal faults that were active during the Miocene. Movement along these hypothetical normal faults may been contemporaneous (approx 17–14 Ma) with sedimentation and local dacitic and basaltic volcanism, possibly in response to crustal extension related to passage of the northwestward-migrating Mendocino triple junction. During the Pliocene and Quaternary, the normal faults and Miocene strata were overridden by Mesozoic rocks, including the Franciscan Complex, along northeastward-vergent reverse and thrust faults of the Berrocal, Shannon, and Monte Vista Fault zones. Movement along these fault zones was accompanied by folding and tilting of strata as young as Quaternary and by uplift of the modern Santa Cruz Mountains; the fault zones remain seismically active. We attribute the Pliocene and Quaternary reverse and thrust faulting, folding, and uplift to compression caused by local San Andreas Fault tectonics and regional transpression along the Pacific-North American Plate boundary. Near the southwestern margin of the Santa Clara Valley, as many as 20 exploratory oil wells were drilled between 1891 and 1929 to total depths as great as 840 m. At least one pump unit is still standing. Although no lithologic or paleontologic samples are available from the wells, driller's logs indicate the presence of thick intervals of brown shale and sandstone resembling nearby outcrops of the Miocene Monterey Formation. Small amounts of oil and gas were observed in several wells, but commercial production was never established. Oil from the Peck well in Los Gatos is highly biodegraded, contains biomarkers commonly found in oils derived from the Monterey Formation, and has a stable-C-isotopic (d13C) composition of –23.32 permil, indicating derivation from a Miocene Monterey Formation source rock. Preliminary calculations suggest that about 1 billion barrels of oil may have been generated from source rocks within the Monterey Formation in the deepest part of the subsurface sedimentary basin between Los Gatos and Cupertino. Most of this oil was probably lost to biodegradation, oxidation, and leakage to the surface, but some oil may have accumulated in as-yet-undiscovered structural and stratigraphic traps along the complex structural boundary between the Santa Clara Valley and the Santa Cruz Mountains. Although some of these undiscovered accumulations of oil may be of commercial size, future petroleum exploration is unlikely because most of the area is currently devoted to residential, recreational, commercial, and industrial uses.

An unexpected twist in viral capsid maturation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gertsman, Ilya; Gan, Lu; Guttman, Miklos

2009-04-14

Lambda-like double-stranded (ds) DNA bacteriophage undergo massive conformational changes in their capsid shell during the packaging of their viral genomes. Capsid shells are complex organizations of hundreds of protein subunits that assemble into intricate quaternary complexes that ultimately are able to withstand over 50 atm of pressure during genome packaging. The extensive integration between subunits in capsids requires the formation of an intermediate complex, termed a procapsid, from which individual subunits can undergo the necessary refolding and structural rearrangements needed to transition to the more stable capsid. Although various mature capsids have been characterized at atomic resolution, no such procapsidmore » structure is available for a dsDNA virus or bacteriophage. Here we present a procapsid X-ray structure at 3.65 {angstrom} resolution, termed prohead II, of the lambda-like bacteriophage HK97, the mature capsid structure of which was previously solved to 3.44 {angstrom}. A comparison of the two largely different capsid forms has unveiled an unprecedented expansion mechanism that describes the transition. Crystallographic and hydrogen/deuterium exchange data presented here demonstrate that the subunit tertiary structures are significantly different between the two states, with twisting and bending motions occurring in both helical and -sheet regions. We also identified subunit interactions at each three-fold axis of the capsid that are maintained throughout maturation. The interactions sustain capsid integrity during subunit refolding and provide a fixed hinge from which subunits undergo rotational and translational motions during maturation. Previously published calorimetric data of a closely related bacteriophage, P22, showed that capsid maturation was an exothermic process that resulted in a release of 90 kJ mol{sup -1} of energy. We propose that the major tertiary changes presented in this study reveal a structural basis for an exothermic maturation process probably present in many dsDNA bacteriophage and possibly viruses such as herpesvirus, which share the HK97 subunit fold.« less

Residence times of groundwater and nitrate transport in coastal aquifer systems: Daweijia area, northeastern China.

PubMed

Han, Dongmei; Cao, Guoliang; McCallum, James; Song, Xianfang

2015-12-15

Groundwater within the coastal aquifer systems of the Daweijia area in northeastern China is characterized by a large of variations (33-521mg/L) in NO3(-) concentrations. Elevated nitrate concentrations, in addition to seawater intrusion in the Daweijia well field, both attributable to anthropogenic activities, may impact future water-management practices. Chemical and stable isotopic (δ(18)O, δ(2)H) analysis, (3)H and CFCs methods were applied to provide a better understanding of the relationship between the distribution of groundwater mean residence time (MRT) and nitrate transport, and to identify sources of nitrate concentrations in the complex coastal aquifer systems. There is a relatively narrow range of isotopic composition (ranging from -8.5 to -7.0‰) in most groundwater. Generally higher tritium contents observed in the wet season relative to the dry season may result from rapid groundwater circulation in response to the rainfall through the preferential flow paths. In the well field, the relatively increased nitrate concentrations of groundwater, accompanied by the higher tritium contents in the wet season, indicate the nitrate pollution can be attributed to domestic wastes. The binary exponential and piston-flow mixing model (BEP) yielded feasible age distributions based on the conceptual model. The good inverse relationship between groundwater MRTs (92-467years) and the NO3(-) concentrations in the shallow Quaternary aquifers indicates that elevated nitrate concentrations are attributable to more recent recharge for shallow groundwater. However, there is no significant relationship between the MRTs (8-411years) and the NO3(-) concentrations existing in the carbonate aquifer system, due to the complex hydrogeological conditions, groundwater age distributions and the range of contaminant source areas. Nitrate in the groundwater system without denitrification effects could accumulate and be transported for tens of years, through the complex carbonate aquifer matrix and the successive inputs of nitrogen from various sources. Copyright © 2015 Elsevier B.V. All rights reserved.

OMVPE Growth of Quaternary (Al,Ga,In)N for UV Optoelectronics (title change from A)

DOE Office of Scientific and Technical Information (OSTI.GOV)

HAN,JUNG; FIGIEL,JEFFREY J.; PETERSEN,GARY A.

We report the growth and characterization of quaternary AlGaInN. A combination of photoluminescence (PL), high-resolution x-ray diffraction (XRD), and Rutherford backscattering spectrometry (RBS) characterizations enables us to explore the contours of constant PL peak energy and lattice parameter as functions of the quaternary compositions. The observation of room temperature PL emission at 351nm (with 20% Al and 5% In) renders initial evidence that the quaternary could be used to provide confinement for GaInN (and possibly GaN). AlGaInN/GrdnN MQW heterostructures have been grown; both XRD and PL measurements suggest the possibility of incorporating this quaternary into optoelectronic devices.

Database and Map of Quaternary Faults and Folds in Peru and its Offshore Region

USGS Publications Warehouse

Machare, Jose; Fenton, Clark H.; Machette, Michael N.; Lavenu, Alain; Costa, Carlos; Dart, Richard L.

2003-01-01

This publication consists of a main map of Quaternary faults and fiolds of Peru, a table of Quaternary fault data, a region inset map showing relative plate motion, and a second inset map of an enlarged area of interest in southern Peru. These maps and data compilation show evidence for activity of Quaternary faults and folds in Peru and its offshore regions of the Pacific Ocean. The maps show the locations, ages, and activity rates of major earthquake-related features such as faults and fault-related folds. These data are accompanied by text databases that describe these features and document current information on their activity in the Quaternary.

Quaternary Geologic Map of Connecticut and Long Island Sound Basin

USGS Publications Warehouse

Stone, Janet Radway; Schafer, John P.; London, Elizabeth Haley; DiGiacomo-Cohen, Mary L.; Lewis, Ralph S.; Thompson, Woodrow B.

2005-01-01

The Quaternary geologic map (sheet 1) and explanatory figures and cross sections (sheet 2) portray the geologic features formed in Connecticut during the Quaternary Period, which includes the Pleistocene (glacial) and Holocene (postglacial) Epochs. The Quaternary Period has been a time of development of many details of the landscape and of all the surficial deposits. At least twice in the late Pleistocene, continental ice sheets swept across Connecticut. Their effects are of pervasive importance to the present occupants of the land. The Quaternary geologic map illustrates the geologic history and the distribution of depositional environments during the emplacement of glacial and postglacial surficial deposits and the landforms resulting from those events.

Filled Co (sub X) Ni (sub 4-x) Sb (sub 12-y) Sn (sub Y) Skutterudites: Processing and Thermoelectric Properties

NASA Technical Reports Server (NTRS)

Mackey, Jon; Sehirlioglu, Alp; Dynys, Fred

2015-01-01

Skutterudites have proven to be a useful thermoelectric system as a result of their enhanced figure of merit (ZT1), cheap material cost, favorable mechanical properties, and good thermal stability. The majority of skutterudite interest in recent years has been focused on binary skutterudites like CoSb3 or CoAs3. Binary skutterudites are often double and triple filled, with a range of elements from the lanthanide series, in order to reduce the lattice component of thermal conductivity. Ternary and quaternary skutterudites, such as Co4Ge6Se6 or Ni4Sb8Sn4, provide additional paths to tune the electronic structure. The thermal conductivity can further be improved in these complex skutterudites by the introduction of fillers. The Co (sub X) Ni (sub 4-x) Sb (sub 12-y) Sn (sub Y) system has been investigated as both a p- and n-type thermoelectric material, and is stable up to 200 degrees Centigrade. Yb, Ce, and Dy fillers have been introduced into the skutterudite to study the influence of both the type and the quantity of fillers on processing conditions and thermoelectric properties. The system was processed through a multi-step technique that includes solidification, mechano-chemical alloying, and hot pressing which will be discussed along with thermoelectric transport properties.

Electrostatically driven resonance energy transfer in "cationic" biocompatible indium phosphide quantum dots.

PubMed

Devatha, Gayathri; Roy, Soumendu; Rao, Anish; Mallick, Abhik; Basu, Sudipta; Pillai, Pramod P

2017-05-01

Indium Phosphide Quantum Dots (InP QDs) have emerged as an alternative to toxic metal ion based QDs in nanobiotechnology. The ability to generate cationic surface charge, without compromising stability and biocompatibility, is essential in realizing the full potential of InP QDs in biological applications. We have addressed this challenge by developing a place exchange protocol for the preparation of cationic InP/ZnS QDs. The quaternary ammonium group provides the much required permanent positive charge and stability to InP/ZnS QDs in biofluids. The two important properties of QDs, namely bioimaging and light induced resonance energy transfer, are successfully demonstrated in cationic InP/ZnS QDs. The low cytotoxicity and stable photoluminescence of cationic InP/ZnS QDs inside cells make them ideal candidates as optical probes for cellular imaging. An efficient resonance energy transfer ( E ∼ 60%) is observed, under physiological conditions, between the cationic InP/ZnS QD donor and anionic dye acceptor. A large bimolecular quenching constant along with a linear Stern-Volmer plot confirms the formation of a strong ground state complex between the cationic InP/ZnS QDs and the anionic dye. Control experiments prove the role of electrostatic attraction in driving the light induced interactions, which can rightfully form the basis for future nano-bio studies between cationic InP/ZnS QDs and anionic biomolecules.

Theory and Application of Photoelectron Diffraction for Complex Oxide Systems

NASA Astrophysics Data System (ADS)

Chassé, Angelika; Chassé, Thomas

2018-06-01

X-ray photoelectron diffraction (XPD) has been used to investigate film structures and local sites of surface and dopant atoms in complex oxide materials. We have performed angular-resolved measurements of intensity distribution curves (ADCs) and patterns (ADPs) of elemental core level intensities from binary to quaternary mixed oxide samples and compared them to multiple-scattering cluster (MSC) calculations in order to derive information on structural models and related parameters. MSC calculations permitted to describe both bulk diffraction features of binary oxide MnO(001) and the thickness-dependence of the tetragonal distortion of epitaxial MnO films on Ag(001). XPD was further used to investigate the surface termination of perovskite SrTiO3 and BaTiO3 substrates in order to evaluate influence of different ex situ and in situ preparation procedures on the surface layers, which are crucial for quality of following film growth. Despite the similarity of local environments of Sr (Ba) and Ti atoms in the perovskite film structure an angular region in the ADCs was identified as a fingerprint with the help of MSC simulations which provided clear conclusions on the perovskite oxide surfaces. Dopant sites in quaternary perovskite manganites La1-xCaxMnO3, La1-xSrxMnO3, and La1-xCexMnO3 were studied with polar angle scans of the photoemission intensities of host and dopant atoms. Both direct comparison of experimental ADCs and to the simulations within MSC models confirm the occupation of A sites by the dopants and the structural quality of the complex oxide films.

Precursor Ion–Ion Aggregation in the Brust–Schiffrin Synthesis of Alkanethiol Nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Graham, Trent R.; Renslow, Ryan; Govind, Niranjan

Tetraoctylammonium bromide is used in the Brust-Schiffrin nanoparticle synthesis to phase-transfer chloroaurate ions from the aqueous phase to the organic phase. While it is established that the quaternary ammonium complex self-associates in the organic phase, the actual self-assembled structure is debated. We have confirmed the presence of ion-ion aggregates through quantitative 1H Nuclear Magnetic Resonance spectroscopy (NMR), pulsed field gradient, diffusion-ordered NMR (DOSY-NMR) and density functional theory (DFT) based NMR shift calculations. Tetraoctylammonium complexes (TOA-X, where X = Br, Cl, AuCl4-xBrx, AuBr4/Br and AuCl4-xBrx/Br) were investigated to measure the extraction of water into the organic phase. 1H NMR and DFTmore » based NMR shielding calculations indicated that deshielding of water is due to hydration of the anion and not the formation of the aqueous core of a reverse micelle. DOSYNMR results were consistent with the formation of small aggregates at typical Brust-Schiffrin synthesis concentrations. The extent of aggregation correlated with the size and electronegativity of the anion and was analyzed with a modified, isodesmic, indefinite aggregation model. The substitution of bromoauric acid for chlororoauric acid at conditions emulating the Brust-Schiffrin synthesis increased the aggregation of the quaternary ammonium complex. The increase in aggregation corresponded with an increase in the size of the produced nanoparticles from 4.3 to 4.6 nm. Understanding the selfassembly and supramolecular structure of precursors in the Brust-Schiffrin synthesis will enable further refinement of models that predict the growth of noble metal nanoparticles.« less

Different applications of isosbestic points, normalized spectra and dual wavelength as powerful tools for resolution of multicomponent mixtures with severely overlapping spectra.

PubMed

Mohamed, Ekram H; Lotfy, Hayam M; Hegazy, Maha A; Mowaka, Shereen

2017-05-25

Analysis of complex mixture containing three or more components represented a challenge for analysts. New smart spectrophotometric methods have been recently evolved with no limitation. A study of different novel and smart spectrophotometric techniques for resolution of severely overlapping spectra were presented in this work utilizing isosbestic points present in different absorption spectra, normalized spectra as a divisor and dual wavelengths. A quaternary mixture of drotaverine (DRO), caffeine (CAF), paracetamol (PCT) and para-aminophenol (PAP) was taken as an example for application of the proposed techniques without any separation steps. The adopted techniques adopted of successive and progressive steps manipulating zero /or ratio /or derivative spectra. The proposed techniques includes eight novel and simple methods namely direct spectrophotometry after applying derivative transformation (DT) via multiplying by a decoding spectrum, spectrum subtraction (SS), advanced absorbance subtraction (AAS), advanced amplitude modulation (AAM), simultaneous derivative ratio (S 1 DD), advanced ratio difference (ARD), induced ratio difference (IRD) and finally double divisor-ratio difference-dual wavelength (DD-RD-DW) methods. The proposed methods were assessed by analyzing synthetic mixtures of the studied drugs. They were also successfully applied to commercial pharmaceutical formulations without interference from other dosage form additives. The methods were validated according to the ICH guidelines, accuracy, precision, repeatability, were found to be within the acceptable limits. The proposed procedures are accurate, simple and reproducible and yet economic. They are also sensitive and selective and could be used for routine analysis of complex most of the binary, ternary and quaternary mixtures and even more complex mixtures.

Late Quaternary Palaeoceanographic Changes in Sea Surface Conditions in the Tropical Atlantic

NASA Astrophysics Data System (ADS)

Fischel, Andrea; Seidenkrantz, Marit-Solveig; Kuijpers, Antoon; Nürnberg, Dirk

2013-04-01

Palaeoceanographic changes and the variability in surface water mass hydrography are reconstructed in order to track tropical ocean and climate variability and inter-hemispheric heat exchange through the last 42,000 year BP. Our studies are based on the relative abundance of planktonic foraminifera combined with sea surface temperature approximation based Mg/Ca measurements, XRF scanning and stable oxygen isotope analyses in a 5 m long gravity core Ga307-Win-12GC (17°50.80N, 64°48.7290W), retrieved in the Virgin Island Basin in approx. 3,960 m water depth. The Virgin Island Basin is the deepest part of the Anegada-Jungfern Passage in the northeast Caribbean, one of the most important pathways for water mass exchange between the Central Atlantic and the Caribbean Sea. Due to its bathymetry surface waters as well as deep water mass strata from the northern and southern hemisphere enter the basin, comprising Caribbean Surface Water (CSW), Antarctic Intermediate Water (AAIW), Atlantic Intermediate Water (AIW) and North Atlantic Deep Water (NADW). The planktonic foraminiferal assemblage suggests rather stable sea-surface conditions during the Holocene in the NE Caribbean. However, major changes in the hydrographic setting could be identified within the glacial period. During the glacial period, clear millennial-scale variability in sea-surface temperature and productivity are present. Fluctuations in the relative abundance of Globigerinoides ruber in the sediment core may be correlated to Dansgaard-Oeschger events in the northern North Atlantic. Furthermore an increase in relative abundance of Globorotalia rubescens occurs synchronous with ice rafted debris layers described from the North Atlantic. The faunal changes in the tropical Atlantic may thus be correlated to major climate changes in the North Atlantic, mainly D-O cyclicity as well as Heinrich events. Thus, the synchronous change in water mass distribution and hydrographic cyclicity suggests a possible linkage between tropical and North Atlantic Ocean variability during the Late Quaternary.

Climate-mediated nitrogen and carbon dynamics in a tropical watershed

NASA Astrophysics Data System (ADS)

Ballantyne, A. P.; Baker, P. A.; Fritz, S. C.; Poulter, B.

2011-06-01

Climate variability affects the capacity of the biosphere to assimilate and store important elements, such as nitrogen and carbon. Here we present biogeochemical evidence from the sediments of tropical Lake Titicaca indicating that large hydrologic changes in response to global glacial cycles during the Quaternary were accompanied by major shifts in ecosystem state. During prolonged glacial intervals, lake level was high and the lake was in a stable nitrogen-limited state. In contrast, during warm dry interglacials lake level fell and rates of nitrogen concentrations increased by a factor of 4-12, resulting in a fivefold to 24-fold increase in organic carbon concentrations in the sediments due to increased primary productivity. Observed periods of increased primary productivity were also associated with an apparent increase in denitrification. However, the net accumulation of nitrogen during interglacial intervals indicates that increased nitrogen supply exceeded nitrogen losses due to denitrification, thereby causing increases in primary productivity. Although primary productivity in tropical ecosystems, especially freshwater ecosystems, tends to be nitrogen limited, our results indicate that climate variability may lead to changes in nitrogen availability and thus changes in primary productivity. Therefore some tropical ecosystems may shift between a stable state of nitrogen limitation and a stable state of nitrogen saturation in response to varying climatic conditions.

Jealousy Graphs: Structure and Complexity of Decentralized Stable Matching

DTIC Science & Technology

2013-01-01

REPORT Jealousy Graphs: Structure and Complexity of Decentralized Stable Matching 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: The stable matching...Franceschetti 858-822-2284 3. DATES COVERED (From - To) Standard Form 298 (Rev 8/98) Prescribed by ANSI Std. Z39.18 - Jealousy Graphs: Structure and...market. Using this structure, we are able to provide a ner analysis of the complexity of a subclass of decentralized matching markets. Jealousy

Palaeogeographic implications of the Messinian surface in the Valencia trough, northwestern Mediterranean Sea

NASA Astrophysics Data System (ADS)

Escutia, C.; Maldonado, A.

1992-03-01

Sparker (3000 J and 8000 J) and multichannel seismic reflection profiles across the Valencia trough show a Messinian unconformity incised by numerous valleys. The main feature of this surface is a large valley that generally underlies the present Valencia valley and is deeply entrenched into the Miocene deposits. The size of this palaeo-valley ranges from 0.5 km wide and 15-100 m deep at its western end, to 1.6-2.8 km wide and 200-250 m deep downstream. An important tributary system is observed, with a main canyon (6-8 km wide and 150-200 m deep) draining the Ebro margin, as well as many other smaller valleys draining the Catalan and Balearic margins. Downstream, other tributaries underlie the present canyons of the Catalan margin. The location of the tributary system is controlled by the Early Miocene rift structures. The relief of the Messinian surface is affected by post-Miocene deformation that results from salt diapirism, extensional faulting and related volcanism. Late Neogene to Quaternary volcanic edifices cut the Messinian surface and coincide with large residual magnetic anomalies. Lower Pliocene to Quaternary salt diapirism in the abyssal plain north of Menorca has created a series of structural highs. Between these highs are deep interdiapiric troughs or basins that have become sediment depocentres during the Plio-Quaternary. The complex network of erosional valleys from the Valencia trough continental margin demonstrates that the valley system in the basin was not related to the refilling of the Mediterranean, but to the Iberian and Balearic margin palaeodrainage that developed during the Messinian desiccation. The presence of at least three erosional unconformities suggests that there were alternating periods of flooding and retreat of Atlantic water during Messinian time. The Messinian subaerial margin with erosional valleys contrasts sharply with the Pliocene-Quaternary marine margin with progradational turbidite systems.

Cenozoic pulsed compression of Da'an-Dedu Fault Zone in Songliao Basin (NE China) and its implications for earthquake potential: Evidence from seismic data

NASA Astrophysics Data System (ADS)

Yu, Zhongyuan; Zhang, Peizhen; Min, Wei; Wei, Qinghai; Zhao, Bin

2018-01-01

The Da'an-Dedu Fault Zone (DDFZ) is a major tectonic feature cutting through the Songliao Basin from south to north in NE China. Pulsed compression deformation of DDFZ during the Cenozoic implies a complex geodynamic process, and the latest stage of which occurred in the Quaternary directly influences the present seismicity of the interior basin. Although most of the evidence for Quaternary deformation about the Songliao Basin in the past decades was concentrated in marginal faults, all five earthquake swarms with magnitudes over 5.0 along the buried DDFZ with no surface expression during the past 30 years suggest it is a main seismogenic structure with seismic potential, which should deserve more attention of geologists. However, limited by the coverage of the Quaternary sedimentary and absence of strong historic and instrumental earthquakes records (M > 7), the geometric pattern, Quaternary activity and seismic potential of the DDFZ remain poorly understood. Thus, unlike previous geophysical studies focused on crust/mantle velocity structure across the fault and the aim of exploring possible mineral resources in the basin, in this study we have integrated a variety of the latest seismic data and drilling holes from petroleum explorations and shallow-depth seismic reflection profiles, to recognize the Cenozoic pulsed compression deformation of the DDFZ, and to discuss its implication for earthquake potential. The results show that at least four stages of compression deformation have occurred along the DDFZ in the Cenozoic: 65 Ma, 23 Ma, 5.3 Ma, and 1.8 Ma, respectively, although the geodynamic process behind which still in dispute. The results also imply that the tectonic style of the DDFZ fits well with the occurrence of modern seismic swarms. Moderate earthquake potential (M ≤ 7.0) is suggested along the DDFZ.

Synthesis and anticoagulant activity of the quaternary ammonium chitosan sulfates.

PubMed

Fan, Lihong; Wu, Penghui; Zhang, Jinrong; Gao, Song; Wang, Libo; Li, Mingjia; Sha, Mingming; Xie, Weiguo; Nie, Min

2012-01-01

Quaternary ammonium chitosan sulfates with diverse degrees of substitution (DS) ascribed to sulfate groups between 0.52 and 1.55 were synthesized by reacting quaternary ammonium chitosan with an uncommon sulfating agent (N(SO(3)Na)(3)) that was prepared from sodium bisulfite (NaHSO(3)) through reaction with sodium nitrite (NaNO(2)) in the aqueous system homogeneous. The structures of the derivatives were characterized by FTIR, (1)H NMR and (13)C NMR. The factors affecting DS of quaternary ammonium chitosan sulfates which included the molar ratio of NaNO(2) to quaternary ammonium chitosan, sulfated temperature, sulfated time and pH of sulfated reaction solution were investigated in detail. Its anticoagulation activity in vitro was determined by an activated partial thromboplastin time (APTT) assay, a thrombin time (TT) assay and a prothrombin time (PT) assay. Results of anticoagulation assays showed quaternary ammonium chitosan sulfates significantly prolonged APTT and TT, but not PT, and demonstrated that the introduction of sulfate groups into the quaternary ammonium chitosan structure improved its anticoagulant activity obviously. The study showed its anticoagulant properties strongly depended on its DS, concentration and molecular weight. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.

Reconnaissance geologic map of the Kuskokwim Bay region, southwest Alaska

USGS Publications Warehouse

Wilson, Frederic H.; Hults, Chad P.; Mohadjer, Solmaz; Coonrad, Warren L.

2013-01-01

The rocks of the map area range from Proterozoic age metamorphic rocks of the Kanektok metamorphic complex (Kilbuck terrane) to Quaternary age mafic volcanic rocks of Nunivak Island. The map area encompasses much of the type area of the Togiak-Tikchik Complex. The geologic maps used to construct this compilation were, for the most part, reconnaissance studies done in the time period from the 1950s to 1990s. Pioneering work in the map area by J.M. Hoare and W.L. Coonrad forms the basis for much of this map, either directly or as the stepping off point for later studies compiled here. Physiographically, the map area ranges from glaciated mountains, as much as 1,500 m high, in the Ahklun Mountains to the coastal lowlands of northern Bristol Bay and the Kuskokwim River delta. The mountains and the finger lakes (drowned fiords) on the east have been strongly affected by Pleistocene and Holocene glaciation. Within the map area are a number of major faults. The Togiak-Tikchik Fault and its extension to the northeast, the Holitna Fault, are considered extensions of the Denali fault system of central Alaska. Other sub-parallel faults include the Golden Gate, Sawpit, Goodnews, and East Kulukak Faults. Northwest-trending strike-slip faults crosscut and offset northeast-trending fault systems. Rocks of the area are assigned to a number of distinctive lithologic packages. Most distinctive among these packages are the high-grade metamorphic rocks of the Kanektok metamorphic complex or Kilbuck terrane, composed of a high-grade metamorphic orthogneiss core surrounded by greenschist and amphibolite facies schist, gneiss, and rare marble and quartzite. These rocks have yielded radiometric ages strongly suggestive of a 2.05 Ga emplacement age. Poorly known Paleozoic rocks, including Ordovician to Devonian and Permian limestone, are found east of the Kanektok metamorphic complex. A Triassic(?) ophiolite complex is on the southeast side of Kuskokwim Bay; otherwise only minor Triassic rock units are known. The most widespread rocks of the area are Jurassic and Early Cretaceous(?) volcanic and volcaniclastic rocks. The Kuskokwim Group flysch is restricted largely to the northeast part of the map area. It consists primarily of shelf and minor nearshore facies rocks. Primarily exposed in the lowlands west of the Ahklun Mountains, extensive latest Tertiary and Quaternary alkalic basalt flows and lesser pyroclastic rocks form much of the bedrock of the remaining area. On Saint Matthew Island, Cretaceous volcanic and pyroclastic rocks occur that are not found elsewhere within the map area. The Kuskokwim Group and older rocks, including on Saint Matthew Island, but not the Kanektok metamorphic complex, are intruded by widely dispersed Late Cretaceous and (or) Early Tertiary granitic rocks. Much of the lowland area is mantled by unconsolidated deposits that include glacial, alluvial and fluvial, marine, estuarine, and eolian deposits. These formed during several episodes of Quaternary glaciation.

A multidisciplinary study in the geodynamic active western Eger rift (Central Europe): The Quaternary volcanic complex Mytina and the recent CO2-degassing zone Hartousov

NASA Astrophysics Data System (ADS)

Flechsig, C.; Heinicke, J.; Kaempf, H. W.; Nickschick, T.; Mrlina, J.

2013-12-01

The Eger rift (Central Europe) belongs to the European Cenozoic rift system and represents an approximately 50 km wide and 300 km long ENE-WSW striking continental rift that formed during the Upper Cretaceous-Tertiary transition. This rift zone is one of the most active seismic regions in Central Europe. Especially, the western part of the Eger rift area is dominated by ongoing hidden magmatic processes in the intra-continental lithospheric mantle. Besides of known quaternary volcanoes, these processes take place in absence of any presently active volcanism at the surface. However, they are expressed by a series of phenomena distributed over a relatively large area, like occurrence of repeated earthquake swarms, surface exhalation of mantle-derived and CO2-enriched fluids at mofettes and mineral springs, and enhanced heat flow. At present this is the only known intra-continental region where such deep-seated, active lithospheric processes currently occur. The aim of the project is to investigate the tectonic/geologic near surface structure and the degassing processes of the mofette field of Hartousov, where soil gas measurements (concentration and flux rate) in an area of appr. 3x2 km traced a permeable NS extended segment of a fault zone and revealed highly permeable Diffuse Degassing Structures (DDS). The second target is volcanic environment of the Quaternary volcanic complex Mytina maar and the cinder cone Zelezna hurka/Eisenbühl. The investigations are intended to clarify: a) the spatio-temporal reconstruction of the maar complex, and the palaeo volcanic scenario (geological model, tectonic settings, distribution of pyroclastica, b) the geological structure and the tectonic control of the recent degassing zone, and c) the comperative interpretation of both regions in the consideration of potential future volcanic risk assessment in sub-regions of the western Eger Rift. To investigate both regions the following methods are used: geoelectrics, geomagnetics, shallow seismics, gravity and CO2-soil gas measurements, petrographic/petrophysical and remote sensing data. The results will be serve as for better understanding of geologic, volcanic and tectonic settings of the two regions as well as for the preparation of the ICDP drilling project 'Drilling the Eger rift' with a multidisciplinary approach consisting of geophysical, geochemical and other disciplines to understand the role of crustal fluid activity for swarm earthquake generation.

Micropaleontologic record of Quaternary paleoenvironments in the Central Albemarle Embayment, North Carolina, U.S.A.

USGS Publications Warehouse

Culver, Stephen J.; Farrell, Kathleen M.; Mallinson, David J.; Willard, Debra A.; Horton, Benjamin P.; Riggs, Stanley R.; Thieler, E. Robert; Wehmiller, John F.; Parham, Peter; Snyder, Scott W.; Hillier, Caroline

2011-01-01

To understand the temporal and spatial variation of eustatic sea-level fluctuations, glacio-hydro-isostacy, tectonics, subsidence, geologic environments and sedimentation patterns for the Quaternary of a passive continental margin, a nearly complete stratigraphic record that is fully integrated with a three dimensional chronostratigraphic framework, and paleoenvironmental information are necessary. The Albemarle Embayment, a Cenozoic regional depositional basin in eastern North Carolina located on the southeast Atlantic coast of the USA, is an ideal setting to unravel these dynamic, interrelated processes.Micropaleontological data, coupled with sedimentologic, chronostratigraphic and seismic data provide the bases for detailed interpretations of paleoenvironmental evolution and paleoclimates in the 90. m thick Quaternary record of the Albemarle Embayment. The data presented here come from a transect of cores drilled through a barrier island complex in the central Albemarle Embayment. This area sits in a ramp-like setting between late Pleistocene incised valleys.The data document the episodic infilling of the Albemarle Embayment throughout the Quaternary as a series of transgressive-regressive (T-R) cycles, characterized by inner shelf, midshelf, and shoreface assemblages, that overlie remnants of fluvial to estuarine valley-fill. Barrier island and marginal marine deposits have a low preservation potential. Inner to mid-shelf deposits of the early Pleistocene are overlain by similar middle Pleistocene shelf sediments in the south of the study area but entirely by inner shelf deposits in the north. Late Pleistocene marine sediments are of inner shelf origin and Holocene deposits are marginal marine in nature. Pleistocene marine sediments are incised, particularly in the northern half of the embayment by lowstand paleovalleys, partly filled by fluvial/floodplain deposits and in some cases, overlain by remnants of transgressive estuarine sediments. The shallowing through time of Quaternary sediments reflects the eastward progradational geometry of the continental shelf.The preservation potential of marginal marine deposits (barrier island, shoreface, backbarrier deposits) is not high, except in topographic lows associated with late Pleistocene paleovalleys and inlets because the current interglacial highstand has not yet reached its highest level. Given the documented increase in rate of relative sea-level rise in this region, shallow marine conditions are likely to return to the central Albemarle Embayment in the near future. ?? 2011 Elsevier B.V.

Antimicrobial Polymeric Materials with Quaternary Ammonium and Phosphonium Salts

PubMed Central

Xue, Yan; Xiao, Huining; Zhang, Yi

2015-01-01

Polymeric materials containing quaternary ammonium and/or phosphonium salts have been extensively studied and applied to a variety of antimicrobial-relevant areas. With various architectures, polymeric quaternary ammonium/phosphonium salts were prepared using different approaches, exhibiting different antimicrobial activities and potential applications. This review focuses on the state of the art of antimicrobial polymers with quaternary ammonium/phosphonium salts. In particular, it discusses the structure and synthesis method, mechanisms of antimicrobial action, and the comparison of antimicrobial performance between these two kinds of polymers. PMID:25667977

Synthesis of Quaternary Carbon Stereogenic Centers through Enantioselective Cu-Catalyzed Allylic Substitutions with Vinylaluminum Reagents

PubMed Central

Gao, Fang; McGrath, Kevin P.; Lee, Yunmi; Hoveyda, Amir H.

2010-01-01

Catalytic enantioselective allylic substitution (EAS) reactions, which involve the use of alkyl- or aryl-substituted vinylaluminum reagents and afford 1,4-dienes containing a quaternary carbon stereogenic center at their C-3 site, are disclosed. The C–C bond forming transformations are promoted by 0.5–2.5 mol % of sulfonate bearing chiral bidentate N-heterocyclic carbene (NHC) complexes, furnishing the desired products efficiently (66–97% yield of isolated products) and in high site- (>98% SN2′) and enantioselectivity [up to 99:1 enantiomer ratio (er)]. To the best of our knowledge, the present report puts forward the first cases of allylic substitution reactions that result in the generation of all-carbon quaternary stereogenic centers through the addition of a vinyl unit. The aryl- and vinyl-substituted vinylaluminum reagents, which cannot be prepared in high efficiency through direct reaction with diisobutylaluminum hydride, are accessed through a recently introduced Ni-catalyzed reaction of the corresponding terminal alkynes with the same inexpensive metal-hydride agent. Sequential Ni-catalyzed hydrometallations and Cu-catalyzed C–C bond forming reactions allow for efficient and selective synthesis of a range of enantiomerically enriched EAS products, which cannot cannot be accessed by previously disclosed strategies (due to inefficient vinylmetal synthesis or low reactivity and/or selectivity with Si-substituted derivatives). The utility of the protocols developed is demonstrated through a concise enantioselective synthesis of natural product bakuchiol. PMID:20860365

Quaternary gravitational morpho-genesis of Central Apennines (Italy): Insights from the Mt. Genzana case history

NASA Astrophysics Data System (ADS)

Esposito, C.; Bianchi-Fasani, G.; Martino, S.; Scarascia-Mugnozza, G.

2013-10-01

This paper focuses on a study aimed at defining the role of geological-structural setting and Quaternary morpho-structural evolution on the onset and development of a deep-seated gravitational slope deformation which affects the western slope of Mt. Genzana ridge (Central Apennines, Italy). This case history is particularly significant as it comprises several aspects of such gravitational processes both in general terms and with particular reference to the Apennines. In fact: i) the morpho-structural setting is representative of widespread conditions in Central Apennines; ii) the deforming slope partially evolved in a large rockslide-avalanche; iii) the deformational process provides evidence of an ongoing state of activity; iv) the rockslide-avalanche debris formed a stable natural dam, thus implying significant variations in the morphologic, hydraulic and hydrogeological setting; v) the gravitational deformation as well as the rockslide-avalanche reveal a strong structural control. The main study activities were addressed to define a detailed geological model of the gravity-driven process, by means of geological, structural, geomorphological and geomechanical surveys. As a result, a robust hypothesis about the kinematics of the process was possible, with particular reference to the identification of geological-structural constraints. The process, in fact, involves a specific section of the slope exactly where a dextral transtensional structure is present, thus implying local structural conditions that favor sliding processes: the rock mass is intensively jointed by high angle discontinuity sets and the bedding attitude is quite parallel to the slope angle. Within this frame the gravitational process can be classified as a structurally constrained translational slide, locally evolved into a rockslide-avalanche. The activation of such a deformation can be in its turn related to the Quaternary morphological evolution of the area, which was affected by a significant topographic stress increase, testified by stratigraphic and morphologic evidence.

EF-1 alpha is a target site for an inhibitory effect of quercetin in the peptide elongation process.

PubMed

Marcinkiewicz, C; Gałasiński, W; Gindzieński, A

1995-01-01

The effect of quercetin (3,3',4',5,7-pentahydroxyflavone) on the polypeptide elongation system isolated from rat liver cells, was investigated. Quercetin inhibited [14C]leucine incorporation into proteins in vitro and the inhibitory effect is being directed towards the elongation factor eEF-1, but not to eEF-2 and ribosomes. Quercetin was found to form a complex with EF-1 alpha, which was inactive in GTP-dependent binding to ribosomes. It can be suggested that quercetin can block the total or the part of the domain of EF-1 alpha structure that is responsible for formation of the ternary complex EF-1 alpha-GTP-[14C]Phe-tRNA and therefore preventing formation of the quaternary complex with ribosomes.

Novel polymer electrolytes based on cationic polyurethane with different alkyl chain length

NASA Astrophysics Data System (ADS)

Liu, Libin; Wu, Xiwen; Li, Tianduo

2014-03-01

A series of comb-like cationic polyurethanes (PUs) were synthesized by quaternizing different bromoalkane (C2H5Br, C8H17Br, and C14H29Br) with polyurethane. Solid polymer electrolytes were prepared by complexes cationic PUs with different content of LiClO4. All the solid polymer electrolytes had sufficient thermal stability as confirmed by TGA and exhibited a single-phase behavior evidenced by DSC results. For these electrolytes, FT-IR spectra indicated the formation of polymer-ion complexes. The ac impedance spectra show that the conductivity of the electrolytes follow the Arrhenius behavior, and ionic conductivity is associated with both the charge migration of ions between coordination sites and transmission between aggregates, as confirmed by FT-IR and SEM. Alkyl quaternary ammonium salts in the polymer backbone are recognized as inherent plasticizers, which make the electrolytes exhibit liquid-like behavior. The plasticizing effect of PU-C8 and PU-C14 electrolytes are more effective than that of PU-C2 electrolyte. Maximum ionic conductivity at room temperature for PU-C8 electrolytes containing 50 wt% LiClO4 reached 1.1 × 10-4 S cm-1. This work provides a new research clue that alkyl quaternary ammonium salts could be used as inherent plasticizers and hence make the system behave like a liquid with high ionic conductivity, while preserving the dimensional stability of the solids.

Poly(terphenylene) Anion Exchange Membranes: The Effect of Backbone Structure on Morphology and Membrane Property

DOE PAGES

Lee, Woo-Hyung; Park, Eun Joo; Han, Junyoung; ...

2017-05-05

A new design concept for ion-conducting polymers in anion exchange membranes (AEMs) fuel cells is proposed based on structural studies and conformational analysis of polymers and their effect on the properties of AEMs. Thermally, chemically, and mechanically stable terphenyl-based polymers with pendant quaternary ammonium alkyl groups were synthesized to investigate the effect of varying the arrangement of the polymer backbone and cation-tethered alkyl chains. The results demonstrate that the microstructure and morphology of these polymeric membranes significantly influence ion conductivity and fuel cell performance. Finally, the results of this study provide new insights that will guide the molecular design ofmore » polymer electrolyte materials to improve fuel cell performance.« less

Coevolutionary constraints in the sequence-space of macromolecular complexes reflect their self-assembly pathways.

PubMed

Mallik, Saurav; Kundu, Sudip

2017-07-01

Is the order in which biomolecular subunits self-assemble into functional macromolecular complexes imprinted in their sequence-space? Here, we demonstrate that the temporal order of macromolecular complex self-assembly can be efficiently captured using the landscape of residue-level coevolutionary constraints. This predictive power of coevolutionary constraints is irrespective of the structural, functional, and phylogenetic classification of the complex and of the stoichiometry and quaternary arrangement of the constituent monomers. Combining this result with a number of structural attributes estimated from the crystal structure data, we find indications that stronger coevolutionary constraints at interfaces formed early in the assembly hierarchy probably promotes coordinated fixation of mutations that leads to high-affinity binding with higher surface area, increased surface complementarity and elevated number of molecular contacts, compared to those that form late in the assembly. Proteins 2017; 85:1183-1189. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Quaternary ammonium compounds: an alternative disinfection method for fresh produce wash water.

PubMed

Chaidez, Cristobal; Lopez, Javier; Castro-del Campo, Nohelia

2007-06-01

Irrigation water can serve as a vehicle for transporting pathogenic microorganisms, and numerous cases of bacterial infections from consumption of irrigated fresh produce have been reported in recent years. Chlorine-based disinfectants applied when produce is packed are widely used to control microorganisms. When applied properly, the chlorine products are effective. However, hazardous disinfection breakdown products can be formed, and chlorine disinfectants have high oxidant activity that can affect produce quality and pose a risk to food handlers. Quaternary Ammonium Compounds (QACs) are a disinfectant alternative for the washing of fruits and vegetables. They can control a great number of microorganisms, have low toxicity when used at recommended doses, and are stable in storage. The purpose of this work was to assess the disinfectant activity of QACs against Escherichia coli and Staphylococcus aureus under worst-case and average-case turbidity conditions, (2 and 100 nephelometric units); two disinfectant concentrations (100 and 200 mg/L; and two contact times (30 and 120 seconds). Our research showed that QACs were effective against both bacteria. The percentage reduction of Escherichia coli was significantly higher in the less turbid solution (P = 0.027), while turbidity did not affect the reduction of Staphylococcus aureus (P > 0.05). E. coli was more resistant to QAC treatment than S. aureus. Based on the data obtained we can conclude that QACs could be an alternative in washing processes of fruits and vegetables.

Self-assembly and photopolymerization of a novel quaternary-ammonium functionalized diacetylene on noble metal nanoparticles: A comparative study

NASA Astrophysics Data System (ADS)

Martinez-Espinoza, Maria Isabel; Maccagno, Massimo; Thea, Sergio; Alloisio, Marina

2018-01-01

Stable hydrosols of gold and silver nanoparticles coated with the quaternary-ammonium group endowed diacetylene DAAMM (N,N,N-trimethyl-3-(pentacosa-10,12-diynamido)propan-1-ammonium) were obtained through a ligand-exchange reaction leaving the morphology of the pristine cores unmodified. Photopolymerization of the chemisorbed diacetylene shell occurred in both red and blue phases thanks to the presence of internal, H-bondable amide functions in the monomer chain, which are supposed to help the formation of a packed bilayer on the metal surfaces. Multidisciplinary characterization of the polymerized samples, including spectroscopic, morphological and thermal techniques, highlighted that differences occur in the polymerization process on gold and silver nanoparticles under different experimental conditions, suggesting a higher affinity of the trimethylammonium headgroup for gold substrates in acidic media. With respect to the extensively investigated PCDA (pentacosa-10,12-diynoic acid), DAAMM showed reduced capability of photogenerating thick polymer shells, especially in the more delocalized blue form, probably because of the inefficiency of the cationic monomer to form the multi-bilayered architecture typical of the highly-performing, carboxyl-terminated diacetylene. On the other end, the inner cross-linked structure gives to poly(DAAMM)-coated nanohybrids increased stability in water with respect to self-assembled counterparts deriving from saturated cationic surfactants, making them a promising sensing platform for rapid and cost effective assays of real samples.

Relict colluvial boulder deposits as paleoclimatic indicators in the Yucca Mountain region, southern Nevada

USGS Publications Warehouse

Whitney, J.W.; Harrington, C.D.

1993-01-01

Early to middle Pleistocene boulder deposits are common features on southern Nevada hillslopes. These darkly varnished, ancient colluvial deposits stand out in stark contrast to the underlying light-colored bedrock of volcanic tuffs, and they serve as minor divides between drainage channels on modern hillslopes. To demonstrate the antiquity of these stable hillslope features, six colluvial boulder deposits from Yucca Mountain, Nye County, Nevada, were dated by cation-ratio dating of rock varnish accreted on boulder surfaces. Estimated minimum ages of these boulder deposits range from 760 to 170 ka. Five additional older deposits on nearby Skull and Little Skull Mountains and Buckboard Mesa yielded cation-ratio minimum-age estimates of 1.38 Ma to 800 ka. An independent cosmogenic chlorine-36 surface exposure date was obtained on one deposit, which confirms an estimated early to middle Quaternary age. These deposits have provided the oldest age estimates for unconsolidated hillslope deposits in the southwestern United States. We suggest that the colluvial boulder deposits were produced during early and middle Pleistocene glacial/pluvial episodes and were stabilized during the transition to drier interglacial climates. The preservation of old, thin hillslope deposits and the less-than-2-m incision by hillslope runoff adjacent to these deposits, indicate that extremely low denudation rates have occurred on resistant volcanic hillslopes in the southern Great Basin during Quaternary time. -from Authors

Determination of Betaines by Fast Atom Bombardment Mass Spectrometry 1

PubMed Central

Rhodes, David; Rich, Patrick J.; Myers, Ann C.; Reuter, Carol C.; Jamieson, Gene C.

1987-01-01

A rapid, sensitive, and selective method for the determination of betaines is described and discussed. The method entails derivatizing the quaternary ammonium compounds to increase their sensitivity to detection by fast atom bombardment mass spectrometry. Sensitivity of detection increases markedly as the length of the carbon chain of the alcohol used to esterify the betaine carboxylic acid group is increased (C4 > C3 > C2 > C1 > C0). The lower limit of detection of glycine betaine as the n-propyl ester is 0.05 nanomole per microliter of glycerol. Betaine aldehyde can be readily derivatized to the di-n-butyl or di-n-propyl acetal derivatives which exhibit lower limits of detection of about 5 picomoles and 10 picomoles per microliter of glycerol, respectively. Accurate quantification of these compounds is accomplished by the use of deuterium labeled internal standards or quaternary ammonium compound homologs of distinct mass. Methods for the synthesis of these internal standards are reported. Some applications of these methods are illustrated with stable isotope tracer studies on the kinetics of metabolism of choline to betaine aldehyde and glycine betaine in spinach leaf discs, and the identification of several Zea mays genotypes which appear deficient in glycine betaine. Tracer studies with deuterium labeled betaine aldehyde suggest that the deficiency of glycine betaine in one sweet corn hybrid is probably not due to a deficiency in the capacity to oxidize betaine aldehyde. PMID:16665522

SE Great Basin Play Fairway Analysis

DOE Data Explorer

Adam Brandt

2015-11-15

Within this submission are multiple .tif images with accompanying metadata of magnetotelluric conductor occurrence, fault critical stress composite risk segment (CRS), permeability CRS, Quaternary mafic extrusions, Quaternary fault density, and Quaternary rhyolite maps. Each of these contributed to a final play fairway analysis (PFA) for the SE Great Basin study area.

Attitudes, perceptions and awareness concerning quaternary prevention among family doctors working in the Social Security System, Peru: a cross-sectional descriptive study.

PubMed

Cuba Fuentes, María Sofía; Zegarra Zamalloa, Carlos Orlando; Reichert, Sonja; Gill, Dawn

2016-04-27

Quaternary Prevention is defined as the action taken to identify patients at risk of overtreatment, to protect them from additional medical treatments, and to suggest interventions that are ethically acceptable. Many countries and organizations have joined in the efforts to practice quaternary prevention. These countries started a campaign called Choosing Wisely that implements recommendations in order to avoid harming patients. To determine the attitudes, perceptions and awareness towards Quaternary Prevention and the practice of “Choosing Wisely Canada Recommendations” among family doctors working in the Social Security System in Peru. A questionnaire was developed after reviewing the literature and contacting experts in the field and was sent by email to all 64 family physicians in the Social Security System (Essalud) in Lima Peru. Responses were received from 40 participants. The response rate was 64%. Approximately 95% reported that they understand the concept of quaternary prevention. Agreement with all the recommendations was 90% or higher. In most of the recommendations the applicability was more than 80%. The most important barriers perceived for the practice of Quaternary Prevention were patients’ expectations (33%). There are positive perceptions towards Quaternary Preventions and Choosing Wisely recommendations in the family doctors of social security in Lima Peru.

Fast and stable algorithms for computing the principal square root of a complex matrix

NASA Technical Reports Server (NTRS)

Shieh, Leang S.; Lian, Sui R.; Mcinnis, Bayliss C.

1987-01-01

This note presents recursive algorithms that are rapidly convergent and more stable for finding the principal square root of a complex matrix. Also, the developed algorithms are utilized to derive the fast and stable matrix sign algorithms which are useful in developing applications to control system problems.

Recent Progress on the Stereoselective Synthesis of Cyclic Quaternary α-Amino Acids

PubMed Central

Cativiela, Carlos; Ordóñez, Mario

2010-01-01

The most recent papers describing the stereoselective synthesis of cyclic quaternary α-amino acids are collected in this review. The diverse synthetic approaches are classified according to the size of the ring and taking into account the bond that is formed to complete the quaternary skeleton. PMID:20300486

The ichthyofauna of limnic systems in Quaternary deposits of extreme southern Brazil

PubMed Central

Assumpção, Cindy M.; Quintela, Fernando M.; Corrêa, Fabiano; Loebmann, Daniel

2016-01-01

Abstract The Quaternary in the state of Rio Grande do Sul (RS), southern Brazil, is geologically represented by the coastal plain and was originated by successive events of Pleistocene-Holocene marine transgressions and the occurrence of alluvial deposits. This paper aimed to characterize the fish assemblage occurring in a swampy Quaternary area adjacent to Lagoa Pequena, a lacustrine system connected to the west margin of the Laguna dos Patos estuary. A checklist is also provided of the ichthyofauna so far recorded in limnic systems of Quaternary deposits in the state of Rio Grande do Sul. A total of 42 species was recorded, distributed in nine orders, 18 families and 31 genera. Characidae and Cichlidae were the most representative families, comprising 15 and 4 species respectively. A bibliographic revision associated to our sample data revealed the occurrence of 156 species in limnic systems inserted in RS Quaternary deposits (114 limnic, 15 marine/estuarine/limnic, ten marine/estuarine, nine estuarine/limnic and eight marine). Characiformes and Siluriformes are the most diverse orders, corroborating the Neotropical pattern. Seven species can be considered endemic to RS Quaternary deposits. PMID:28174498

Analysis of multiple quaternary ammonium compounds in the brain using tandem capillary column separation and high resolution mass spectrometric detection.

PubMed

Falasca, Sara; Petruzziello, Filomena; Kretz, Robert; Rainer, Gregor; Zhang, Xiaozhe

2012-06-08

Endogenous quaternary ammonium compounds are involved in various physiological processes in the central nervous system. In the present study, eleven quaternary ammonium compounds, including acetylcholine, choline, carnitine, acetylcarnitine and seven other acylcarnitines of low polarity, were analyzed from brain extracts using a two dimension capillary liquid chromatography-Fourier transform mass spectrometry method. To deal with their large difference in hydrophobicities, tandem coupling between reversed phase and hydrophilic interaction chromatography columns was used to separate all the targeted quaternary ammonium compounds. Using high accuracy mass spectrometry in selected ion monitoring mode, all the compounds could be detected from each brain sample with high selectivity. The developed method was applied for the relative quantification of these quaternary ammonium compounds in three different brain regions of tree shrews: prefrontal cortex, striatum, and hippocampus. The comparative analysis showed that quaternary ammonium compounds were differentially distributed across the three brain areas. The analytical method proved to be highly sensitive and reliable for simultaneous determination of all the targeted analytes from brain samples. Copyright © 2012 Elsevier B.V. All rights reserved.

ODP Sites 967 and 968 (eastern Mediterranean) revisited and implications for the global oxygen stable isotope chronology of the late Pleistocene

NASA Astrophysics Data System (ADS)

Konijnendijk, Tiuri; Lourens, Lucas; Ziegler, Martin

2013-04-01

ODP Sites 967 and 968 (eastern Mediterranean) revisited and implications for the global oxygen stable isotope chronology of the late Pleistocene ODP Sites 967 and 968, located in the Eastern Mediterranean at the Eratosthenes Seamount, are ideally situated to study both regional and global climate signals. Evidently, changes in the titanium to aluminum ratio of the bulk sediment reflect variations in North African aridity, and hence North African monsoon strength: increased levels of titanium are associated with enhanced windblown dust input from the Sahara and increased levels of aluminum with enhanced runoff from the river Nile. In addition, changes in the benthic foraminiferal stable isotope composition reflect primarily changes in global ice volume and deep sea temperature (Lourens et al., 2010; Ziegler et al., 2010). Here we completed and spliced the Ti/Al and benthic d18O data sets of ODP Site 968 and 967 for the past one million years at approximately 200-400 year resolution. The Ti/Al ratio reflect dominantly precession-controlled African monsoon intensity changes and was used to build an astronomically tuned age model for the composite record. This approach enabled us in first instance to establish an alternative and highly accurate chronology for sapropels in the Eastern Mediterranean, and lead to revisions of existing age models, especially around MIS 11 and 19, when the 405-kyr eccentricity cycle is at a minimum. Color reflectance, typically indicative of sapropels, appears incongruent with insolation forcing during these episodes. Secondly our Ti/Al-based chronology provides an independent age model for the benthic d18O record, which may shed new light upon the relationship between insolation and global climate (e.g. ice volume) changes. Our research indicates negligible differences between our record and the global benthic stack of Lisiecki and Raymo (LR04) between the present and MIS 11. However, there are significant discrepancies in the timing of terminations and onset of glaciation for several isotope stages prior to MIS 11 of up to 10,000 years. The direct comparison of our stable isotope record to insolation appears to suggest a dominant role of obliquity forcing in ice volume behavior for much further into the Pleistocene than generally assumed. References Lourens, L.J., J. Becker, R. Bintanja et al. (2010), Linear and non-linear response of late Neogene glacial cycles to obliquity forcing and implications for the Milankovitch theory. Quaternary Science Reviews 29(1-2), pp.352-365. Ziegler, M., E. Tuenter & L.J. Lourens. (2010), The precession phase of the boreal summer monsoon as viewed from the eastern Mediterranean (ODP Site 968). Quaternary Science Reviews 29(11-12), pp.1481-1490.

HUNT STABLE COMPLEX LOOKING NORTHWEST TOWARD DOG KENNEL RUINS ACROSS ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

HUNT STABLE COMPLEX LOOKING NORTHWEST TOWARD DOG KENNEL RUINS ACROSS THE GREAT CIRCUS - Overhills, Fort Bragg Military Reservation, Approximately 15 miles NW of Fayetteville, Overhills, Harnett County, NC

Synthesis and Characterization of Perfluoro Quaternary Ammonium Ion Exchange Membranes for Fuel Cell Applications

DTIC Science & Technology

2012-01-01

complex fuels (2, 4-6). Current research on alkali fuel cells is primarily focused on the development of a solid polymer anion exchange membrane ( AEM ...a collection of information if it does not display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. a...research focus the last few decades due to their high power density and low emissions when operating with hydrogen fuel (1-3). Recently however

Diastereo- and enantioselective iridium-catalyzed allylation of cyclic ketone enolates: synergetic effect of ligands and barium enolates.

PubMed

Chen, Wenyong; Chen, Ming; Hartwig, John F

2014-11-12

We report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from (R)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-catalyzed allylic substitution reactions with the proper choice of enolate countercation. The products of these reactions can be conveniently transformed to various useful polycarbocyclic structures.

Magnetic Properties of the DNA-Quaternary Ammonium Surfactant Complexes Studied by EMR Spectroscopy and SQUID Measurement

DTIC Science & Technology

2008-09-24

Eui Doo Do, Dong Hoon Choi, and Jung -Il Jin∗ Department of Chemistry, Korea University, Seoul 136-701, Korea Chang Hoon Lee Department of Polymer...Electromagnetic Properties of Modified DNA 5a. CONTRACT NUMBER FA48690714023 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Jung -Il Jin 5d...the last temperature- independent χPauli is the Pauli spin susceptibility attributed by delocalized con- ductive spin species. The molar

Diastereo- and enantioselective iridium-catalyzed allylation of cyclic ketone enolates: Synergetic effect of ligands and barium enolates

DOE PAGES

Chen, Wenyong; Chen, Ming; Hartwig, John F.

2014-10-22

Here, we report asymmetric allylic alkylation of barium enolates of cyclic ketones catalyzed by a metallacyclic iridium complex containing a phosphoramidite ligand derived from ( R)-1-(2-naphthyl)ethylamine. The reaction products contain adjacent quaternary and tertiary stereocenters. This process demonstrates that unstabilized cyclic ketone enolates can undergo diastereo- and enantioselective Ir-catalyzed allylic substitution reactions with the proper choice of enolate countercation. The products of these reactions can be conveniently transformed to various useful polycarbocyclic structures.

Origin and late quaternary tectonism of a western Canadian continental shelf trough

NASA Astrophysics Data System (ADS)

Moslow, Thomas F.; Luternauer, John L.; Rohr, Kristin

1991-08-01

Analyses of high resolution and multi-channel seismic profiles from the central continental shelf of western Canada ascribe a late Quaternary glacial origin to large-scale troughs. Along the margins of Moresby Trough, one of three large-scale cross-shelf bathymetric depressions in Queen Charlotte Sound, seismic profiles within Quaternary sediments show a divergence of reflectors, thickening and folding of seismic units, and concavity of reflectors suggestive of drag. Compactional subsidence, growth faulting, and compaction faulting are also observed. Fault traces commonly terminate below the seabed. Deformation of Quaternary sediments due to faulting is plastic in nature and maximum offset of reflectors is 2.5 m. The observed Quaternary deformation appears to be a product of rapid deposition, loading and subsidence of late Quaternary sediment, which is unrelated to seismic activity. In addition, Quaternary faulting was probably activated by post-glacial loading and isostatic rebound of consolidated Tertiary strata along the margins of continental shelf troughs. The presence of mass movement (slump or debris flow) deposits overlying lithified Tertiary strata along the flanks of Moresby Trough provides the only evidence of seismic activity in the study area. The lack of a mud drape over these deposits implies a late Holocene age for the timing of their emplacement. The Quaternary troughs are incised into Tertiary-aged sedimentary fill of the Queen Charlotte basin. Previous workers had interpreted seafloor escarpments paralleling the trough margins to indicate that the location of Moresby Trough was controlled by renewed or continued activity on Tertiary-aged faults. A multi-channel seismic line across Moresby Trough shows that such an escarpment on the seafloor does not correlate to faults either in the Tertiary basin fill or the underlying basement. Tertiary reflectors are continuous underneath Moresby Trough; the seafloor escarpment is an erosional feature and was not created by reactivation of Tertiary structures. Trough erosion and subsequent fill (up to 175 m thick) are entirely of Quaternary age.

Efficiency improvement of green light-emitting diodes by employing all-quaternary active region and electron-blocking layer

NASA Astrophysics Data System (ADS)

Usman, Muhammad; Saba, Kiran; Han, Dong-Pyo; Muhammad, Nazeer

2018-01-01

High efficiency of green GaAlInN-based light-emitting diode (LED) has been proposed with peak emission wavelength of ∼510 nm. By introducing quaternary quantum well (QW) along with the quaternary barrier (QB) and quaternary electron blocking layer (EBL) in a single structure, an efficiency droop reduction of up to 29% has been achieved in comparison to the conventional GaN-based LED. The proposed structure has significantly reduced electrostatic field in the active region. As a result, carrier leakage has been minimized and spontaneous emission rate has been doubled.

Ribosome binding induces repositioning of the signal recognition particle receptor on the translocon

PubMed Central

Kuhn, Patrick; Draycheva, Albena; Vogt, Andreas; Petriman, Narcis-Adrian; Sturm, Lukas; Drepper, Friedel; Warscheid, Bettina; Wintermeyer, Wolfgang

2015-01-01

Cotranslational protein targeting delivers proteins to the bacterial cytoplasmic membrane or to the eukaryotic endoplasmic reticulum membrane. The signal recognition particle (SRP) binds to signal sequences emerging from the ribosomal tunnel and targets the ribosome-nascent-chain complex (RNC) to the SRP receptor, termed FtsY in bacteria. FtsY interacts with the fifth cytosolic loop of SecY in the SecYEG translocon, but the functional role of the interaction is unclear. By using photo-cross-linking and fluorescence resonance energy transfer measurements, we show that FtsY–SecY complex formation is guanosine triphosphate independent but requires a phospholipid environment. Binding of an SRP–RNC complex exposing a hydrophobic transmembrane segment induces a rearrangement of the SecY–FtsY complex, which allows the subsequent contact between SecY and ribosomal protein uL23. These results suggest that direct RNC transfer to the translocon is guided by the interaction between SRP and translocon-bound FtsY in a quaternary targeting complex. PMID:26459600

Cryo-EM Structures Reveal Mechanism and Inhibition of DNA Targeting by a CRISPR-Cas Surveillance Complex.

PubMed

Guo, Tai Wei; Bartesaghi, Alberto; Yang, Hui; Falconieri, Veronica; Rao, Prashant; Merk, Alan; Eng, Edward T; Raczkowski, Ashleigh M; Fox, Tara; Earl, Lesley A; Patel, Dinshaw J; Subramaniam, Sriram

2017-10-05

Prokaryotic cells possess CRISPR-mediated adaptive immune systems that protect them from foreign genetic elements, such as invading viruses. A central element of this immune system is an RNA-guided surveillance complex capable of targeting non-self DNA or RNA for degradation in a sequence- and site-specific manner analogous to RNA interference. Although the complexes display considerable diversity in their composition and architecture, many basic mechanisms underlying target recognition and cleavage are highly conserved. Using cryoelectron microscopy (cryo-EM), we show that the binding of target double-stranded DNA (dsDNA) to a type I-F CRISPR system yersinia (Csy) surveillance complex leads to large quaternary and tertiary structural changes in the complex that are likely necessary in the pathway leading to target dsDNA degradation by a trans-acting helicase-nuclease. Comparison of the structure of the surveillance complex before and after dsDNA binding, or in complex with three virally encoded anti-CRISPR suppressors that inhibit dsDNA binding, reveals mechanistic details underlying target recognition and inhibition. Published by Elsevier Inc.

Analysis of a Soluble (UreD:UreF:UreG)2 Accessory Protein Complex and Its Interactions with Klebsiella aerogenes Urease by Mass Spectrometry

NASA Astrophysics Data System (ADS)

Farrugia, Mark A.; Han, Linjie; Zhong, Yueyang; Boer, Jodi L.; Ruotolo, Brandon T.; Hausinger, Robert P.

2013-09-01

Maturation of the nickel-containing urease of Klebsiella aerogenes is facilitated by the UreD, UreF, and UreG accessory proteins along with the UreE metallo-chaperone. A fusion of the maltose binding protein and UreD (MBP-UreD) was co-isolated with UreF and UreG in a soluble complex possessing a (MBP-UreD:UreF:UreG)2 quaternary structure. Within this complex a UreF:UreF interaction was identified by chemical cross-linking of the amino termini of its two UreF protomers, as shown by mass spectrometry of tryptic peptides. A pre-activation complex was formed by the interaction of (MBP-UreD:UreF:UreG)2 and urease. Mass spectrometry of intact protein species revealed a pathway for synthesis of the urease pre-activation complex in which individual hetero-trimer units of the (MBP-UreD:UreF:UreG)2 complex bind to urease. Together, these data provide important new insights into the structures of protein complexes associated with urease activation.

Asymmetric synthesis of α-amino acids via homologation of Ni(II) complexes of glycine Schiff bases; Part 1: alkyl halide alkylations.

PubMed

Sorochinsky, Alexander E; Aceña, José Luis; Moriwaki, Hiroki; Sato, Tatsunori; Soloshonok, Vadim A

2013-10-01

Alkylations of chiral or achiral Ni(II) complexes of glycine Schiff bases constitute a landmark in the development of practical methodology for asymmetric synthesis of α-amino acids. Straightforward, easy preparation as well as high reactivity of these Ni(II) complexes render them ready available and inexpensive glycine equivalents for preparing a wide variety of α-amino acids, in particular on a relatively large scale. In the case of Ni(II) complexes containing benzylproline moiety as a chiral auxiliary, their alkylation proceeds with high thermodynamically controlled diastereoselectivity. Similar type of Ni(II) complexes derived from alanine can also be used for alkylation providing convenient access to quaternary, α,α-disubstituted α-amino acids. Achiral type of Ni(II) complexes can be prepared from picolinic acid or via recently developed modular approach using simple secondary or primary amines. These Ni(II) complexes can be easily mono/bis-alkylated under homogeneous or phase-transfer catalysis conditions. Origin of diastereo-/enantioselectivity in the alkylations reactions, aspects of practicality, generality and limitations of this methodology is critically discussed.

Liquid-liquid distribution of ion associates of tetrabromoindate(III) with quaternary ammonium counter ions.

PubMed

Yamamoto, K; Matsumoto, A

1997-11-01

The solvent extraction of an ion associate of tetrabromoindate(III) ion, InBr(-)(4), with quaternary ammonium cations (Q(+)) has been studied. The extraction constant (K(ex)) were determined for the ion associates of InBr(-)(4) with Q(+) between an aqueous phase and several organic phases (chloroform, chlorobenzene, benzene and toluene). A linear relationship was found between log K(ex) and the total number of carbon atoms in Q(+); from the slope of the lines, the contribution of a methylene group to log K(ex) was calculated to be 0.91 for the chloroform extraction system and 0.52 for the other extraction systems. The extractability with alkyltrimethylammonium cations was larger than that with symmetrical tetraalkylammonium cations and the mean difference in log K(ex) for two cations (one of each type) with the same number of carbon atoms was about 1.3. From the extraction constant obtained, the extractability of InBr(-)(4) among metal-halogeno complex anions was in the order TlBr(-)(4) > BiI(-)(4) > AuBr(-)(4) > AuCl(-)(4) > TlCl(-)(4) > InBr(-)(4) > CuCl(-)(2).

Simulation of Glacial Cycles Before and After the Mid-Pleistocene Transition

NASA Astrophysics Data System (ADS)

Ganopolski, A.; Willeit, M.; Calov, R.

2017-12-01

In spite of significant progress achieved in understanding of glacial cycles, the cause of Mid-Pleistocene transition (MPT) is still not fully understood. To study possible mechanisms of the MPT we used the Earth system model of intermediate complexity CLIMBER-2 which incorporates all major components of the Earth system - atmosphere, ocean, land surface, northern hemisphere ice sheets, terrestrial biota and soil carbon, aeolian dust and marine biogeochemistry. We run the model through the entire Quaternary. The only prescribed forcing in these simulations is variations in Earth orbital parameters. In addition we prescribed gradually evolving in time terrestrial sediment cover and global volcanic outgassing. We found that gradual removal of terrestrial sediment from the Northern Hemisphere continent by glacial processes is sufficient to explain transition from 40-ka to 100-ka worlds around 1 million years ago. By starting the model at different times and using the same initial conditions we found that modeling results converge to the same solution which depends only on the orbital forcing and lower boundary conditions. Our results thus strongly suggest that Quaternary glacial cycles are externally forced and nearly deterministic.

Seismic imaging beneath an InSAR anomaly in eastern Washington State: Shallow faulting associated with an earthquake swarm in a low-hazard area

USGS Publications Warehouse

Stephenson, William J.; Odum, Jackson K.; Wicks, Chuck; Pratt, Thomas L.; Blakely, Richard J.

2016-01-01

In 2001, a rare swarm of small, shallow earthquakes beneath the city of Spokane, Washington, caused ground shaking as well as audible booms over a five‐month period. Subsequent Interferometric Synthetic Aperture Radar (InSAR) data analysis revealed an area of surface uplift in the vicinity of the earthquake swarm. To investigate the potential faults that may have caused both the earthquakes and the topographic uplift, we collected ∼3  km of high‐resolution seismic‐reflection profiles to image the upper‐source region of the swarm. The two profiles reveal a complex deformational pattern within Quaternary alluvial, fluvial, and flood deposits, underlain by Tertiary basalts and basin sediments. At least 100 m of arching on a basalt surface in the upper 500 m is interpreted from both the seismic profiles and magnetic modeling. Two west‐dipping faults deform Quaternary sediments and project to the surface near the location of the Spokane fault defined from modeling of the InSAR data.

East African Cenozoic vegetation history.

PubMed

Linder, Hans Peter

2017-11-01

The modern vegetation of East Africa is a complex mosaic of rainforest patches; small islands of tropic-alpine vegetation; extensive savannas, ranging from almost pure grassland to wooded savannas; thickets; and montane grassland and forest. Here I trace the evolution of these vegetation types through the Cenozoic. Paleogene East Africa was most likely geomorphologically subdued and, as the few Eocene fossil sites suggest, a woodland in a seasonal climate. Woodland rather than rainforest may well have been the regional vegetation. Mountain building started with the Oligocene trap lava flows in Ethiopia, on which rainforest developed, with little evidence of grass and none of montane forests. The uplift of the East African Plateau took place during the middle Miocene. Fossil sites indicate the presence of rainforest, montane forest and thicket, and wooded grassland, often in close juxtaposition, from 17 to 10 Ma. By 10 Ma, marine deposits indicate extensive grassland in the region and isotope analysis indicates that this was a C 3 grassland. In the later Miocene rifting, first of the western Albertine Rift and then of the eastern Gregory Rift, added to the complexity of the environment. The building of the high strato-volcanos during the later Mio-Pliocene added environments suitable for tropic-alpine vegetation. During this time, the C 3 grassland was replaced by C 4 savannas, although overall the extent of grassland was reduced from the mid-Miocene high to the current low level. Lake-level fluctuations during the Quaternary indicate substantial variation in rainfall, presumably as a result of movements in the intertropical convergence zone and the Congo air boundary, but the impact of these fluctuations on the vegetation is still speculative. I argue that, overall, there was an increase in the complexity of East African vegetation complexity during the Neogene, largely as a result of orogeny. The impact of Quaternary climatic fluctuation is still poorly understood. © 2017 Wiley Periodicals, Inc.

Pre-Quaternary divergence and subsequent radiation explain longitudinal patterns of genetic and morphological variation in the striped skink, Heremites vittatus.

PubMed

Baier, Felix; Schmitz, Andreas; Sauer-Gürth, Hedwig; Wink, Michael

2017-06-09

Many animal and plant species in the Middle East and northern Africa have a predominantly longitudinal distribution, extending from Iran and Turkey along the eastern Mediterranean coast into northern Africa. These species are potentially characterized by longitudinal patterns of biological diversity, but little is known about the underlying biogeographic mechanisms and evolutionary timescales. We examined these questions in the striped skink, Heremites vittatus, one such species with a roughly longitudinal distribution across the Middle East and northern Africa, by analyzing range-wide patterns of mitochondrial DNA (mtDNA) sequence and multi-trait morphological variation. The striped skink exhibits a basic longitudinal organization of mtDNA diversity, with three major mitochondrial lineages inhabiting northern Africa, the eastern Mediterranean coast, and Turkey/Iran. Remarkably, these lineages are of pre-Quaternary origin, and are characterized by p-distances of 9-10%. In addition, within each of these lineages a more recent Quaternary genetic diversification was observed, as evidenced by deep subclades and high haplotype diversity especially in the Turkish/Iranian and eastern Mediterranean lineages. Consistent with the genetic variation, our morphological analysis revealed that the majority of morphological traits show significant mean differences between specimens from northern Africa, the eastern Mediterranean coast, and Turkey/Iran, suggesting lineage-specific trait evolution. In addition, a subset of traits exhibits clinal variation along the eastern Mediterranean coast, potentially indicating selection gradients at the geographic transition from northern Africa to Anatolia. The existence of allopatric, morphologically and genetically divergent lineages suggests that Heremites vittatus might represent a complex with several taxa. Our work demonstrates that early divergence events in the Pliocene, likely driven by both climatic and geological factors, established the longitudinal patterns and distribution of Heremites vittatus. Subsequent radiation during the Pleistocene generated the genetic and morphological diversity observed today. Our study provides further evidence that longitudinal diversity patterns and species distributions in the Middle East and northern Africa were shaped by complex evolutionary processes, involving the region's intricate geological history, climatic oscillations, and the presence of the Sahara.

Evaluation of simple geochemical indicators of aeolian sand provenance: Late Quaternary dune fields of North America revisited

USGS Publications Warehouse

Muhs, Daniel

2017-01-01

Dune fields of Quaternary age occupy large areas of the world's arid and semiarid regions. Despite this, there has been surprisingly little work done on understanding dune sediment provenance, in part because many techniques are time-consuming, prone to operator error, experimental, highly specialized, expensive, or require sophisticated instrumentation. Provenance of dune sand using K/Rb and K/Ba values in K-feldspar in aeolian sands of the arid and semiarid regions of North America is tested here. Results indicate that K/Rb and K/Ba can distinguish different river sands that are sediment sources for dunes and dune fields themselves have distinctive K/Rb and K/Ba compositions. Over the Basin and Range and Great Plains regions of North America, the hypothesized sediment sources of dune fields are reviewed and assessed using K/Rb and K/Ba values in dune sands and in hypothesized source sediments. In some cases, the origins of dunes assessed in this manner are consistent with previous studies and in others, dune fields are found to have a more complex origin than previously thought. Use of K/Rb and K/Ba for provenance studies is a robust method that is inexpensive, rapid, and highly reproducible. It exploits one of the most common minerals found in dune sand, K-feldspar. The method avoids the problem of using simple concentrations of key elements that may be subject to interpretative bias due to changes in mineralogical maturity of Quaternary dune fields that occur over time.

Polarized Infrared Reflectance Studies of Quaternary In0.04Al0.06Ga0.90N

NASA Astrophysics Data System (ADS)

Bakhori, S. K. Mohd; Lee, S. C.; Ahmad, M. A.; Ng, S. S.; Hassan, H. Abu

2010-07-01

Group III-nitride has re-gained considerable interest recently as wide direct band gap semiconductor materials for opto-electronic and high power devices. The quaternary InAlGaN have great flexibility in tailoring their band gap profile while maintaining their lattice-matching and structural integrity. In this study, we report for the first time the polarized infrared (IR) reflectance studies of quaternary In0.04Al0.06Ga0.90N by using Fourier transform infrared spectroscopy of Perkin-Elmer. The quaternary In0.04Al0.06Ga0.90N epilayers was grown on sapphire by molecular beam epitaxy. The polarized IR reflectance spectra obtained at incident angle of 15° were then compared with modeling spectrum of damped harmonic oscillator. Through this study, the transverse and longitudinal optical phonon modes of quaternary In0.04Al0.06Ga0.90N epilayers were obtained.

Multi-valued logic gates based on ballistic transport in quantum point contacts.

PubMed

Seo, M; Hong, C; Lee, S-Y; Choi, H K; Kim, N; Chung, Y; Umansky, V; Mahalu, D

2014-01-22

Multi-valued logic gates, which can handle quaternary numbers as inputs, are developed by exploiting the ballistic transport properties of quantum point contacts in series. The principle of a logic gate that finds the minimum of two quaternary number inputs is demonstrated. The device is scalable to allow multiple inputs, which makes it possible to find the minimum of multiple inputs in a single gate operation. Also, the principle of a half-adder for quaternary number inputs is demonstrated. First, an adder that adds up two quaternary numbers and outputs the sum of inputs is demonstrated. Second, a device to express the sum of the adder into two quaternary digits [Carry (first digit) and Sum (second digit)] is demonstrated. All the logic gates presented in this paper can in principle be extended to allow decimal number inputs with high quality QPCs.

Letter Report: Stable Hydrogen and Oxygen Isotope Analysis of B-Complex Groundwater Samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Brady D.; Moran, James J.; Nims, Megan K.

Report summarizing stable oxygen and hydrogen isotope analysis of two groundwater samples from the B-Complex. Results from analyses were compared to perched water and pore water analyses performed previously.

Using vegetation model-to-data comparisons to test the role of abiotic factors in the Neogene and Quaternary origins of modern C4 grasslands

NASA Astrophysics Data System (ADS)

Fox, D. L.; Strömberg, C.; Pau, S.; Taylor, L.; Lehmann, C.; Osborne, C.; Beerling, D. J.; Still, C. J.

2014-12-01

Grasslands dominated by taxa using the C4 photosynthetic pathway evolved on several continents during the Neogene and Quaternary, long after C4 photosynthesis first evolved among grasses. The histories of these ecosystems are relatively well documented in the geological record from stable carbon isotopes (fossil vertebrate herbivores, paleosols) and the plant microfossil record (pollen, phytoliths). The distinct biogeography and ecophysiology of modern C3 and C4 grasses have led to hypotheses explaining the origins of C4 grasslands in terms of long term changes in the Earth system such as increased aridity and decreasing atmospheric pCO2. However, proxies for key parameters of these hypotheses (e.g., temperature, precipitation, pCO2) are still in development, not yet widely applied, or remain contentious, so testing the hypotheses globally remains difficult. To understand better possible links between changes in the Earth system and the origin of C4 grasslands on different continents, we are undertaking a global scale comparison between observational records of C4 grass abundances in Miocene and Pliocene localities compiled from the literature, and three increasingly complex models of C4 dominance and abundance. The literature compilation comprises >2,600 δ13C values of both fossil vertebrates and of paleosol carbonates and >6,700 paleobotanical records. We are using paleoclimate output from the HadCM3L GCM over a range of pCO2 values for each epoch to model C4 dominance or abundance in grid cells as (Model 1) months per year exceeding the temperature at which net assimilation is greater for C4 than C3 photosynthesis (crossover temperature); (Model 2) the number of months per year exceeding the crossover temperature and having sufficient precipitation for growth (≥25 cm/yr; Collatz model); and (Model 3) the Sheffield Dynamic Global Vegetation Model (SDGVM), output from which includes biomass (g C/m2/yr) for distinct structural components (roots, stems, leaves) of multiple plant functional types (C3 and C4 grasses, evergreen and deciduous trees). Statistical comparisons of the isotopic and paleobotanical databases with the paleoclimate and vegetation model outputs allows us to assess the possible role of abiotic factors in the evolution of modern C4 grasslands during the late Neogene.

Versatile methods for synthesizing organic acid salts of quaternary berberine-type alkaloids as anti-ulcerative colitis agents.

PubMed

Zhang, Zhi-Hui; Li, Jing; Zhang, Hai-Jing; Deng, An-Jun; Wu, Lian-Qiu; Li, Zhi-Hong; Song, Hong-Rui; Wang, Wen-Jie; Qin, Hai-Lin

2016-06-01

Two versatile methods to synthesize kinds of organic acid salts of quaternary berberine-type alkaloids were investigated in order to determine which is more efficient to improve the liposolubility of the target compounds and to explore the efficacy of the target compounds as anti-ulcerative colitis (UC) agents. Overall evaluation according to the reaction results and yields of the final products indicated that the synthetic method using tertiary (±)-8-acylmethyldihydroberberine-type alkaloids as key intermediates is superior to that of using tertiary dihydroberberine-type alkaloids as intermediates. Ten target compounds were synthesized using quaternary berberine chloride and quaternary coptisine chloride as starting materials, respectively, and the anti-UC activity of some target compounds was evaluated in an in vitro x-box-binding protein 1 (XBP1) transcriptional activity assay using dual luciferase reporter detection. At 10 μM, the tested compounds were found to activate the transcription of XBP1 target at almost the same level as that of quaternary coptisine chloride. The synthesized target compounds were also found to share higher liposolubility than the inorganic acid salts of quaternary berberine-type alkaloid.

Quaternary extensional growth folding beneath Reno, Nevada, imaged by urban seismic profiling

USGS Publications Warehouse

Stephenson, William J.; Frary, Roxy N.; Louie, John; Odum, Jackson K.

2013-01-01

We characterize shallow subsurface faulting and basin structure along a transect through heavily urbanized Reno, Nevada, with high‐resolution seismic reflection imaging. The 6.8 km of P‐wave data image the subsurface to approximately 800 m depth and delineate two subbasins and basin uplift that are consistent with structure previously inferred from gravity modeling in this region of the northern Walker Lane. We interpret two primary faults that bound the uplift and deform Quaternary deposits. The dip of Quaternary and Tertiary strata in the western subbasin increases with greater depth to the east, suggesting recurrent fault motion across the westernmost of these faults. Deformation in the Quaternary section of the western subbasin is likely evidence of extensional growth folding at the edge of the Truckee River through Reno. This deformation is north of, and on trend with, previously mapped Quaternary fault strands of the Mt. Rose fault zone. In addition to corroborating the existence of previously inferred intrabasin structure, these data provide evidence for an active extensional Quaternary fault at a previously unknown location within the Truckee Meadows basin that furthers our understanding of both the seismotectonic framework and earthquake hazards in this urbanized region.

Late Quaternary Environmental Changes Inferred from the stable Oxygen Isotope Composition of Aquatic Insects (Chironomidae: Diptera) and Stable Hydrogen Isotope Composition of bulk sediments from Idavain Lake, Southwest Alaska

NASA Astrophysics Data System (ADS)

Wang, Y.; Finney, B.; Wooller, M. J.

2007-12-01

Several techniques are available to examine the isotopic composition of historic lake waters, providing data that can subsequently be used to examine environmental changes. Recently-developed techniques are the stable oxygen isotope analysis of subfossil chironomid (Diptera: Chironomidae) head capsules (mostly chitin) preserved in lake sediments and stable hydrogen isotope analyses directly on bulk sediments. An advantage of using δ18O of chironomids is that the chitinous chironomid headcapsules preserve well in lake sediments, retaining the stable oxygen isotope signature of the lake in which they lived. An advantage of δD analyses of bulk sediments is that a sediment core can be analyzed relatively easily and when the %C (total organic carbon) and %H profiles correlate the data can be used to infer past δD changes of the organics in the sediments. We present results from these analyses of a lake sediment core from Idavain Lake (58°46'N, 155°57'W, 223m above sea level) in southwest Alaska in concert with other paleolimnological proxies, including δ15N, δ13C, LOI, magnetic susceptibility, organic content and opal concentrations for a better understanding of paleolimnological changes since deglaciation for the region. Our preliminilary result shows that downcore shifts of δ18O analyzed from chironomid head capsules coincide well with LOI and pollen changes. The δD of sediments and TOM showed large magnitude changes and reflected the relative lake level changes during the record. This study aim to test the correlation between stable isotope analyese on chiornomid head capsules, lake water, and bulk sediments. In the addition, our study will add to the relatively small database of paleoenvironmental reconstructions from terrestrial sites in Southwest Alaska.

The Influence of Inherited Topography and/or Tectonics on Paleo-channel Systems and Incised Valleys Offshore of South Carolina

NASA Astrophysics Data System (ADS)

Long, A. M.; Hill, J. C.

2016-12-01

The Quaternary paleo-channel and incised valley systems of the Southeastern United States have been well documented onshore; however, few studies have focused on the positions and fill histories of these systems on the continental shelf. The effects of inherited topography can be studied through the integration of seismo-acoustic and core data. Existing offshore datasets have been used to document underlying structural and stratigraphic fabrics deeper than the Quaternary in the sedimentary record. By integrating these results with the published tectonic setting and onshore interpretations, some of the controls on paleo-channel/incised valley positions can be inferred. Preliminary results suggest the stress caused by the uplift along the Cape Fear Arch has been accommodated by shallow folding and reactivation of deeper structures in the South Carolina offshore province. The resultant topography may have dictated both the position and geometry of the fluvial incisions across the shelf. This in turn influences the accommodation space available to be filled in as sea level fluctuates. The depositional facies within the paleo-channel and incised valley range from single, uninterrupted fill to complex and repeated scour and fill with at least four different episodes of erosion and deposition. The observations and interpretations proposed here are the first steps in unraveling the complex interplay between sea level, climate, and tectonic changes on the morphology and stratigraphy of incised valleys and paleo-channels observed offshore of South Carolina.

Brownian dynamics simulations of interactions between aldolase and G- or F-actin.

PubMed Central

Ouporov, I V; Knull, H R; Thomasson, K A

1999-01-01

Compartmentation of proteins in cells is important to proper cell function. Interactions of F-actin and glycolytic enzymes is one mechanism by which glycolytic enzymes can compartment. Brownian dynamics (BD) simulations of the binding of the muscle form of the glycolytic enzyme fructose-1,6-bisphosphate aldolase (aldolase) to F- or G-actin provide first-encounter snapshots of these interactions. Using x-ray structures of aldolase, G-actin, and three-dimensional models of F-actin, the electrostatic potential about each protein was predicted by solving the linearized Poisson-Boltzmann equation for use in BD simulations. The BD simulations provided solution complexes of aldolase with F- or G-actin. All complexes demonstrate the close contacts between oppositely charged regions of the protein surfaces. Positively charged surface regions of aldolase (residues Lys 13, 27, 288, 293, and 341 and Arg 257) are attracted to the negatively charged amino terminus (Asp 1 and Glu 2 and 4) and other patches (Asp 24, 25, and 363 and Glu 361, 364, 99, and 100) of actin subunits. According to BD results, the most important factor for aldolase binding to actin is the quaternary structure of aldolase and actin. Two pairs of adjacent aldolase subunits greatly add to the positive electrostatic potential of each other creating a region of attraction for the negatively charged subdomain 1 of the actin subunit that is exposed to solvent in the quaternary F-actin structure. PMID:9876119

Sequential character of low-energy ternary and quaternary nuclear fission

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kadmensky, S. G., E-mail: kadmensky@phys.vsu.ru; Bulychev, A. O.

2016-09-15

An analysis of low-energy true ternary (quaternary) nuclear fission leads to the conclusion that these fission modes have a sequential two-step (three-step) character such that the emission of a third particle (third and fourth particles) and the separation of fission fragments occur at distinctly different instants, in contrast to the simultaneous emergence of all fission products in the case of onestep ternary (quaternary) fission. This conclusion relies on the following arguments. First, the emission of a third particle (third and fourth particles) from a fissile nucleus is due to a nonevaporative mechanism associated with a nonadiabatic character of the collectivemore » deformation motion of this nucleus at the stages preceding its scission. Second, the axial symmetry of the deformed fissile compound nucleus and the direction of its symmetry axis both remain unchanged at all stages of ternary (quaternary) fission. This circumstancemakes it possible to explain themechanism of the appearance of observed anisotropies and T — odd asymmeries in the angular distributions of products of ternary (quaternary) nuclear fission. Third, the T —odd asymmetry discovered experimentally in ternary nuclear fission induced by cold polarized neutrons obeys the T —invariance condition only in the case of a sequential two-step (three-step) character of true ternary (quaternary) nuclear fission. At the same time, this asymmetry is not a T —invariant quantity in the case of the simultaneous emission of products of true ternary (quaternary) nuclear fission from the fissile compound nucleus.« less

Pleistocene changes in the fauna and flora of South america.

PubMed

Vuilleumier, B S

1971-08-27

In recent years, the view that Pleistocene climatic events played a major role in the evolution of the biotas of southern, primarily tropical continents has begun to displace the previously held conviction that these areas remained relatively stable during the Quaternary. Studies of speciation patterns of high Andean plant and avian taxa (7-14) have led to the conclusion that Pleistocene climatic events were the factors that ultimately shaped the patterns now observed in the paramo-puna and the related Patagonian flora and fauna. The final uplift of the Andes at the end of the Tertiary automatically limits the age of the high Andean habitats and their biotas to the Quaternary. Within this period, the number of ecological fluctuations caused by the glaciations could easily have provided the mechanism behind the patterns now present in these habitats (Appendix, 1; Figs. 1 and 2; Table 1). In glacial periods, when vegetation belts, were lowered, organisms in the paramo-puna habitat were allowed to expand their ranges. In interglacial periods, these taxa were isolated on disjunct peaks, where differentiation could occur. At times of ice expansion, glacial tongues and lakes provided local barriers to gene exchange, whereas in warm, interglacial times, dry river valleys were a major deterrent to the interbreeding of populations on different mountains (Fig. 2; Table 2). A preliminary analysis of about 10 to 12 percent of the total South American avifauna (14), subsequent to the study of the high Andean biota, suggested that the birds of all the major habitats of the continent possess, with about equal frequency, similar stages of speciation. This correspondence in levels of evolution indicated that the avifauna of vegetation zones which were thought to have been more stable (for example, tropical rainforests) are as actively speciating as are those of the more recent paramo-puna habitats. More intensive work on lowland tropical taxa (16, 19-21) and recent work on montane forest elements (40) now justify the conclusion that the floras and faunas of these areas were also greatly affected by Pleistocene climatic shifts. In the broad region of South America that lies within the tropics, a series of humid-arid cycles (Appendix, 6, 8-10) drastically and repeatedly altered vegetation patterns during the Quaternary. Both montane and lowland rainforests were fragmented during dry periods and were able to reexpand during humid phases. Speciation of forest elements was initiated-and sometimes completed-in isolated patches of the fragmented forest. Secondary contact, with hybridization or reunition of populations that did not become reproductively isolated, occurred in periods of reexpansion. These biological data, combined with supportive geological evidence (Appendix, 1-11), show that climatic events during the last million or so years have affected the biota of South America as much as the Pleistocene glacial changes affected the biotas of Eurasia and North America. Since most of South America lies within tropical latitudes, it is suggested here that part of the diversity of species in the tropical areas of this continent is due to two historical factors: the lack of wholesale elimination of species (compared with northern and high latitudes), and ample opportunity for speciation in successive periods of ecological isolation. The apparent paradox of the wealth of species in the "stable tropics" is partially explained by the fact that the tropics have probably been quite unstable, from the point of view of their biotas, during the Pleistocene and perhaps part of the Tertiary.

Simultaneous acquisition of Sparker and airgun seismic data - a key to understanding the interaction of deep structures and the Quaternary in the Kattegat area

NASA Astrophysics Data System (ADS)

Nørmark, Egon; Jensen, Jørn B.; Bendixen, Carina; Clausen, Ole R.; Trinhammer, Per L.; Boldreel, Lars O.; Seidenkrantz, Marit S.; Fanget, Anne-Sophie

2014-05-01

The geological evolution of the Kattegat and Baltic Sea area during the last 130,000 years encompasses a complex series of glacial advances with highly oscillating ice margins interrupted by marine inundations and significant glacial lake deposition. One of the most significant lacustrine episodes is related to the build-up and drainage of the Baltic Glacial Lake during the last deglaciation. The link of these major depositional events to global climate as well as their impact on local and regional environment is, however, still poorly understood. The relation between the deep structures and Quaternary deposition is also not well resolved. In order to improve this understanding we aim at acquiring an understanding of the 3-dimensional evolution of the Quaternary sediments in the Kattegat and Baltic Sea areas using seismic studies. We relate these seismic data to the palaeoclimatic and sedimentological information obtained through the sedimentological and micropalaeontological analyses of both short sediment gravity cores and of samples from IODP Expedition 347 drilled in the fall of 2013. Different types of seismic data are needed for studying the relationship between the crustal structure, pre-Quaternary topography, and Quaternary deposition than seismic data needed for studying the detailed depositional dynamics within the Quaternary deposits. This is because when using airguns with a deep penetration needed for studying deep-laying structures the resulting seismic data has too poor resolution for studying the very shallow parts. In contrast the very high resolution sparker data has a poor penetration depth. Traditionally, these two different types of seismic data are for practical reasons not been collected simultaneously, or even on the same cruise. As a result, these two (complementary) dataset are difficult to compare, especially when they are acquired under different conditions (changes in positioning, noise levels, etc.). In this study, we have solved the problem by acquiring both seismic datasets simultaneously during the same leg. Both the sparker and airgun energy sources are towed behind the vessel, and the common streamer is placed in the middle behind the energy sources. In order to optimize the acquisition hydrophones are spaced with 3.125m for the uppermost 125m of the layout, where the main part of the reflections for the Sparker data is acquired, whereas the spacing is 6.25m at the remaining 400m of the streamer. The energy release of the different sources is timed in order to minimize the interference between the two systems. The resulting seismic sections are excellent examples of different data from the same area that is resolved at different depth intervals and vertical resolution. This allows us to directly compare the data and gives a hitherto unseen differentiation of seismic resolution in different parts of the succession. A preliminary geological analysis of the data shows that deposition in a number of the Quaternary mini-basins is controlled by the underlying structures, which can be related to the Sorgenfrei-Tornquist fault Zone. This infers that deep structures in some areas may still control the present bathymetry, even within smaller basins. The dating of the events and the relation to global climatic changes awaits the biostratigraphical analysis of the IODP boreholes.

The influence of novel gemini surfactants containing cycloalkyl side-chains on the structural phases of DNA in solution.

PubMed

Pietralik, Zuzanna; Kumita, Janet R; Dobson, Christopher M; Kozak, Maciej

2015-07-01

Very important to gene therapy is the delivery system of the nucleic acids (called a vector), which will enhance the efficiency of the transport of new DNA into cells whilst protecting against damage. A promising alternative to the currently used viral vectors are the systems based on amphiphilic compounds - lipoplexes. Among them, gemini surfactants, which consist of two hydrophobic chains and two cationic heads connected by a linker - spacer group, appear to be promising candidates. The subject of this study involves two gemini surfactants, alkoxy derivatives of bis-imidazolium quaternary salts, differing in the length of their spacer groups and how they interact with two types of salmon sperm DNA (low and high molecular weight (MW)) or plasmid DNA (pDNA). The mixtures of gemini surfactants with nucleic acids of differing p/n ratios (positive-to-negative charge ratio) were characterised by small angle X-ray scattering (SAXS) of synchrotron radiation, dynamic light scattering (DLS), circular dichroism (CD) spectroscopy, atomic force microscopy (AFM), transmission electron microscopy (TEM) and gel electrophoresis techniques. This analysis allows for the selection of the most suitable and promising candidates for non-viral vectors in gene therapy, determination of the conditions needed to form stable complexes, identification of conformational changes in the DNA molecules upon interactions with gemini surfactants and in some cases, determination of the structures formed in these lipoplexes. Copyright © 2015 Elsevier B.V. All rights reserved.

Stable powders made from photosensitive polycrystalline complexes of heterocyclic monomers and their polymers

NASA Technical Reports Server (NTRS)

Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor); Hodko, Dalibor (Inventor)

1999-01-01

The present invention relates to a low electronic conductivity polymer composition having well dispersed metal granules, a stable powder made from photosensitive polycrystalline complexes of pyrrole, or its substituted derivatives and silver cations for making the polymer composition, and methods of forming the stable powder and polymer composition, respectively. A polycrystalline complex of silver and a monomer, such as pyrrole, its substituted derivatives or combinations thereof, is precipitated in the form of a stable photosensitive powder upon addition of the monomer to a solvent solution, such as toluene containing an electron acceptor. The photosensitive powder can be stored in the dark until needed. The powder may be dissolved in a solvent, cast onto a substrate and photopolymerized.

De nouveaux éléments structuraux du complexe aquifère profond du bassin du Rharb (Maroc) : implications hydrogéologiques

NASA Astrophysics Data System (ADS)

Kili, Malika; El Mansouri, Bouabid; Chao, Jamal; Fora, Abderrahman Ait

2006-12-01

The Rharb basin is located in northwestern Morocco. It is a part of one of the most important hydrogeological basins of Morocco, and extends over some 4000 km 2. The nature of its Plio-Quaternary sedimentary fill and its structural and palaeoenvironmental contexts are reflected by great variations in aerial and temporal facies distribution. This distribution, in turn, is a direct cause of the observed complexity in the geometry of potentially water-bearing beds. In the present work, we present an image of potential new hydrogeological reservoirs and define new structures that partially explain their architecture. To cite this article: M. Kili et al., C. R. Geoscience 338 (2006).

The Effects of Aseismic Ridge Collision on Upper Plate Deformation: Cocos Ridge Collision and Deformation of the Western Caribbean

NASA Astrophysics Data System (ADS)

La Femina, P. C.; Govers, R. M. A.; Ruiz, G.; Geirsson, H.; Camacho, E.; Mora-Paez, H.

2015-12-01

The collision of the Panamanian isthmus with northwestern South America is thought to have initiated as early as Oligocene - Miocene time (23-25 Ma) based on geologic and geophysical data and paleogeographic reconstructions. This collision was driven by eastward-directed subduction beneath northwestern South America. Cocos - Caribbean convergence along the Middle America Trench, and Nazca - Caribbean oblique convergence along the South Panama Deformed Belt have resulted in complex deformation of the southwestern Caribbean since Miocene - Pliocene time. Subduction and collision of the aseismic Cocos Ridge is thought to have initiated <3.5 Ma and has been linked to: 1) late Miocene-Pliocene cessation of volcanism and uplift of the Cordillera de Talamanca, Costa Rica; 2) Quaternary migration of the volcanic arc toward the back-arc in Costa Rica; 3) Quaternary to present deformation within the Central Costa Rica Deformed Belt; 4) Quaternary to present shortening across the fore-arc Fila Costeña fold and thrust belt and back-arc North Panama Deformed Belt (NPDB); 5) Quaternary to present outer fore-arc uplift of Nicoya Peninsula above the seamount domain, and the Osa and Burica peninsulas above the ridge; and 6) Pleistocene to present northwestward motion of the Central American Fore Arc (CAFA) and northeastward motion of the Panama Region. We investigate the geodynamic effects of Cocos Ridge collision on motion of the Panama Region with a new geodynamic model. The model is compared to a new 1993-2015 GPS-derived three-dimensional velocity field for the western Caribbean and northwestern South America. Specifically, we test the hypotheses that the Cocos Ridge is the main driver for upper plate deformation in the western Caribbean. Our models indicate that Cocos Ridge collision drives northwest-directed motion of the CAFA and the northeast-directed motion of the Panama Region. The Panama Region is driven into the Caribbean across the NPDB and into northwestern South America, which is also converging with the Panama Region, pushing it toward the west-northwest. Therefore, recent (<3.5 Ma) collision of Panama with northwestern South America is driven by Cocos Ridge collision.

The Cocos Ridge drives collision of Panama with northwestern South America

NASA Astrophysics Data System (ADS)

LaFemina, Peter; Govers, Rob; Mora-Paez, Hector; Geirsson, Halldor; Cmacho, Eduardo

2015-04-01

The collision of the Panamanian isthmus with northwestern South America is thought to have initiated as early as Oligocene - Miocene time (23-25 Ma) based on geologic and geophysical data and paleogeographic reconstructions. This collision was driven by eastward-directed subduction beneath northwestern South America. Cocos - Caribbean convergence along the Middle America Trench, and Nazca - Caribbean oblique convergence along the South Panama Deformed Belt have resulted in complex deformation of the southwestern Caribbean since Miocene - Pliocene time. Subduction and collision of the aseismic Cocos Ridge is thought to have initiated <3.5 Ma and has been linked to: 1) late Miocene-Pliocene cessation of volcanism and uplift of the Cordillera de Talamanca; 2) Quaternary migration of the volcanic arc toward the back-arc; 3) Quaternary to present deformation within the Central Costa Rica Deformed Belt; 4) Quaternary to present shortening across the fore-arc Fila Costeña fold and thrust belt and back-arc North Panama Deformed Belt (NPDB); 5) Quaternary to present outer fore-arc uplift of Nicoya Peninsula above the seamount domain, and the Osa and Burica peninsulas above the ridge; and 6) Pleistocene to present northwestward motion of the Central American Fore Arc (CAFA) and northeastward motion of the Panama Region. We investigate the geodynamic effects of Cocos Ridge collision on motion of the Panama Region with a new geodynamic model. The model is compared to a new 1993-2015 GPS-derived three-dimensional velocity field for the western Caribbean and northwestern South America. Specifically, we test the hypotheses that the Cocos Ridge is the main driver for upper plate deformation in the western Caribbean. Our models indicate that Cocos Ridge collision drives northwest-directed motion of the CAFA and the northeast-directed motion of the Panama Region. The Panama Region is driven into the Caribbean across the NPDB and into northwestern South America, which is also converging with the Panama Region, pushing it toward the west-northwest. Therefore, modern collision of Panama with northwestern South America is driven by collision of the Cocos Ridge.

Understanding the major transitions in Quaternary climate dynamics

NASA Astrophysics Data System (ADS)

Willeit, Matteo; Ganopolski, Andrey

2017-04-01

Climate dynamics over the past 3 million years was characterized by strong variability associated with glacial cycles and several distinct regime changes. The Pliocene-Pleistocene Transition (PPT), which happened around 2.7 million years ago, was characterized by the appearance of the large continental ice sheets over Northern Eurasia and North America. For two million years after the PPT climate variability was dominated by relatively symmetric 40 kyr cycles. At around 1 million years ago the dominant mode of climate variability experienced a relatively rapid transition from 40 kyr to strongly asymmetric 100 kyr cycles of larger amplitude (Mid-Pleistocene Transition). Additionally, during the past 800 kyr there are clear differences between the earlier and the later glacial cycles with the last five cycles characterized by larger magnitude of variability (Mid-Brunhes Event). Here, we use the Earth system model of intermediate complexity CLIMBER-2 to explore possible mechanisms that could explain these regime shifts. CLIMBER-2 incorporates all major components of the Earth system - atmosphere, ocean, land surface, northern hemisphere ice sheets, terrestrial biota and soil carbon, marine biogeochemistry and aeolian dust. The model was optimally tuned to reproduce climate, ice volume and CO2 variability over the last 400,000 years. Using the same model version, we performed a large set of simulations covering the entire Quaternary (3 million years) starting from identical initial conditions and using a parallelization in time technique which consists of starting the model at different times (every 100,000 years) and running each simulation for 500,000 years. The Earth's orbital variations are the only prescribed radiative forcing. Several sets of the Northern Hemisphere orography and sediment thickness representing different stages of landscape evolution during the Quaternary are prescribed as boundary conditions for the ice sheet model and volcanic CO2 outgassing is used as the external forcing for the carbon cycle to allow for different background atmospheric CO2 concentrations. We show that by varying only these two model boundary conditions and volcanic forcing the model is able to reproduce the major regime changes of Quaternary long-term climate dynamics.

Effect of alkali cations on two-dimensional networks of two new quaternary thioarsenates (III) prepared by a facile surfactant-thermal method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Dongming; Hou, Peipei; Liu, Chang

2016-09-15

Two new quaternary thioarsenates(III) NaAg{sub 2}AsS{sub 3}·H{sub 2}O (1) and KAg{sub 2}AsS{sub 3} (2) with high yields have been successfully prepared through a facile surfactant-thermal method. It is interesting that 2 can only be obtained with the aid of ethanediamine (en), which indicates that weak basicity of solvent is beneficial to the growth of 2 compared with 1. Both 1 and 2 feature the similar two-dimensional (2D) layer structures. However, the distortion of the primary honeycomb-like nets in 2 is more severe than that of 1, which demonstrates that Na{sup +} and K{sup +} cations have different structure directing effectsmore » on these two thioarsenates(III). Both experimental and theoretical studies confirm 1 and 2 are semiconductors with band gaps in the visible region. Our success in preparing these two quaternary thioarsenates(III) proves that surfactant-thermal technique is a powerful yet facile synthetic method to explore new complex chalcogenides. - Graphical abstract: Two new quaternary thioarsenates(III) NaAg{sub 2}AsS{sub 3}·H{sub 2}O (1) and KAg{sub 2}AsS{sub 3} (2) with high yields have been successfully prepared through a facile surfactant-thermal method. X-ray single crystal diffraction analyses demonstrate that Na{sup +} and K{sup +} cations have different structure directing effects on these two thioarsenates(III). Both experimental and theoretical studies confirm 1 and 2 are semiconductors with band gaps in the visible region. Display Omitted - Highlights: • NaAg{sub 2}AsS{sub 3}⋅H{sub 2}O (1) and KAg{sub 2}AsS{sub 3} (2) were prepared through surfactant-thermal method. • Crystal structures show Na{sup ±} and K{sup ±} have different structure directing effects. • The weak basicity of solvent is benefit to the growth of 2 compared with 1. • Experimental and theoretical studies confirm 1 and 2 are semiconductors.« less

Synthesis and Characterization of Perfluoro Quaternary Ammonium Anion Exchange Membranes

DTIC Science & Technology

2012-01-01

study, new alkaline exchange membranes were prepared from the perfluorinated 3M ionomer with various quaternary ammonium cations attached with...ammonium anion exchange membranes Report Title ABSTRACT In this study, new alkaline exchange membranes were prepared from the perfluorinated 3M ionomer...exchange membranes were prepared from the perfluorinated 3M ionomer with vari- ous quaternary ammonium cations attached with sulfonamide linkage. The

Self-Assembly of Helical Ribbons

DTIC Science & Technology

1999-07-01

detergent, a phosphatidylcholine or a fatty acid , and a steroid analog of cholesterol. In almost all systems, two different pitch types of helical...quater- nary sterol systems (QSS), on a quaternary fatty acid system (QFAS), and on two lipid concentrate systems, as defined below. In addition to high...lipid concentrate; QSS, quaternary sterol systems; QFAS, quaternary fatty acid system; NaTC, sodium taurocholate; DOPC, 1,2-dioleoyl-glycero- 3

Transmetallation from CCC-NHC pincer Zr complexes in the synthesis of air-stable CCC-NHC pincer Co(iii) complexes and initial hydroboration trials.

PubMed

Reilly, Sean W; Webster, Charles Edwin; Hollis, T Keith; Valle, Henry U

2016-02-21

Development of CCC-NHC pincer Co complexes via transmetalation from Zr is reported. Formation of these air-stable Co(iii) complexes was achieved through use of a CoCl2 or Co(acac)3in situ or with a discrete CCC-NHC pincer Zr transmetallating agent. Preliminary activity in the hydroboration of styrene is reported. This facile methodology will further the development of CCC-NHC pincer first-row transition metal complexes.

Analysis of La Dehesa paleo-landslide. Central Pre-Andes of Argentina

NASA Astrophysics Data System (ADS)

Tapia Baldis, Carla; Rothis, Luis Martín; Perucca, Laura; Esper Angillieri, María; Vargas, Horacio; Ponce, David; Allis, Carlos

2018-04-01

The main objective of this paper is to consider the influence of Quaternary faults as likely triggering factor for rockslides occurrence in the Central Pre-Andes, a region with intense shallow seismic activity. A rockslide deposit was selected as study case, placed in the western flank of La Dehesa and Talacasto (DT) range (31°3‧37″ S and 68°46‧ 8″ W). Applied methodology includes the characterization of main discontinuities, reconstruction of the topography using a high-resolution digital elevation model, safety factor calculation along the sliding surface and, Newmark displacements estimation for three different hypothetical seismic scenarios, recreated from existing neotectonic local information. Equilibrium-limit method's results confirm that study case, La Dehesa rockslide (LDR), had a stable and safe slope's configuration under static conditions. However, a seismic horizontal coefficient between 0.2 and 0.3 decreases safety factor below the safety threshold. Newmark's displacements for different seismic reconstructed scenarios varies between 4.1 and 15.9 cm, values that agreed with a coherent failure process, likely triggered by Pleistocene to Holocene seismogenic sources in Central Pre-Andes. LDR trigger could be assigned mainly to an earthquake related to La Dehesa Quaternary fault (LDF) activity; however, similar movements produced by neighboring faults should not be discarded. LDR triggering related to climatic conditions is despised. Finally, the methodology presented in this work is easy to reproduce and may be applied to other rockslides located in the mountainous areas of the Central Pre-Andes of Argentina.

Structure-based Design of Cyclically Permuted HIV-1 gp120 Trimers That Elicit Neutralizing Antibodies*

PubMed Central

Kesavardhana, Sannula; Das, Raksha; Citron, Michael; Datta, Rohini; Ecto, Linda; Srilatha, Nonavinakere Seetharam; DiStefano, Daniel; Swoyer, Ryan; Joyce, Joseph G.; Dutta, Somnath; LaBranche, Celia C.; Montefiori, David C.; Flynn, Jessica A.; Varadarajan, Raghavan

2017-01-01

A major goal for HIV-1 vaccine development is an ability to elicit strong and durable broadly neutralizing antibody (bNAb) responses. The trimeric envelope glycoprotein (Env) spikes on HIV-1 are known to contain multiple epitopes that are susceptible to bNAbs isolated from infected individuals. Nonetheless, all trimeric and monomeric Env immunogens designed to date have failed to elicit such antibodies. We report the structure-guided design of HIV-1 cyclically permuted gp120 that forms homogeneous, stable trimers, and displays enhanced binding to multiple bNAbs, including VRC01, VRC03, VRC-PG04, PGT128, and the quaternary epitope-specific bNAbs PGT145 and PGDM1400. Constructs that were cyclically permuted in the V1 loop region and contained an N-terminal trimerization domain to stabilize V1V2-mediated quaternary interactions, showed the highest homogeneity and the best antigenic characteristics. In guinea pigs, a DNA prime-protein boost regimen with these new gp120 trimer immunogens elicited potent neutralizing antibody responses against highly sensitive Tier 1A isolates and weaker neutralizing antibody responses with an average titer of about 115 against a panel of heterologous Tier 2 isolates. A modest fraction of the Tier 2 virus neutralizing activity appeared to target the CD4 binding site on gp120. These results suggest that cyclically permuted HIV-1 gp120 trimers represent a viable platform in which further modifications may be made to eventually achieve protective bNAb responses. PMID:27879316

A biomarker stable isotope record of late Quaternary climate and organic matter export in Southwestern Taiwan

NASA Astrophysics Data System (ADS)

Chang, Q.; Hren, M. T.; Lin, A. T.; Eley, Y.; Yu, S. W.; Harris, G.

2017-12-01

We present new leaf wax n-alkane hydrogen (δD) and carbon (δ13C) isotopic data from a 36-m-long core from off-shore southwestern Taiwan to evaluate late Quaternary changes in climate and the source of organic matter exported from the landscape. The core (MD178-3291) is located on the flank of the Gaoping Submarine Canyon that connects with the Gaoping river catchment in southwestern Taiwan. The sediment deposition in this core spans the last 26 kyr, providing a unique record of glacial-interglacial changes in organic matter export from the Taiwan orogen. The δD and δ13C both show a shift in isotopic compositions at 15 kyr, that coincides with the shift in planktonic foraminifera δ18O record from the same core as well as the global sea level. We therefore interpret this dominant shift as affected by the global glacial to interglacial transition. Following by this transition and through the interglacial period, both biomarker δD and δ13C data record fluctuations that we suggest result from short timescale changes in the distribution of organic inputs to the offshore site. This change in source is most likely caused by increases in storm and landslide frequency or intensity during warmer intervals. This interpretation is supported by terrestrial records that show an increase in landslides in the Gaoping catchment and evidence for enhanced rainfall intensity and a corresponding increase in the frequency of turbidity currents.

Structural, electronic, magnetic, half-metallic, mechanical, and thermodynamic properties of the quaternary Heusler compound FeCrRuSi: A first-principles study.

PubMed

Wang, Xiaotian; Khachai, Houari; Khenata, Rabah; Yuan, Hongkuan; Wang, Liying; Wang, Wenhong; Bouhemadou, Abdelmadjid; Hao, Liyu; Dai, Xuefang; Guo, Ruikang; Liu, Guodong; Cheng, Zhenxiang

2017-11-23

In this paper, we have investigated the structural, electronic, magnetic, half-metallic, mechanical, and thermodynamic properties of the equiatomic quaternary Heusler (EQH) compound FeCrRuSi using the density functional theory (DFT) and the quasi-harmonic Debye model. Our results reveal that FeCrRuSi is a half-metallic material (HMM) with a total magnetic moment of 2.0 μ B in agreement with the well-known Slater-Pauling rule M t  = Z t  - 24. Furthermore, the origin of the half-metallic band gap in FeCrRuSi is well studied through a schematic diagram of the possible d-d hybridization between Fe, Cr and Ru elements. The half-metallic behavior of FeCrRuSi can be maintained in a relatively wide range of variations of the lattice constant (5.5-5.8 Å) under uniform strain and the c/a ratio (0.96-1.05) under tetragonal distortion. The calculated phonon dispersion, cohesive and formation energies, and mechanical properties reveal that FeCrRuSi is stable with an EQH structure. Importantly, the compound of interest has been prepared and is found to exist in an EQH type structure with the presence of some B2 disorder. Moreover, the thermodynamic properties, such as the thermal expansion coefficient α, the heat capacity C V , the Grüneisen constant γ, and the Debye temperature Θ D are calculated.

Short-term climate changes in the Holsteinian Interglacial - EGU2012-132

NASA Astrophysics Data System (ADS)

Nitychoruk, J.; Bińka, K.; Ruppert, H.; Tudryn, A.

2012-04-01

Oxygen and carbon stable isotopes from fossil lake sediments of the Holsteinian age (eastern Poland) give evidence for the abrupt climate shifts in this interglacial that coincide with the changes in vegetation inferred from palaeobotanical data. Especially changes of the stable isotope ratios as well as decrease in the carbonate content in the deposits and increase in silicate redeposited from the area around the lake are synchronous with the short-term climatic deteriorations within the interglacial pollen flora. Two distinct climate shifts are recorded in the Holsteinian. The first one is marked by the very characteristic pine-birch cold phase after the yew (Taxus) domination that is reported from numerous pollen diagrams from Central Europe. This distinct cooling resembles a phenomenon known as 8.2 ka event in the Holocene, when waters of the Agassiz Lake in North America drained into the Atlantic Ocean (Koutsodendris et al. 2010). Enormous volumes of freshwater from melting of the Laurentian ice-sheet caused disturbances in the Gulf Stream and as a result some decrease in regional temperatures. The second distinct cooling of a lower rank took place within the younger part of the climatic optimum of the Holsteinian. It is relatively less known, because most often pollen records lack sufficient temporal resolution needed to identify this event. A well documented cooling in the Holsteinian deposits from Dethlingen, northern Germany (Koutsodendris et al. 2010) and from the Ossówka, eastern Poland (Nitychoruk et al. 2005) are exceptional. In the sequence from Dethlingen, a distinct increase in the percentage of pioneer trees is accompanied by a lower content of temperate taxa. At Ossówka, the shift of climate is noted as the rise of ratio of oxygen and carbon isotopes. According to Nitychoruk (2000) the cold event is coincident with volcanic eruptions evidenced by volcanic ash found in the lake deposits at that time. Literature Koutsodendris, A., Müller, U.C., Pross, J., Brauer, A., Kotthoff, U., Lotter, A.F. 2010. Vegetation dynamics and climate variability during the Holsteinian interglacial based on a pollen record from Dethlingen (northern Germany). Quaternary Science Reviews, 29, 3298-3307. Nitychoruk, J. 2000. Climate reconstruction from stable-isotope composition of the Mazovian Interglacial (Holsteinian) lake sediments in eastern Poland. Acta Geologica Polonica, 50, 247-294. Nitychoruk, J., Bińka, K., Hoefs, J., Ruppert, H. & Schneider, J. 2005. Climate reconstruction for the Holsteinian Interglacial in Eastern Poland and its comparison with isotopic data from Marine Isotope Stage 11. Quaternary Science Reviews, 24, 631-644.

Viscosities of nonelectrolyte liquid mixtures. III. Selected binary and quaternary mixtures

NASA Astrophysics Data System (ADS)

Wakefield, D. L.

1988-05-01

This paper is the final in a series of three viscosity and density studies of pure n-alkanes and selected binary and quaternary mixtures. A standard U-tube viscometer was used for viscosity measurements, and a Pyrex flask-type pycnometer was used for density determinations. Results are given here for pure alkane and selected binary mixtures of n-tetradecane + n-octane, for selected quaternary mixtures of n-hexadecane + n-dodecane + n-decane + n-hexane, and for pure and selected quaternary mixtures of n-hexadecane + n-dodecane + n-nonane + n-heptane at 303.16 and 308.16 K. The principle of congruence was tested, as was the Grunberg and Nissan equation, as they have been shown to be useful as prediction techniques for other n-alkane binary mixtures. Comparisons were made between the two groups of quaternary alkane mixtures and the binary n-tetradecane + n-octane mixtures of the same “pseudo” composition to understand better the dependence of mixture viscosities on the composition parameter.

Evaluation of chitosan quaternary ammonium salt-modified resin denture base material.

PubMed

Song, Rong; Zhong, Zhaohua; Lin, Lexun

2016-04-01

Chitosan quaternary ammonium salt displays good antioxidant and antibacterial characteristics and it shows appreciable solubility in water. When added to the traditional denture material to form a resin base, it could promote good oral health by improving the oral environment. In this study, chitosan quaternary ammonium salt was added to the denture material following two different methods. After three months of immersion in artificial saliva, the specimens were tested for tensile strength and were scanned by electron microscope. The murine fibroblast cytotoxicity and antibacterial properties were also tested. The result showed no significant differences in the tensile strength and in the proliferation of murine L929 fibroblast cells. The two structures of chitosan quaternary ammonium salt-modified denture material had different degrees of corrosion resistance and antimicrobial properties. These results indicate that chitosan quaternary ammonium salt-modified resin denture base material has the potential to become a new generation oral denture composite material. Copyright © 2015 Elsevier B.V. All rights reserved.

The competition of charge remote and charge directed fragmentation mechanisms in quaternary ammonium salt derivatized peptides--an isotopic exchange study.

PubMed

Cydzik, Marzena; Rudowska, Magdalena; Stefanowicz, Piotr; Szewczuk, Zbigniew

2011-12-01

Derivatization of peptides as quaternary ammonium salts (QAS) is a promising method for sensitive detection by electrospray ionization tandem mass spectrometry (Cydzik et al. J. Pept. Sci. 2011, 17, 445-453). The peptides derivatized by QAS at their N-termini undergo fragmentation according to the two competing mechanisms - charge remote (ChR) and charge directed (ChD). The absence of mobile proton in the quaternary salt ion results in ChR dissociation of a peptide bond. However, Hofmann elimination of quaternary salt creates an ion with one mobile proton leading to the ChD fragmentation. The experiments on the quaternary ammonium salts with deuterated N-alkyl groups or amide NH bonds revealed that QAS derivatized peptides dissociate according to the mixed ChR-ChD mechanism. The isotopic labeling allows differentiation of fragments formed according to ChR and ChD mechanisms. © The Author(s) 2011. This article is published with open access at Springerlink.com

Poly(3,4-ethylenedioxythiophene)-Poly(styrenesulfonate) Interlayer Insertion Enables Organic Quaternary Memory.

PubMed

Cheng, Xue-Feng; Hou, Xiang; Qian, Wen-Hu; He, Jing-Hui; Xu, Qing-Feng; Li, Hua; Li, Na-Jun; Chen, Dong-Yun; Lu, Jian-Mei

2017-08-23

Herein, for the first time, quaternary resistive memory based on an organic molecule is achieved via surface engineering. A layer of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) was inserted between the indium tin oxide (ITO) electrode and the organic layer (squaraine, SA-Bu) to form an ITO/PEDOT-PSS/SA-Bu/Al architecture. The modified resistive random-access memory (RRAM) devices achieve quaternary memory switching with the highest yield (∼41%) to date. Surface morphology, crystallinity, and mosaicity of the deposited organic grains are greatly improved after insertion of a PEDOT-PSS interlayer, which provides better contacts at the grain boundaries as well as the electrode/active layer interface. The PEDOT-PSS interlayer also reduces the hole injection barrier from the electrode to the active layer. Thus, the threshold voltage of each switching is greatly reduced, allowing for more quaternary switching in a certain voltage window. Our results provide a simple yet powerful strategy as an alternative to molecular design to achieve organic quaternary resistive memory.

Influence of chemical disorder on energy dissipation and defect evolution in concentrated solid solution alloys

PubMed Central

Zhang, Yanwen; Stocks, G. Malcolm; Jin, Ke; Lu, Chenyang; Bei, Hongbin; Sales, Brian C.; Wang, Lumin; Béland, Laurent K.; Stoller, Roger E.; Samolyuk, German D.; Caro, Magdalena; Caro, Alfredo; Weber, William J.

2015-01-01

A grand challenge in materials research is to understand complex electronic correlation and non-equilibrium atomic interactions, and how such intrinsic properties and dynamic processes affect energy transfer and defect evolution in irradiated materials. Here we report that chemical disorder, with an increasing number of principal elements and/or altered concentrations of specific elements, in single-phase concentrated solid solution alloys can lead to substantial reduction in electron mean free path and orders of magnitude decrease in electrical and thermal conductivity. The subsequently slow energy dissipation affects defect dynamics at the early stages, and consequentially may result in less deleterious defects. Suppressed damage accumulation with increasing chemical disorder from pure nickel to binary and to more complex quaternary solid solutions is observed. Understanding and controlling energy dissipation and defect dynamics by altering alloy complexity may pave the way for new design principles of radiation-tolerant structural alloys for energy applications. PMID:26507943

Use of spectroscopic technique to develop a reagent for Mo(VI) utilizing micellar effects on complex formation

NASA Astrophysics Data System (ADS)

Taşcioğlu, Sülin; Kaki, E.; Taşcioğlu, Senay

2012-09-01

Ultraviolet and visible spectral properties of aqueous solutions of molybdenum(VI) (Mo), gallic acid (GA), Lalanine (Ala), and L-Phenylalanine (Phe), and of their binary and ternary solutions were investigated in the absence and presence of anionic, cationic, and nonionic surfactant micelles. Evaluation of the spectra in a comparative way revealed that both Ala and Phe form ternary complexes with Mo and GA. The formation of a quaternary complex between Mo, GA, Phe, and cetyltrimethylammonium bromide at pH 4.5 provided a reagent system with a strikingly high sensitivity (1.2•106 l/(mol•cm)) for use in the spectrophotometric determination of Mo. A mechanism of micellar effects was discussed in terms of the substrate molecular charge and hydrophobicity, and rationalized on the basis of the spectral data obtained above and below the isoelectric pH of the amino acids.

Progress report. Task 1 - quaternary tectonics, 1 October 1991--30 September 1992

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

1992-09-30

Progress is reported on a study concerned with the quaternary tectonics of Yucca Mountain, the proposed site for an underground disposal facility for high-level radioactive wastes. Refinement and revision of crater Flat Quaternary stratigraphy continued and consisted of several activities: revision of rock varnish cation leaching curve; sample comparison of RV manganese;,iron microlaminations;and correlation of Crater Flat allostratigraphic units with regional chronologies.

INTERNATIONAL CONFERENCE ON SEMICONDUCTOR INJECTION LASERS SELCO-87: Simple formula for the thermal conductivity of a quaternary solid solution

NASA Astrophysics Data System (ADS)

Nakwaski, W.

1988-11-01

An analysis is made of the thermal conductivity of quaternary solid solutions (alloys) allowing for their disordered structure on the basis of a phenomenological analysis proposed by Abeles. This method is applied to a quaternary solid solution In1 - xGaxAsyP1 - y. A simple analytic expression is derived for the thermal conductivity of this material.

Advances in the synthesis of α-quaternary α-ethynyl α-amino acids.

PubMed

Boibessot, Thibaut; Bénimélis, David; Meffre, Patrick; Benfodda, Zohra

2016-09-01

α-Quaternary α-ethynyl α-amino acids are an important class of non-proteinogenic amino acids that play an important role in the development of peptides and peptidomimetics as therapeutic agents and in the inhibition of enzyme activities. This review provides an overview of the literature concerning synthesis and applications of α-quaternary α-ethynyl α-amino acids covering the period from 1977 to 2015.

Classification of protein quaternary structure by functional domain composition

PubMed Central

Yu, Xiaojing; Wang, Chuan; Li, Yixue

2006-01-01

Background The number and the arrangement of subunits that form a protein are referred to as quaternary structure. Quaternary structure is an important protein attribute that is closely related to its function. Proteins with quaternary structure are called oligomeric proteins. Oligomeric proteins are involved in various biological processes, such as metabolism, signal transduction, and chromosome replication. Thus, it is highly desirable to develop some computational methods to automatically classify the quaternary structure of proteins from their sequences. Results To explore this problem, we adopted an approach based on the functional domain composition of proteins. Every protein was represented by a vector calculated from the domains in the PFAM database. The nearest neighbor algorithm (NNA) was used for classifying the quaternary structure of proteins from this information. The jackknife cross-validation test was performed on the non-redundant protein dataset in which the sequence identity was less than 25%. The overall success rate obtained is 75.17%. Additionally, to demonstrate the effectiveness of this method, we predicted the proteins in an independent dataset and achieved an overall success rate of 84.11% Conclusion Compared with the amino acid composition method and Blast, the results indicate that the domain composition approach may be a more effective and promising high-throughput method in dealing with this complicated problem in bioinformatics. PMID:16584572

Characterization of complexes of nucleoside-5'-phosphorothioate analogues with zinc ions.

PubMed

Sayer, Alon Haim; Itzhakov, Yehudit; Stern, Noa; Nadel, Yael; Fischer, Bilha

2013-10-07

On the basis of the high affinity of Zn(2+) to sulfur and imidazole, we targeted nucleotides such as GDP-β-S, ADP-β-S, and AP3(β-S)A, as potential biocompatible Zn(2+)-chelators. The thiophosphate moiety enhanced the stability of the Zn(2+)-nucleotide complex by about 0.7 log units. ATP-α,β-CH2-γ-S formed the most stable Zn(2+)-complex studied here, log K 6.50, being ~0.8 and ~1.1 log units more stable than ATP-γ-S-Zn(2+) and ATP-Zn(2+) complexes, and was the major species, 84%, under physiological pH. Guanine nucleotides Zn(2+) complexes were more stable by 0.3-0.4 log units than the corresponding adenine nucleotide complexes. Likewise, AP3(β-S)A-zinc complex was ~0.5 log units more stable than AP3A complex. (1)H- and (31)P NMR monitored Zn(2+) titration showed that Zn(2+) coordinates with the purine nucleotide N7-nitrogen atom, the terminal phosphate, and the adjacent phosphate. In conclusion, replacement of a terminal phosphate by a thiophosphate group resulted in decrease of the acidity of the phosphate moiety by approximately one log unit, and increase of stability of Zn(2+)-complexes of the latter analogues by up to 0.7 log units. A terminal phosphorothioate contributed more to the stability of nucleotide-Zn(2+) complexes than a bridging phosphorothioate.

Influence of chemical disorder on energy dissipation and defect evolution in concentrated solid solution alloys

DOE PAGES

Zhang, Yanwen; Stocks, George Malcolm; Jin, Ke; ...

2015-10-28

A long-standing objective in materials research is to understand how energy is dissipated in both the electronic and atomic subsystems in irradiated materials, and how related non-equilibrium processes may affect defect dynamics and microstructure evolution. Here we show that alloy complexity in concentrated solid solution alloys having both an increasing number of principal elements and altered concentrations of specific elements can lead to substantial reduction in the electron mean free path and thermal conductivity, which has a significant impact on energy dissipation and consequentially on defect evolution during ion irradiation. Enhanced radiation resistance with increasing complexity from pure nickel tomore » binary and to more complex quaternary solid solutions is observed under ion irradiation up to an average damage level of 1 displacement per atom. Understanding how materials properties can be tailored by alloy complexity and their influence on defect dynamics may pave the way for new principles for the design of radiation tolerant structural alloys.« less

Aerial gamma ray and magnetic survey: Mississippi and Florida airborne survey, Russellville quadrangle, Arkansas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

1980-09-01

The Russellville quadrangle in north central Arkansas overlies thick Paleozoic sediments of the Arkoma Basin. These Paleozoics dominate surface exposure except where covered by Quaternary alluvial materials. Examination of available literature shows no known uranium deposits (or occurrences) within the quadrangle. Eighty-eight groups of uranium samples were defined as anomalies and are discussed briefly. None were considered significant, and most appeared to be of cultural origin. Magnetic data show character that suggest structural and/or lithologic complexity, but imply relatively deep-seated sources.

Rapid Construction of Complex 2-Pyrrolines through Lewis Acid-Catalyzed, Sequential Three-Component Reactions via in Situ-Generated 1-Azaallyl Cations.

PubMed

Schlegel, Marcel; Schneider, Christoph

2018-05-09

The first Sc(OTf) 3 -catalyzed dehydration of 2-hydroxy oxime ethers to generate benzylic stabilized 1-azaallyl cations, which are captured by 1,3-carbonyls, is described. A subsequent addition of primary amines in a sequential three-component reaction affords highly substituted and densely functionalized tetrahydroindeno[2,1- b]pyrroles as single diastereomers with up to quantitative yield. Thus, three new σ-bonds and two vicinal quaternary stereogenic centers are generated in a one-pot operation.

Impacts of climate change on the formation and stability of late Quaternary sand sheets and falling dunes, Black Mesa region, southern Colorado Plateau, USA

USGS Publications Warehouse

Ellwein, Amy L.; Mahan, Shannon; McFadden, Leslie D.

2015-01-01

Widely used predictive models of eolian system dynamics are typically based entirely on climatic variables and do not account for landscape complexity and geomorphic history. Climate-only assumptions fail to give accurate predictions of the dynamics of this and many other dune fields. A growing body of work suggests that eolian deposits in wind-driven semiarid climates may be more strongly related to increases in sediment supply than to increases in aridity.

A Tunable and Enantioselective Hetero-Diels-Alder Reaction Provides Access to Distinct Piperidinoyl Spirooxindoles.

PubMed

Jayakumar, Samydurai; Louven, Kathrin; Strohmann, Carsten; Kumar, Kamal

2017-12-11

The active complexes of chiral N,N'-dioxide ligands with dysprosium and magnesium salts catalyze the hetero-Diels-Alder reaction between 2-aza-3-silyloxy-butadienes and alkylidene oxindoles to selectively form 3,3'- and 3,4'-piperidinoyl spirooxindoles, respectively, in very high yields and with excellent enantioselectivities. The exo-selective asymmetric cycloaddition successfully regaled the construction of sp 3 -rich and highly substituted natural-product-based spirooxindoles supporting many chiral centers, including contiguous all-carbon quaternary centers. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mapping the North Sea base-Quaternary: using 3D seismic to fill a gap in the geological record

NASA Astrophysics Data System (ADS)

Lamb, Rachel; Huuse, Mads; Stewart, Margaret; Brocklehurst, Simon H.

2014-05-01

The identification and mapping of the base-Quaternary boundary in the central parts of the North Sea is problematic due to the change from an unconformable transition between Pliocene and Pleistocene deltaic deposits in the southern North Sea to a conformable one further north (Sejrup et al 1991; Gatliff et al 1994). The best estimates of the transition use seismic reflection data to identify a 'crenulated reflector' (Buckley 2012), or rely on correlating sparse biostratigraphy (Cameron et al 1987). Recent integration of biostratigraphy, pollen analysis, paleomagnetism and amino acid analysis in the Dutch and Danish sectors (Rasmussen et al 2005; Kuhlmann et al 2006) allows greater confidence in the correlation to a regional 3D seismic dataset and show that the base-Quaternary can be mapped across the entire basin. The base-Quaternary has been mapped using the PGS MegaSurvey dataset from wells in the Danish Sector along the initially unconformable horizon and down the delta front into the more conformable basin giving a high degree of confidence in the horizon pick. The mapped horizon is presented here alongside the difference between this new interpretation and the previously interpreted base-Quaternary (Buckley 2012). The revised base-Quaternary surface reaches a depth of 1248 ms TWT or approximately 1120 m (assuming average velocity of 1800 m/s) showing an elongate basin shape that follows the underlying structure of the Central Graben. The difference between the revised base-Quaternary and the traditional base-Quaternary reaches a maximum of over 600 ms TWT or approximately 540 m in the south-west with over 300 ms TWT or approximately 270 m at the Josephine well (56° 36.11'N, 2° 27.09'E) in the centre of the basin. Mapping this new base-Quaternary allows for the interpretation of the paleo-envionrment during the earliest Quaternary. Seismic attribute analysis indicates a deep water basin with sediment deposition from multiple deltas and redistribution by deep water currents. This has strong implications for both the Quaternary climate archive and petroleum systems in the North Sea. Key Words: base-Quaternary; chronostratigraphy: seismic interpretation; paleoenvironments References Buckley, F.A., (2012) 'An Early Pleistocene grounded ice sheet in the Central North Sea' From: Huuse, M., Redfern, J., Le Heron, D.P., Dixon, R.J., Moscariello, A., Craig, J. (eds) 'Glaciogenic reservoirs and Hydrocarbon Systems' Geological Society, London, Special Publications, 368 Cameron, T.D.J., Stoker, M.S., Long, D., (1987) 'The history of Quaternary sedimentation in the UK sector of the North Sea Basin' Journal of the Geological Society, 144, 43-58 Gatliff, R.W, Richards, P.C, Smith, K, Graham, C.C, McCormac, M, Smith, N.J.P, Long, D, Cameron, T.D.J, Evans, D, Stevenson, A.G, Bulat, J, Ritchie, J.D, (1994) 'United Kingdom offshore regional report: the geology of the central North Sea.' London: HMSO for the British Geological Survey Kulhmann, G., Langereis C.G., Munsterman, D., van Leeuwen, R.-J., Verreussel, R., Meulenkamp, J.E., Wong, Th.E., 2006 'Intergrated chronostratigraphy of the Pliocene-Pliestocene interval and its relation to the regional stratigraphical stages in the Southern North Sea region' Netherlands Journal of Geosciences 85(1), 29-45 Rasmussen, E.A., Vejb?k O.V., Bidstrup, T., Piasecki, S., Dybkj?r, K., 2005 'Late Cenozoic depositional history of the Danish North Sea Basin: implications for the petroleum systems in the Kraka, Halfdan, Siri and Nini fields', Petroleum Geology Conference series 6, 1347-1358 Sejrup, H.P., Aareseth, I., Haflidason, H., 1991 'The Quaternary succession in the northern North Sea' Marine Geology 101 103-111

A model of late quaternary landscape development in the Delaware Valley, New Jersey and Pennsylvania

USGS Publications Warehouse

Ridge, J.C.; Evenson, E.B.; Sevon, W.D.

1992-01-01

In the Delaware Valley of New Jersey and eastern Pennsylvania the late Quaternary history of colluviation, fluvial adjustment, and soil formation is based on the ages of pre-Wisconsinan soils and glacial deposits which are indicated by feld relationships and inferred from mid-latitude climate changes indicated by marine oxygen-isotope records. The area is divided into four terranes characterized by sandstone, gneiss, slate and carbonate rocks. Since the last pre-Wisconsinan glaciation (> 130 ka, inferred to be late Illinoian), each terrane responded differently to chemical and mechanical weathering. During the Sangamon interglacial stage (??? 130-75 ka) in situ weathering is inferred to have occurred at rates greater than transportation of material which resulted in the formation of deep, highly weathered soil and saprolite, and dissolution of carbonate rocks. Cold climatic conditions during the Wisconsinan, on the other hand, induced erosion of the landscape at rates faster than soil development. Upland erosion during the Wisconsinan removed pre-Wisconsinan soil and glacial sediment and bedrock to produce muddy to blocky colluvium, gre??zes lite??es, and alluvial fans on footslopes. Fluvial gravel and overlying colluvium in the Delaware Valley, both buried by late Wisconsinan outwash, are inferred to represent episodes of early and middle Wisconsinan (??? 75-25 ka) upland erosion and river aggradiation followed by river degradation and colluvium deposition. Early-middle Wisconsinan colluvium is more voluminous than later colluvium despite colder, possibly permafrost conditions during the late Wisconsinan ??? 25-10 ka). Extensive colluviation during the early and middle Wisconsinan resulted from a longer (50 kyr), generally cold interval of erosion with a greater availability of easily eroded pre-Wisconsinan surficial materials on uplands than during the late Wisconsinan. After recession of late Wisconsinan ice from its terminal position, soil formation and landscape stability were delayed until the Holocene by a lingering cold climate, slope erosion, colluvium and alluvial fan deposition, and eolian sedimentation. Late Quaternary erosion in the Delaware Valley was dominated by glacial and periglacial processes during glacial stages. During the warm interglacial stages, soils developed on a more stable landscape. These souls were easily colluviated by periglacial erosion during periods of intermittent cold climate. ?? 1992.

Phylogeography of the sand dune ant Mycetophylax simplex along the Brazilian Atlantic Forest coast: remarkably low mtDNA diversity and shallow population structure.

PubMed

Cardoso, Danon Clemes; Cristiano, Maykon Passos; Tavares, Mara Garcia; Schubart, Christoph D; Heinze, Jürgen

2015-06-10

During past glacial periods, many species of forest-dwelling animals experienced range contractions. In contrast, species living outside such moist habitats appear to have reacted to Quaternary changes in different ways. The Atlantic Forest represents an excellent opportunity to test phylogeographic hypotheses, because it has a wide range of vegetation types, including unforested habitats covered predominantly by herbaceous and shrubby plants, which are strongly influenced by the harsh environment with strong wind and high insolation. Here, we investigated the distribution of genetic diversity in the endemic sand dune ant Mycetophylax simplex across its known range along the Brazilian coast, with the aim of contributing to the understanding of alternative phylogeographic patterns. We used partial sequences of the mitochondrial gene cytochrome oxidase I and nuclear gene wingless from 108 specimens and 51 specimens, respectively, to assess the phylogeography and demographic history of this species. To achieve this we performed different methods of phylogenetic and standard population genetic analyses. The observed genetic diversity distribution and historical demographic profile suggests that the history of M. simplex does not match the scenario suggested for other Atlantic Forest species. Instead, it underwent demographic changes and range expansions during glacial periods. Our results show that M. simplex presents a shallow phylogeographic structure with isolation by distance among the studied populations, living in an almost panmictic population. Our coalescence approach indicates that the species maintained a stable population size until roughly 75,000 years ago, when it underwent a gradual demographic expansion that were coincident with the low sea-level during the Quaternary. Such demographic events were likely triggered by the expansion of the shorelines during the lowering of the sea level. Our data suggest that over evolutionary time M. simplex did not undergo dramatic range fragmentation, but rather it likely persisted in largely interconnected populations. Furthermore, we add an important framework about how both glacial and interglacial events could positively affect the distribution and diversification of species. The growing number of contrasting phylogeographic patterns within and among species and regions have shown that Quaternary events influenced the distribution of species in more ways than first supposed.

Regional variations in provenance and abundance of ice-rafted clasts in Arctic Ocean sediments: Implications for the configuration of late Quaternary oceanic and atmospheric circulation in the Arctic

USGS Publications Warehouse

Phillips, R.L.; Grantz, A.

2001-01-01

The composition and distribution of ice-rafted glacial erratics in late Quaternary sediments define the major current systems of the Arctic Ocean and identify two distinct continental sources for the erratics. In the southern Amerasia basin up to 70% of the erratics are dolostones and limestones (the Amerasia suite) that originated in the carbonate-rich Paleozoic terranes of the Canadian Arctic Islands. These clasts reached the Arctic Ocean in glaciers and were ice-rafted to the core sites in the clockwise Beaufort Gyre. The concentration of erratics decreases northward by 98% along the trend of the gyre from southeastern Canada basin to Makarov basin. The concentration of erratics then triples across the Makarov basin flank of Lomonosov Ridge and siltstone, sandstone and siliceous clasts become dominant in cores from the ridge and the Eurasia basin (the Eurasia suite). The bedrock source for the siltstone and sandstone clasts is uncertain, but bedrock distribution and the distribution of glaciation in northern Eurasia suggest the Taymyr Peninsula-Kara Sea regions. The pattern of clast distribution in the Arctic Ocean sediments and the sharp northward decrease in concentration of clasts of Canadian Arctic Island provenance in the Amerasia basin support the conclusion that the modem circulation pattern of the Arctic Ocean, with the Beaufort Gyre dominant in the Amerasia basin and the Transpolar drift dominant in the Eurasia basin, has controlled both sea-ice and glacial iceberg drift in the Arctic Ocean during interglacial intervals since at least the late Pleistocene. The abruptness of the change in both clast composition and concentration on the Makarov basin flank of Lomonosov Ridge also suggests that the boundary between the Beaufort Gyre and the Transpolar Drift has been relatively stable during interglacials since that time. Because the Beaufort Gyre is wind-driven our data, in conjunction with the westerly directed orientation of sand dunes that formed during the last glacial maximum on the North Slope of Alaska, suggests that atmospheric circulation in the western Arctic during late Quaternary was similar to that of the present. ?? 2001 Elsevier Science B.V.

Stable isotopes in Lithuanian bioarcheological material

NASA Astrophysics Data System (ADS)

Skipityte, Raminta; Jankauskas, Rimantas; Remeikis, Vidmantas

2015-04-01

Investigation of bioarcheological material of ancient human populations allows us to understand the subsistence behavior associated with various adaptations to the environment. Feeding habits are essential to the survival and growth of ancient populations. Stable isotope analysis is accepted tool in paleodiet (Schutkowski et al, 1999) and paleoenvironmental (Zernitskaya et al, 2014) studies. However, stable isotopes can be useful not only in investigating human feeding habits but also in describing social and cultural structure of the past populations (Le Huray and Schutkowski, 2005). Only few stable isotope investigations have been performed before in Lithuanian region suggesting a quite uniform diet between males and females and protein intake from freshwater fish and animal protein. Previously, stable isotope analysis has only been used to study a Stone Age population however, more recently studies have been conducted on Iron Age and Late medieval samples (Jacobs et al, 2009). Anyway, there was a need for more precise examination. Stable isotope analysis were performed on human bone collagen and apatite samples in this study. Data represented various ages (from 5-7th cent. to 18th cent.). Stable carbon and nitrogen isotope analysis on medieval populations indicated that individuals in studied sites in Lithuania were almost exclusively consuming C3 plants, C3 fed terrestrial animals, and some freshwater resources. Current investigation demonstrated social differences between elites and country people and is promising in paleodietary and daily life reconstruction. Acknowledgement I thank prof. dr. G. Grupe, Director of the Anthropological and Palaeoanatomical State Collection in Munich for providing the opportunity to work in her laboratory. The part of this work was funded by DAAD. Antanaitis-Jacobs, Indre, et al. "Diet in early Lithuanian prehistory and the new stable isotope evidence." Archaeologia Baltica 12 (2009): 12-30. Le Huray, Jonathan D., and Holger Schutkowski. "Diet and social status during the La Tène period in Bohemia: carbon and nitrogen stable isotope analysis of bone collagen from Kutná Hora-Karlov and Radovesice." Journal of Anthropological Archaeology 24.2 (2005): 135-147. Schutkowski, Holger, et al. "Diet, status and decomposition at Weingarten: trace element and isotope analyses on early mediaeval skeletal material." Journal of Archaeological Science 26.6 (1999): 675-685. Zernitskaya, Valentina, et al. "Vegetation pattern and sedimentation changes in the context of the Lateglacial climatic events: Case study of Staroje Lake (Eastern Belarus)." Quaternary International (2014).

[The action of quaternary ammonium derivatives on respiration and nitrate reduction in Pseudomonas aeruginosa].

PubMed

Bievskiĭ, A N

1994-01-01

It was revealed that the same dosages of quaternary ammonium derivatives, such as decamethoxin and cetyltrimethylammonium bromide, inhibited the respiratory chains and caused destruction of Pseudomonas aeruginosa under aerobic conditions more effectively than under anaerobic ones when anions of nitric acid were the terminal acceptors of electrons. It was also registered that Pseudomonas were able to dissimilatory nitrate reduction in the media under the polysaccharide layer that was produced by these bacteria: this fact possibly proves the possibility of survival of denitrifying bacteria in solutions with high concentrations of quaternary ammonium salts. The data obtained permit supposing that inhibitors of respiratory chains and oxidizers may be used as potentiators of the antimicrobial action of quaternary ammonium derivatives.

Derivatization of peptides as quaternary ammonium salts for sensitive detection by ESI-MS.

PubMed

Cydzik, Marzena; Rudowska, Magdalena; Stefanowicz, Piotr; Szewczuk, Zbigniew

2011-06-01

A series of model peptides in the form of quaternary ammonium salts at the N-terminus was efficiently prepared by the solid-phase synthesis. Tandem mass spectrometric analysis of the peptide quaternary ammonium derivatives was shown to provide sequence confirmation and enhanced detection. We designed the 2-(1,4-diazabicyclo[2.2.2] octylammonium)acetyl quaternary ammonium group which does not suffer from neutral losses during MS/MS experiments. The presented quaternization of 1,4-diazabicyclo[2.2.2]octane (DABCO) by iodoacetylated peptides is relatively easy and compatible with standard solid-phase peptide synthesis. This methodology offers a novel sensitive approach to analyze peptides and other compounds. Copyright © 2011 European Peptide Society and John Wiley & Sons, Ltd.

A Systematic Comparison of the Anisotropy of Magnetic Susceptibility (AMS) and Anisotropy of Remanence (ARM) Fabrics of Ignimbrites: Examples from the Quaternary Bandelier Tuff, Jemez Mountains, New Mexico and Miocene Ignimbrites Near Gold Point, Nevada

NASA Astrophysics Data System (ADS)

Lycka, Ranyah

Anisotropy of magnetic susceptibility (AMS) has been widely used to define petrofabrics in silicic, elevated-temperature pyroclastic deposits (i.e., ignimbrites) and these fabrics have been successfully utilized to infer pyroclastic emplacement, or transport, directions in many cases. Selected exposures of the Quaternary Bandelier Tuff, exposed in the Jemez Mountains, New Mexico, have been studied to systematically compare anisotropy of remanence (mainly anhysteretic remanent magnetization, AARM) with AMS data from the same sites. In addition, as part of a broad study to understand the Neogene history of deformation associated with a displacement transfer system in the western Great Basin, paleomagnetic and magnetic fabric data have been collected from ignimbrites that originated from the Timber Mountain Caldera complex, active from about 14 to 11.5 Ma. Here, AMS and AARM are compared for 21 (9-12 samples per site) sites in the Quaternary Bandelier Tuff, and 15 (9-10 samples per site) sites in Timber Mountain ignimbrites, with each chosen to examine the effects of varying degrees of welding and crystal content on the fabrics obtained. The relationships between AARM and AMS fabrics for the selected sites are not uniform, and include normal, intermediate, reverse, and oblique fabrics. The differences may be controlled by the degree of welding and/or crystal content, which requires further explanation. Ultimately, the fabrics identified in both suites of rocks are compared with anisotropy of isothermal remanent magnetization (AIRM) data, along with other rock magnetic data, to more fully evaluate the domain state control on the fabrics.

Utilization of deep eutectic solvents as novel mobile phase additives for improving the separation of bioactive quaternary alkaloids.

PubMed

Tan, Ting; Zhang, Mingliang; Wan, Yiqun; Qiu, Hongdeng

2016-01-01

Deep eutectic solvents (DESs) were used as novel mobile phase additives to improve chromatographic separation of four quaternary alkaloids including coptisine chloride, sanguinarine, berberine chloride and chelerythrine on a C18 column. DESs as a new class of ionic liquids are renewably sourced, environmentally benign, low cost and easy to prepare. Seven DESs were obtained by mixing different hydrogen acceptors and hydrogen-bond donors. The effects of organic solvents, the concentration of DESs, the types of DESs and the pH values of the buffer solution on the separation of the analytes were investigated. The composition of acetonitrile and 1.0% deep eutectic solvents aqueous solution (pH 3.3, adjusted with hydrochloric acid) in a 32:68 (v/v) ratio was used as optimized mobile phase, with which four quaternary alkaloids were well separated. When a small amount of DESs was added in the mobile phase for the separation of alkaloids on the C18 column, noticeable improvements were distinctly observed such as decreasing peak tailing and improving resolution. The separation mechanism mediated by DESs as mobile phase additives can be attributed to combined effect of both hydrogen acceptors and hydrogen-bond donors. For example, choline chloride can effectively cover the residual silanols on silica surface and ethylene glycol can reduce the retention time of analytes. The proposed method has been applied to determine BerbC in Lanqin Chinese herbal oral solution and BerbC tablet. Utilization of DESs in mobile phase can efficiently improve separation and selectivity of analytes from complex samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Holocene and latest Pleistocene oblique dextral faulting on the southern Inyo Mountains fault, Owens Lake basin, California

USGS Publications Warehouse

Bacon, S.N.; Jayko, A.S.; McGeehin, J.P.

2005-01-01

The Inyo Mountains fault (IMF) is a more or less continuous range-front fault system, with discontinuous late Quaternary activity, at the western base of the Inyo Mountains in Owens Valley, California. The southern section of the IMF trends ???N20??-40?? W for at least 12 km at the base of and within the range front near Keeler in Owens Lake basin. The southern IMF cuts across a relict early Pliocene alluvial fan complex, which has formed shutter ridges and northeast-facing scarps, and which has dextrally offset, well-developed drainages indicating long-term activity. Numerous fault scarps along the mapped trace are northeast-facing, mountain-side down, and developed in both bedrock and younger alluvium, indicating latest Quaternary activity. Latest Quaternary multiple- and single-event scarps that cut alluvium range in height from 0.5 to 3.0 m. The penultimate event on the southern IMF is bracketed between 13,310 and 10,590 cal years B.P., based on radiocarbon dates from faulted alluvium and fissure-fill stratigraphy exposed in a natural wash cut. Evidence of the most recent event is found at many sites along the mapped fault, and, in particular, is seen in an ???0.5-m northeast-facing scarp and several right-stepping en echelon ???0.5-m-deep depressions that pond fine sediment on a younger than 13,310 cal years B.P. alluvial fan. A channel that crosses transverse to this scarp is dextrally offset 2.3 ?? 0.8 m, providing a poorly constrained oblique slip rate of 0.1-0. 3 m/ k.y. The identified tectonic geomorphology and sense of displacement demonstrate that the southern IMF accommodates predominately dextral slip and should be integrated into kinematic fault models of strain distribution in Owens Valley.

Analysis of a Soluble (UreD:UreF:UreG)2 Accessory Protein Complex and its Interactions with Klebsiella aerogenes Urease by Mass Spectrometry

PubMed Central

Farrugia, Mark A.; Han, Linjie; Zhong, Yueyang; Boer, Jodi L.; Ruotolo, Brandon T.; Hausinger, Robert P.

2013-01-01

Maturation of the nickel-containing urease of Klebsiella aerogenes is facilitated by the UreD, UreF, and UreG accessory proteins along with the UreE metallo-chaperone. A fusion of the maltose binding protein and UreD (MBP-UreD) was co-isolated with UreF and UreG in a soluble complex possessing a (MBP-UreD:UreF:UreG)2 quaternary structure. Within this complex a UreF:UreF interaction was identified by chemical cross-linking of the amino termini of its two UreF protomers, as shown by mass spectrometry of tryptic peptides. A pre-activation complex was formed by the interaction of (MBP-UreD:UreF:UreG)2 and urease. Mass spectrometry of intact protein species revealed a pathway for synthesis of the urease pre-activation complex in which individual hetero-trimer units of the (MBP-UreD:UreF:UreG)2 complex bind to urease. Together, these data provide important new insights into the structures of protein complexes associated with urease activation. PMID:23797863

Formation and characterization of chitosan-protein particles with fractal whey protein aggregates.

PubMed

Ahmed, Khouloud Fekih; Aschi, Adel; Nicolai, Taco

2018-05-15

Hybrid protein-polysaccharide particles were formed by complexation of fractal whey protein aggregates and the cationic polysaccharide chitosan. The fractal aggregates were preformed by heating native whey protein isolate at pH 7 and subsequently mixed with chitosan at pH 3 where these proteins and polysaccharides don't interact with each other. Stable dispersions of protein-polysaccharide particles were formed spontaneously when the pH was gradually increased between 4.1 and 6.8, whereas in the absence of chitosan the fractal aggregates precipitated between pH 4.1 and 5.4. Potentiometric titration of the mixtures showed that deprotonation of both components was affected by complexation. With increasing pH, the size of the complexes increased sharply between pH 4.1. and pH 4.5, remained constant up to pH 5.6 and then increased again. A minimum amount of chitosan was needed to form stable complexes at pH 5.0 and the size of the complexes decreased with increasing chitosan concentration. Light scattering showed that the complexes were stable to dilution and had a self similar structure with a fractal dimensions close to two. The effect of changing the pH on the size and stability of the complexes was investigated. Suspensions of complexes of preformed whey protein aggregates and chitosan are more stable up to high pH (6.8) than complexes between native WPI and chitosan as reported in the literature. Copyright © 2018. Published by Elsevier B.V.

Green and scalable production of colloidal perovskite nanocrystals and transparent sols by a controlled self-collection process

NASA Astrophysics Data System (ADS)

Liu, Shuangyi; Huang, Limin; Li, Wanlu; Liu, Xiaohua; Jing, Shui; Li, Jackie; O'Brien, Stephen

2015-07-01

Colloidal perovskite oxide nanocrystals have attracted a great deal of interest owing to the ability to tune physical properties by virtue of the nanoscale, and generate thin film structures under mild chemical conditions, relying on self-assembly or heterogeneous mixing. This is particularly true for ferroelectric/dielectric perovskite oxide materials, for which device applications cover piezoelectrics, MEMs, memory, gate dielectrics and energy storage. The synthesis of complex oxide nanocrystals, however, continues to present issues pertaining to quality, yield, % crystallinity, purity and may also suffer from tedious separation and purification processes, which are disadvantageous to scaling production. We report a simple, green and scalable ``self-collection'' growth method that produces uniform and aggregate-free colloidal perovskite oxide nanocrystals including BaTiO3 (BT), BaxSr1-xTiO3 (BST) and quaternary oxide BaSrTiHfO3 (BSTH) in high crystallinity and high purity. The synthesis approach is solution processed, based on the sol-gel transformation of metal alkoxides in alcohol solvents with controlled or stoichiometric amounts of water and in the stark absence of surfactants and stabilizers, providing pure colloidal nanocrystals in a remarkably low temperature range (15 °C-55 °C). Under a static condition, the nanoscale hydrolysis of the metal alkoxides accomplishes a complete transformation to fully crystallized single domain perovskite nanocrystals with a passivated surface layer of hydroxyl/alkyl groups, such that the as-synthesized nanocrystals can exist in the form of super-stable and transparent sol, or self-accumulate to form a highly crystalline solid gel monolith of nearly 100% yield for easy separation/purification. The process produces high purity ligand-free nanocrystals excellent dispersibility in polar solvents, with no impurity remaining in the mother solution other than trace alcohol byproducts (such as isopropanol). The afforded stable and transparent suspension/solution can be treated as inks, suitable for printing or spin/spray coating, demonstrating great capabilities of this process for fabrication of high performance dielectric thin films. The simple ``self-collection'' strategy can be described as green and scalable due to the simplified procedure from synthesis to separation/purification, minimum waste generation, and near room temperature crystallization of nanocrystal products with tunable sizes in extremely high yield and high purity.Colloidal perovskite oxide nanocrystals have attracted a great deal of interest owing to the ability to tune physical properties by virtue of the nanoscale, and generate thin film structures under mild chemical conditions, relying on self-assembly or heterogeneous mixing. This is particularly true for ferroelectric/dielectric perovskite oxide materials, for which device applications cover piezoelectrics, MEMs, memory, gate dielectrics and energy storage. The synthesis of complex oxide nanocrystals, however, continues to present issues pertaining to quality, yield, % crystallinity, purity and may also suffer from tedious separation and purification processes, which are disadvantageous to scaling production. We report a simple, green and scalable ``self-collection'' growth method that produces uniform and aggregate-free colloidal perovskite oxide nanocrystals including BaTiO3 (BT), BaxSr1-xTiO3 (BST) and quaternary oxide BaSrTiHfO3 (BSTH) in high crystallinity and high purity. The synthesis approach is solution processed, based on the sol-gel transformation of metal alkoxides in alcohol solvents with controlled or stoichiometric amounts of water and in the stark absence of surfactants and stabilizers, providing pure colloidal nanocrystals in a remarkably low temperature range (15 °C-55 °C). Under a static condition, the nanoscale hydrolysis of the metal alkoxides accomplishes a complete transformation to fully crystallized single domain perovskite nanocrystals with a passivated surface layer of hydroxyl/alkyl groups, such that the as-synthesized nanocrystals can exist in the form of super-stable and transparent sol, or self-accumulate to form a highly crystalline solid gel monolith of nearly 100% yield for easy separation/purification. The process produces high purity ligand-free nanocrystals excellent dispersibility in polar solvents, with no impurity remaining in the mother solution other than trace alcohol byproducts (such as isopropanol). The afforded stable and transparent suspension/solution can be treated as inks, suitable for printing or spin/spray coating, demonstrating great capabilities of this process for fabrication of high performance dielectric thin films. The simple ``self-collection'' strategy can be described as green and scalable due to the simplified procedure from synthesis to separation/purification, minimum waste generation, and near room temperature crystallization of nanocrystal products with tunable sizes in extremely high yield and high purity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02351c

Quaternary dinoflagellate cysts in the Arctic Ocean: Potential and limitations for stratigraphy and paleoenvironmental reconstructions

NASA Astrophysics Data System (ADS)

Matthiessen, Jens; Schreck, Michael; De Schepper, Stijn; Zorzi, Coralie; de Vernal, Anne

2018-07-01

The Arctic Ocean is a siliciclastic depositional environment which lacks any rock-forming biogenic calcareous and siliceous components during large parts of its Quaternary history. These hemipelagic sediments are nevertheless suitable for the study of organic-walled microfossils of which the fossil remains of dinoflagellates - dinoflagellate cysts - are the most important group. Dinoflagellate cysts have become an important tool in paleoceanography of the high northern latitudes, but their potential for Quaternary biostratigraphy has remained largely unexplored. Dinoflagellate cysts are the dominant marine palynomorph group which is more continuously present in the marginal seas (e.g. Barents Sea, Bering Sea) than in the Arctic Ocean itself throughout the Quaternary. Most species have long stratigraphic ranges, are temporary absent and show abundance variations on glacial-interglacial timescales. Of the more than 30 taxa recorded, only Habibacysta tectata and Filisphaera filifera became extinct in the Pleistocene. The highest persistent occurrence of H. tectata at ca. 2.0 Ma and the top of F. filifera acme at ca. 1.8 Ma can be used for supra-regional stratigraphic correlation between the Arctic Ocean and adjacent basins. These events corroborate a slow sedimentation rate model for the Quaternary section on the central Lomonosov Ridge, but a combination of different methods will have to be applied to provide a detailed chronostratigraphy. The occurrence of cysts of phototrophic dinoflagellates in certain stratigraphic intervals on Lomonosov Ridge supports published evidence of episodic opening of the multiyear Arctic sea ice cover during the Quaternary probably related to a stronger inflow of Atlantic water. This contradicts the hypothesis of a permanently ice covered central Arctic Ocean in the Quaternary.

Surface modification and antimicrobial properties of cellulose nanocrystals

NASA Astrophysics Data System (ADS)

Bespalova, Yulia A.

Surface modification of cellulose nanocrystals (CNC) was performed by acetylation and subsequent reaction with various tertiary amines with different lengths of alkyl groups. Chloroacetic anhydride (95%) was used for acetylation. The acetylation of CNC was confirmed using IR spectroscopy. The bands associated with C=0 stretching (1740 cm-1) and C-Cl stretching (793 cm -1) was present in the acetylated CNC but they were absent in the neat CNC. It has been suggested that the primary hydroxyl groups of CNC are substituted by chloro acetyl groups during acetylation reaction. Subsequent reaction of chloro acetylated CNC with N, N - Dimethyl ethylamine, N, N - Dimethyl hexylamine, N, N - Dimethyl dodecylamine, N, N - Dimethyl hexadecylamine and N, N - Dimethyl decylamine formed quaternary ammonium salts. These quaternary ammonium salts were characterized by FTIR and solid state13C NMR spectroscopy. FTIR spectra of five types of quaternary ammonium salts of CNC are similar and they showed infrared bands at 2905 -1 and 2850 cm-1, attributed to symmetrical and unsymmetrical C-H stretching vibration. The absence of C-Cl band at 793 cm-1 proves that quaternary salt formation was successful. The 13C NMR spectrum of quaternary ammonium modified CNC with N, N - Dimethyl dodecylamine shows several additional resonances ranging from 14.5 ppm to 58.0 ppm when compared to 13C NMR spectrum of pure CNC. This evidence proves that long alkyl chains have been added to the pure CNC. The disc diffusion method confirmed that quaternary ammonium modified CNCs with a chain longer than ten carbons are effective antimicrobial agents against Staphylococcus aureus and E. coli bacteria. Pure CNC and quaternary ammonium modified CNCs with an alkyl chain length of ten or less were not able to inhibit bacteria growth.

A novel assay to measure tertiary and quaternary amines in wastewater: An indicator for NDMA wastewater precursors.

PubMed

Woods-Chabane, Gwen C; Glover, Caitlin M; Marti, Erica J; Dickenson, Eric R V

2017-07-01

This study examined the potential of using a novel bulk amine assay as an approximation for the tertiary and quaternary amine load in wastewaters and surface water samples, and this approximation was compared to N-nitrosodimethylamine (NDMA) formation potential using chloramines. An existing colorimetric method was examined and optimized for the detection of amines in environmental water samples. The method consists of liquid-liquid extraction followed by a catalyzed reaction to form a yet-undefined product that is known to be both a strong chromophore and fluorophore. Previous work verified that this reaction was effectively catalyzed by a number of compounds containing tertiary and quaternary amine moieties. Many tertiary and quaternary compounds are also efficient producers of NDMA under chloramination conditions, and a linear correlation was consequently derived from the bulk amine signals vs. NDMA formation potential in various wastewater samples (R 2  = 0.74; n = 24; p-value < 0.05). The results provide evidence that approximately 2% of the tertiary and quaternary amines measured can form NDMA and an estimated 0.01-1.3% of nitrogen in dissolved organic nitrogen originates from these bulk amines. The normalization of NDMA concentration by the amine measurement revealed that ozone effectively destroyed those tertiary and quaternary amine structures more likely to form NDMA in treated wastewater samples. This bulk amine assay illustrates that proxy measurements of tertiary and quaternary amines can be linked to the NDMA formation potential of a given sample, and this approach may prove useful as a characterizing tool for NDMA precursors in wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

Is the Ordos Basin floored by a trapped oceanic plateau?

NASA Astrophysics Data System (ADS)

Kusky, Tim; Mooney, Walter

2015-11-01

The Ordos Basin in China has about 10 km of Neoarchean to Quaternary sediments covering an enigmatic basement of uncertain origin. The basement is tectonically stable, has a thick mantle root, low heat flow, few earthquakes, and has been slowly subsiding for billions of years. The basement has geophysical signatures that indicate it is dominantly intermediate to mafic in composition, and is similar to some other cratons world-wide, and also to several major oceanic plateaus. It was accreted to the amalgamated Eastern Block and Central Orogenic belt of the North China Craton (NCC) in the Paleoproterozoic, then involved in several Proterozoic tectonic events including being over-thrust by an accretionary orogen, and intruded by Andean arc-related magmas, and then involved in a continent-continent collision during amalgamation with the Columbia Supercontinent. Thus, the basement rocks are deformed, metamorphosed to granulite facies, and determining their initial origin is difficult. We suggest that the data is consistent with an origin as an oceanic plateau that accreted to the NCC and, later experienced different episodes of differentiation associated with later subduction and collisions. Formation of cratonic lithosphere by accretion of oceanic plateaus may be one mechanism to create stable cratons. Other cratons that apparently formed by partial melting of underplated and imbricated oceanic slabs are stable in some cases, but also re-activated and ;de-cratonized; in some cases in Asia, where they have been affected by younger subduction, hydration, slab roll-back, and melt-peridotite reactions. This suggests that the initial mode of craton formation may be a factor in the preservation of stable cratons, and de-cratonization is not only influenced by younger tectonic activity.

Amphibian beta diversity in the Brazilian Atlantic Forest: contrasting the roles of historical events and contemporary conditions at different spatial scales.

PubMed

da Silva, Fernando Rodrigues; Almeida-Neto, Mário; Arena, Mariana Victorino Nicolosi

2014-01-01

Current patterns of biodiversity distribution result from a combination of historical and contemporary processes. Here, we compiled checklists of amphibian species to assess the roles of long-term climate stability (Quaternary oscillations), contemporary environmental gradients and geographical distance as determinants of change in amphibian taxonomic and phylogenetic composition in the Brazilian Atlantic Forest. We calculated beta diversity as both variation in species composition (CBD) and phylogenetic differentiation (PBD) among the assemblages. In both cases, overall beta diversity was partitioned into two basic components: species replacement and difference in species richness. Our results suggest that the CBD and PBD of amphibians are determined by spatial turnover. Geographical distance, current environmental gradients and long-term climatic conditions were complementary predictors of the variation in CBD and PBD of amphibian species. Furthermore, the turnover components between sites from different regions and between sites within the stable region were greater than between sites within the unstable region. On the other hand, the proportion of beta-diversity due to species richness difference for both CBD and PBD was higher between sites in the unstable region than between sites in the stable region. The high turnover components from CBD and PBD between sites in unstable vs stable regions suggest that these distinct regions have different biogeographic histories. Sites in the stable region shared distinct clades that might have led to greater diversity, whereas sites in the unstable region shared close relatives. Taken together, these results indicate that speciation, environmental filtering and limited dispersal are complementary drivers of beta-diversity of amphibian assemblages in the Brazilian Atlantic Forest.

Curare-Like Activity of Mono-Quaternary Salts Containing Adamantyl Residue at the Nitrogen Atom

DTIC Science & Technology

As shown in previous works, mono-quaternary salts of alkamine esters of benzoic and cinnamic acids types and exhibit a pronounced curare like action...A series of methiodides of alkamine esters of benzoic and cinnamic acids were synthesized, containing at the quaternary nitrogen atom a 1-adamantyl...adamantyl causes a change of the substance’s mechanism of action, this applying both to the benzoic acid derivatives and to the cinnamic acid derivatives

Why Do Tropical Mountains Support Exceptionally High Biodiversity? The Eastern Arc Mountains and the Drivers of Saintpaulia Diversity

PubMed Central

Dimitrov, Dimitar; Nogués-Bravo, David; Scharff, Nikolaj

2012-01-01

We combine information about the evolutionary history and distributional patterns of the genus Saintpaulia H. Wendl. (Gesneriaceae; ‘African violets’) to elucidate the factors and processes behind the accumulation of species in tropical montane areas of high biodiversity concentration. We find that high levels of biodiversity in the Eastern Arc Mountains are the result of pre-Quaternary speciation processes and environmental stability. Our results support the hypothesis that climatically stable mountaintops may have acted as climatic refugia for lowland lineages during the Pleistocene by preventing extinctions. In addition, we found evidence for the existence of lowland micro-refugia during the Pleistocene, which may explain the high species diversity of East African coastal forests. We discuss the conservation implications of the results in the context of future climate change. PMID:23185283

Ni-catalyzed reductive homocoupling of unactivated alkyl bromides at room temperature and its synthetic application.

PubMed

Peng, Yu; Luo, Long; Yan, Chang-Song; Zhang, Jian-Jian; Wang, Ya-Wen

2013-11-01

A room-temperature Ni-catalyzed reductive approach to homocoupling of unactivated primary, secondary, and tertiary alkyl bromides is described. The catalytic system can be easily generated from air-stable and cheap materials and demonstrates broad functional group tolerance, thus allowing facile access to useful dimeric triterpene and lignan-like molecules. Moreover, the dimerization of tertiary bromide 6 efficiently establishes sterically hindered vicinal quaternary carbons (C3a and C3a'), which is a key linkage of intriguing bispyrrolo[2,3-b]indoline alkaloids, thereby enabling us to complete the total syntheses of racemic chimonanthine (9) and folicanthine (10). In addition, this dimerization method can be expanded to the highly stereoselective synthesis of bisperhydrofuro[2,3-b]furan (5a) and the dimeric spiroketal 5b, signifying the involvement of possible radical species.

Evaluation of novel derivatisation reagents for the analysis of oxysterols

PubMed Central

Crick, Peter J.; Aponte, Jennifer; Bentley, T. William; Matthews, Ian; Wang, Yuqin; Griffiths, William J.

2014-01-01

Oxysterols are oxidised forms of cholesterol that are intermediates in the synthesis of bile acids and steroid hormones. They are also ligands to nuclear and G protein-coupled receptors. Analysis of oxysterols in biological systems is challenging due to their low abundance coupled with their lack of a strong chromophore and poor ionisation characteristics in mass spectrometry (MS). We have previously used enzyme-assisted derivatisation for sterol analysis (EADSA) to identify and quantitate oxysterols in biological samples. This technique relies on tagging sterols with the Girard P reagent to introduce a charged quaternary ammonium group. Here, we have compared several modified Girard-like reagents and show that the permanent charge is vital for efficient MSn fragmentation. However, we find that the reagent can be extended to include sites for potential stable isotope labels without a loss of performance. PMID:24525124

Structural Analysis of a Family 81 Glycoside Hydrolase Implicates Its Recognition of β-1,3-Glucan Quaternary Structure.

PubMed

Pluvinage, Benjamin; Fillo, Alexander; Massel, Patricia; Boraston, Alisdair B

2017-09-05

Family 81 glycoside hydrolases (GHs), which are known to cleave β-1,3-glucans, are found in archaea, bacteria, eukaryotes, and viruses. Here we examine the structural and functional features of the GH81 catalytic module, BhGH81, from the Bacillus halodurans protein BH0236 to probe the molecular basis of β-1,3-glucan recognition and cleavage. BhGH81 displayed activity on laminarin, curdlan, and pachyman, but not scleroglucan; the enzyme also cleaved β-1,3-glucooligosaccharides as small as β-1,3-glucotriose. The crystal structures of BhGH81 in complex with various β-1,3-glucooligosaccharides revealed distorted sugars in the -1 catalytic subsite and an arrangement consistent with an inverting catalytic mechanism having a proposed conformational itinerary of 2 S 0 → 2,5 B ‡ → 5 S 1 . Notably, the architecture of the catalytic site, location of an adjacent ancillary β-1,3-glucan binding site, and the surface properties of the enzyme indicate the likely ability to recognize the double and/or triple-helical quaternary structures adopted by β-1,3-glucans. Copyright © 2017 Elsevier Ltd. All rights reserved.

Variation in Inflammatory/Regulatory Cytokines in Secondary, Tertiary, and Quaternary Challenges with Dengue Virus

PubMed Central

Sierra, Beatriz; Pérez, Ana B.; Alvarez, Mayling; García, Gissel; Vogt, Katrin; Aguirre, Eglys; Schmolke, Kathrin; Volk, Hans-Dieter; Guzmán, María G.

2012-01-01

Secondary heterologous dengue infection is a risk factor for severe disease manifestations because of the immune-enhancement phenomenon. Succeeding clinical infections are seldom reported, and the clinical course of tertiary and quaternary dengue infections is not clear. Cuba represents a unique environment to study tertiary/quaternary dengue infections in a population with known clinical and serologic dengue markers and no dengue endemicity. We took advantage of this exceptional epidemiologic condition to study the effect of primary, secondary, tertiary, and quaternary dengue infection exposure on the expression of pro-inflammatory and regulatory cytokines, critical in dengue infection pathogenesis, by using a dengue infection ex vivo model. Whereas secondary exposure induced a high cytokine response, we found a significantly lower expression of tumor necrosis factor-α, interferon-γ, interleukin-10, and tumor growth factor-β after tertiary and quaternary infectious challenge. Significant differences in expression of the cytokines were seen between the dengue immune profiles, suggesting that the sequence in which the immune system encounters serotypes may be important in determining the nature of the immune response to subsequent infections. PMID:22802438

A study of Quaternary structures in the Qom region, West Central Iran

NASA Astrophysics Data System (ADS)

Babaahmadi, A.; Safaei, H.; Yassaghi, A.; Vafa, H.; Naeimi, A.; Madanipour, S.; Ahmadi, M.

2010-12-01

West Central Iran comprises numerous Quaternary faults. Having either strike-slip or thrust mechanisms, these faults are potentially active and therefore capable of creating destructive earthquakes. In this paper, we use satellite images as well as field trips to identify these active faults in the Qom region. The Qom and Indes faults are the main NW-trending faults along which a Quaternary restraining step-over zone has formed. Kamarkuh, Mohsen Abad, and Ferdows anticlines are potentially active structures that formed in this restraining step-over zone. There are some thrusts and anticlines, such as the Alborz anticline and Alborz fault, which are parallel to strike-slip faults such as the Qom fault, indicating deformation partitioning in the area. In addition to NW-trending structures, there is an important NE-trending fault known as the Qomrud fault that has deformed Quaternary deposits and affected Kushk-e-Nosrat fault, Alborz anticline, and Qomrud River. The results of this study imply that the major Quaternary faults of West Central Iran and their restraining step-over zones are potentially active.

Ancient dna from pleistocene fossils: Preservation, recovery, and utility of ancient genetic information for quaternary research

NASA Astrophysics Data System (ADS)

Yang, Hong

Until recently, recovery and analysis of genetic information encoded in ancient DNA sequences from Pleistocene fossils were impossible. Recent advances in molecular biology offered technical tools to obtain ancient DNA sequences from well-preserved Quaternary fossils and opened the possibilities to directly study genetic changes in fossil species to address various biological and paleontological questions. Ancient DNA studies involving Pleistocene fossil material and ancient DNA degradation and preservation in Quaternary deposits are reviewed. The molecular technology applied to isolate, amplify, and sequence ancient DNA is also presented. Authentication of ancient DNA sequences and technical problems associated with modern and ancient DNA contamination are discussed. As illustrated in recent studies on ancient DNA from proboscideans, it is apparent that fossil DNA sequence data can shed light on many aspects of Quaternary research such as systematics and phylogeny. conservation biology, evolutionary theory, molecular taphonomy, and forensic sciences. Improvement of molecular techniques and a better understanding of DNA degradation during fossilization are likely to build on current strengths and to overcome existing problems, making fossil DNA data a unique source of information for Quaternary scientists.

Elusive silane-alane complex [Si-H⋅⋅⋅Al]: isolation, characterization, and multifaceted frustrated Lewis pair type catalysis.

PubMed

Chen, Jiawei; Chen, Eugene Y-X

2015-06-01

The super acidity of the unsolvated Al(C6F5)3 enabled isolation of the elusive silane-alane complex [Si-H⋅⋅⋅Al], which was structurally characterized by spectroscopic and X-ray diffraction methods. The Janus-like nature of this adduct, coupled with strong silane activation, effects multifaceted frustrated-Lewis-pair-type catalysis. When compared with the silane-borane system, the silane-alane system offers unique features or clear advantages in the four types of catalytic transformations examined in this study, including: ligand redistribution of tertiary silanes into secondary and quaternary silanes, polymerization of conjugated polar alkenes, hydrosilylation of unactivated alkenes, and hydrodefluorination of fluoroalkanes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quaternary remagnetization of the Neoproterozoic limestone of Negash Synclinorium (Arabian-Nubian Shield, northern Ethiopia): With implications of no paleomagnetic testing for the proposed Snowball Earth events

NASA Astrophysics Data System (ADS)

Kidane, Tesfaye; Bachtadse, Valerian; Alene, Mulugeta

2014-10-01

Eighty-one paleomagnetic cores were collected from 10 locations across a black limestone unit within the core of Negash Synclinorium, northern Ethiopia in order to test the proposed Snowball Earth events for the diamictite unit of the Tambien Group. Cores were cut into two standard paleomagnetic specimens and were subjected to stepwise demagnetizations using both Thermal (TH) and alternating field (AF) techniques. Rock magnetic analyses on representative specimens were done and results revealed goethite, pyrrhotite, titano-magnetite, and titano-hematite to be the major magnetic materials carrying the magnetizations with PSD (pseudo single domain) grain size range. In most cases paleomagnetic directions are defined by a single component of magnetization, where a viscous component is present it is usually removed by heating to a temperature of ∼200 °C or an AF of ∼10 mT. The high stability component isolated above temperature of 200 °C or AF of 15 mT, defined straight line trajectories directed towards the origin and considered as the Characteristic Remanent Magnetization Direction (ChRM). The direction of magnetization of the ChRM is determined for samples with stable straight line segments by the best-fit line using the least square technique of Kirschvink (1980). In the cases of overlapping spectra and unblocking temperatures, direction of magnetization is determined by remagnetization circles of Halls (1976, 1978). When site mean ChRM directions are plotted on stereogram, their distribution is relatively clustered in geographic coordinates and the overall mean direction is Decg = 358.5°, Incg = 16.6° (α95 = 3.8°, K = 162.8, N = 10). After a structural restoration to the horizontal is made the directions disperse and fail the fold test of both McElhinny’s and McFadden’s tests and the mean direction is Decs = 353.5°, Incs = 8.8° (α95 = 18.9°, K = 7.5, N = 10). This is interpreted to result from a later remagnetization of the black limestone. All directions are normal in polarity and have mean unrestored paleomagnetic directions comparable to the Quaternary paleomagnetic directions. Virtual Geomagnetic poles (VGP) in the unrestored position is used to calculate overall mean VGP position resulting long = 235.7°E, latg = 84.5°N (A95 = 3.0°, N = 10). Comparison of the obtained pole with the apparent polar wander path (APWP) curve for Africa of Besse and Courtillot (1991, 2003) and with the 2 Ma reference pole of stable Africa (Kidane et al., 2003) is found to be consistent with remagnetizations during the Quaternary period. Hence supporting evidence for the proposed Snowball Earth event of the Sturtian glaciation in the Negash rocks could not, unfortunately, be obtained from paleomagnetism.

Disentangling the impacts of climate and human colonization on the flora and fauna of the Australian arid zone over the past 100 ka using stable isotopes in avian eggshell

NASA Astrophysics Data System (ADS)

Miller, Gifford H.; Fogel, Marilyn L.; Magee, John W.; Gagan, Michael K.

2016-11-01

Throughout the Quaternary, the flora and fauna of Australia evolved and adapted to the high-amplitude, low- and high-frequency climate changes that characterized the ice-age cycles. However, during the last glacial cycle, between ∼120 and 15 ka, unprecedented irreversible changes in flora and fauna occurred, and in that same interval modern humans established their first firm presence in the landscape. Disentangling the impacts of the first-order trend toward a colder, drier planet through the Late Quaternary from the impacts of human colonization has been challenging, from both the chronological and paleoenvironmental perspectives. We utilize the stable isotopes of carbon and oxygen preserved in near-continuous time series of Dromaius (emu) eggshell from five regions across Australia to provide independent reconstructions of ecosystem status and climate over the past 100 ka. Carbon isotopes are determined by the diet consumed by the female bird, whereas oxygen isotopes record the status of local moisture balance in the months prior to breeding. Together, δ13C and δ18O provide ecosystem status and climate from the same dated sample, reducing correlation uncertainties between proxies. Combined with recent improvements in the chronologies of Late Quaternary shorelines fringing inland lake basins and deflation during arid times, these data collectively reaffirm that Australia generally became increasingly, albeit irregularly, drier from the last interglaciation through to the last glacial maximum. Dromaius eggshell δ18O documents peak aridity between 30 and 15 ka, but shows no evidence of exceptional climate change between 60 and 40 ka. In contrast, Dromaius δ13Cdiet documents an irreversible loss of the majority of palatable summer-rainfall-related C4 grasses across the Australian arid zone between 50 and 45 ka, about the same time that the giant megafaunal bird, Genyornis, became extinct, and coincident with human dispersal across the continent. Our data indicate that changes unique to Australia occurred between 50 and 45 ka that led to a new climate-vegetation relationship and an overall reduction in effective moisture across much of the continent. The large summer-rainfall-dominated lakes of interior Australia failed to re-fill subsequently, despite a wide range of global climate states. A full explanation for the mechanisms behind these changes remains elusive, but they are almost certainly related to human agency. Plausible explanations include a change in fire regime resulting from human-lit fires, a change in fire regime following extinction of megafaunal browsers, and/or a threshold response to increasing aridity. Of these, the climate change explanation is least likely, given the lack of evidence for unprecedented aridity between 60 and 40 ka, and the successful adaptation of Australian ecosystems to 2.5 Ma of similar changes.

A high-throughput immobilized bead screen for stable proteins and multi-protein complexes

PubMed Central

Lockard, Meghan A.; Listwan, Pawel; Pedelacq, Jean-Denis; Cabantous, Stéphanie; Nguyen, Hau B.; Terwilliger, Thomas C.; Waldo, Geoffrey S.

2011-01-01

We describe an in vitro colony screen to identify Escherichia coli expressing soluble proteins and stable, assembled multiprotein complexes. Proteins with an N-terminal 6His tag and C-terminal green fluorescent protein (GFP) S11 tag are fluorescently labeled in cells by complementation with a coexpressed GFP 1–10 fragment. After partial colony lysis, the fluorescent soluble proteins or complexes diffuse through a supporting filtration membrane and are captured on Talon® resin metal affinity beads immobilized in agarose. Images of the fluorescent colonies convey total expression and the level of fluorescence bound to the beads indicates how much protein is soluble. Both pieces of information can be used together when selecting clones. After the assay, colonies can be picked and propagated, eliminating the need to make replica plates. We used the method to screen a DNA fragment library of the human protein p85 and preferentially obtained clones expressing the full-length ‘breakpoint cluster region-homology' and NSH2 domains. The assay also distinguished clones expressing stable multi-protein complexes from those that are unstable due to missing subunits. Clones expressing stable, intact heterotrimeric E.coli YheNML complexes were readily identified in libraries dominated by complexes of YheML missing the N subunit. PMID:21642284

Late Quaternary paleohydrology deduced from new marine sediment cores taken on the proximal Amazon continental margin

NASA Astrophysics Data System (ADS)

Nace, T.; Baker, P. A.; Dwyer, G. S.; Hollander, D. J.; Silva, C. G.

2010-12-01

Throughout the late Quaternary the Amazon Basin has been influenced by abrupt North-South climate forcing and has undergone several large climate variations as recorded in previously reported speleothem records. Despite its importance in the global carbon cycle there are few continuous, high-resolution records of the Amazon Basin that date back to and beyond the last glacial period. In this study, we report the first results of a marine geological expedition to the Amazon continental shelf and fan region. During this expedition we collected eight ~30 meter piston cores along with gravity, box and multicores. At both sites we undertook complementary multibeam and high resolution seismic reflection profiling. Analyses will be presented from two sets of box/gravity/piston cores. One core (32m) is from a high sedimentation site on the northern flank of the main submarine canyon within the Amazon Fan complex at 1700m water depth. The other core (30m) is located on a seamount to the south of the Amazon Fan complex at 3100m water depth. A mixed assemblage of foraminifera is used for 14C dating to obtain an age model and bulk organic geochemistry is analyzed to determine percent organic carbon, C/N ratios, δ13C and δ15N. The cores were continuously measured shipboard for magnetic susceptibility and gamma density using a GEOTEK logger. These findings uncover the contribution of pelagic and terrestrial organic matter, whether the terrigenous carbon is derived from C3 versus C4 vegetation, and whether the marine organic matter is composed of phytoplankton or marine algae.

Late Quaternary slip rate determination by CRN dating on the Haiyuan fault, China, and implication for complex geometry fault systems

NASA Astrophysics Data System (ADS)

Matrau, Rémi; Klinger, Yann; Van der Woerd, Jérôme; Liu-Zeng, Jing; Li, Zhanfei; Xu, Xiwei

2017-04-01

Late Quaternary slip rate determination by CRN dating on the Haiyuan fault, China, and implication for complex geometry fault systems Matrau Rémi, Klinger Yann, Van der Woerd Jérôme, Liu-Zeng Jing, Li Zhanfei, Xu Xiwei The Haiyuan fault in Gansu Province, China, is a major left-lateral strike-slip fault forming the northeastern boundary of the Tibetan plateau and accommodating part of the deformation from the India-Asia collision. Geomorphic and geodetic studies of the Haiyuan fault show slip rates ranging from 4 mm/yr to 19 mm/yr from east to west along 500 km of the fault. Such discrepancy could be explained by the complex geometry of the fault system, leading to slip distribution on multiple branches. Combining displacement measurements of alluvial terraces from high-resolution Pléiades images and 10Be - 26Al cosmogenic radionuclides (CRN) dating, we bracket the late Quaternary slip rate along the Hasi Shan fault segment (37°00' N, 104°25' E). At our calibration site, terrace riser offsets for 5 terraces ranging from 6 m to 227 m and CRN ages ranging from 6.5±0.6 kyr to 41±4 kyr - yield geological left-lateral slip rates from 2.0 mm/yr to 4.4 mm/yr. We measured consistent terrace riser offset values along the entire 25 km-long segment, which suggests that some external forcing controls the regional river-terrace emplacement, regardless of each specific catchment. Hence, we extend our slip rate determination to the entire Hasi Shan fault segment to be 4.0±1.0 mm/yr since the last 40 kyr. This rate is consistent with other long-term rates of 4 mm/yr to 5 mm/yr east and west of Hasi Shan - as well as geodetic rates of 4 mm/yr to 6 mm/yr west of Hasi Shan. However, Holocene terraces and moraines offsets have suggested higher rates of 15 to 20 mm/yr further west. Such disparate rates may be explained by slip distribution on multiple branches. In particular, the Zhongwei fault splay in the central part of the Haiyuan fault, with a slip rate of 4-5 mm/yr could partly explain the faster rates on the western single stranded Haiyuan fault. In addition we constrained 0.55±0.1 mm/yr of uplift rate along the Hasi Shan, where the fault strike veers southward, indicating slip partitioning. Our slip rate along the Hasi Shan segment is consistent with most of the long-term and short-term slip rates ( 5 mm/yr) measured along the central and eastern parts of the Haiyuan fault. However the discrepancy with other studies to the west highlights the major implication of complex geometries on the slip distribution over large fault systems.

Glycosaminoglycan-resistant and pH-sensitive lipid-coated DNA complexes produced by detergent removal method.

PubMed

Lehtinen, Julia; Hyvönen, Zanna; Subrizi, Astrid; Bunjes, Heike; Urtti, Arto

2008-10-21

Cationic polymers are efficient gene delivery vectors in in vitro conditions, but these carriers can fail in vivo due to interactions with extracellular polyanions, i.e. glycosaminoglycans (GAG). The aim of this study was to develop a stable gene delivery vector that is activated at the acidic endosomal pH. Cationic DNA/PEI complexes were coated by 1,2-dioleylphosphatidylethanolamine (DOPE) and cholesteryl hemisuccinate (CHEMS) (3:2 mol/mol) using two coating methods: detergent removal and mixing with liposomes prepared by ethanol injection. Only detergent removal produced lipid-coated DNA complexes that were stable against GAGs, but were membrane active at low pH towards endosome mimicking liposomes. In relation to the low cellular uptake of the coated complexes, their transfection efficacy was relatively high. PEGylation of the coated complexes increased their cellular uptake but reduced the pH-sensitivity. Detergent removal was thus a superior method for the production of stable, but acid activatable, lipid-coated DNA complexes.

Quaternary Tectonic and Climatic Processes shaping the Central Andean hyperarid forearc (southern Peru)

NASA Astrophysics Data System (ADS)

Audin, Laurence; Benavente, Carlos; Zerathe, Swann; Saillard, Marianne; Hall, Sarah R.; Farber, Daniel L.

2015-04-01

Understanding the forearc structure and processes related to Quaternary evolution and uplift of the Western Andean Cordillera remains an outstanding scientific issue. Models of Andean Plateau evolution based on Tertiary volcanic stratigraphy since 5Ma suggest that the deformation was focused along the eastern margin of the plateau and that minimal uplift occurred along the Pacific margin. On the contrary, new tectonic data and Quaternary surface 10Be dating highlight the presence of recently active deformation, incision and alluvial processes within the upper Andean forearc together with a regional uplift of the coastal zone. Additionally, the high obliquity observed in the northern Arica Bend region makes it an ideal target to discuss whether partitioning of the oblique convergence is accommodated by the neotectonic features that dissect the Quaternary forearc. Our goals are both to decipher the Quaternary tectonic and climatic processes shaping the hyperarid forearc along strike and across strike. Finally, we aim to quantify the respective influence of these factors in the overall uplift of the Western Andes. Indeed, sequences of pediment surfaces, landslide products, paleolake deposits and marine terraces found along the oblique Peruvian margin are a unique set of datable markers that can be used to quantify the rates of Quaternary processes. In this study, we focus on the southern Peru hyperarid Atacama area where regional surfaces and tectonic markers (scarps, folds, temporary streams and paleolake levels offsets…) are well preserved for the Quaternary timescale. Numerous landsliding events align on the major fault segments and reflect Plio-Pleistocene climatic and tectonic activity together with filled and strath terraces. As the present day sea-level is one of the highest levels recorded for Quaternary time span, any emerged marine terrace is preserved by tectonic coastal uplift. In particular, the geomorphic and chronologic correlation between marine and continental planation surfaces or terraces permit to deduce net vertical rates and suggests that the along strike uplift affected not only the coast but also the overall ~50 km-wide forearc of the Western Andes. We produced a chronology of remnant low-relief surfaces and a new neotectonic map of the Central Andean forearc between ~14° and 18°S based on detailed field mapping and 10Be cosmogenic dating. We address 1) the spatial and temporal correlations of various markers, and 2) the correlation of the surface abandonment ages to various regional climatic events and 3) the description of neotectonic activity accommodating both uplift and partitioning. Multiple markers yield 10Be surface abandonment ages that spanning 35 ka to >2 Ma. Erosion surfaces >2 Ma yield low erosion rates of <0.1mm/yr. However uplift rates of ~0.1-1mm/yr and multiple surfaces dated at ~35 ka suggest that the hyperarid forearc landscape has been recently modified through Quaternary surface uplift and climatic events, contradicting the Miocene fossil forearc hypothesis. Generally, surface abandonment ages and activated landslides periods tend to correlate with cold wet periods preceding Plio Pleistocene deglaciation on the Altiplano. Finally, neotectonic oblique faults connecting at depth participate to topography building in the Arica Bend region and suggest that Quaternary surface abandonment is the result of both surface uplift in the forearc and specific high-discharge climate periods in the high Andes. Obtained Quaternary regional uplift rates and individual slip-rates suggest that the Andean forearc may accommodate as much as 0.5 to 1 mm/yr of regional uplift for the Quaternary time period.

What can one sample tell us? Stable isotopes can assess complex processes in national assessments of lakes, rivers and streams.

EPA Science Inventory

Stable isotopes can be very useful in large-scale monitoring programs because samples for isotopic analysis are easy to collect, and isotopes integrate information about complex processes such as evaporation from water isotopes and denitrification from nitrogen isotopes. Traditi...

Algicidal Activity of a Surface-Bonded Organosilicon Quaternary Ammonium Chloride

PubMed Central

Walters, P. A.; Abbott, E. A.; Isquith, A. J.

1973-01-01

The hydrolysis product of a quaternary amine-containing organosilicon salt, 3-(trimethoxysilyl)-propyldimethyloctadecyl ammonium chloride, was found to exhibit algicidal activity while chemically bonded to a variety of substrates. Six representative species of Chlorophyta, Cyanophyta, and Chrysophyta were used to evaluate the algicidal activity. Substrate-bonded 14C-labeled organosilicon quaternary ammonium salt when attached to nonwoven fibers was durable to repeated washings, and algicidal activity could not be attributed to slow release of the chemical. Images PMID:4632852

Map showing thickness of saturated Quaternary deposits, Sugar House quadrangle, Salt Lake County, Utah, February 1972

USGS Publications Warehouse

Mower, R.W.

1973-01-01

Saturated Quaternary deposits in the Sugar Horse quadrangle supply significant quantities of water to wells from which water is withdrawn for domestic, municipal, industrial, and irrigation uses. The deposits consist of clay, silt, sand, and gravel; individual beds range from a few inches to several tens of feet thick. The principal aquifer, which is almost completely within the Quaternary deposits, supplied about 4 percent, or 9,000 acre-feet, of the municipal and industrial water used annually in Salt Lake County during 1964-68.As a general rule, more water is stored and more water will be yielded to a well where aquifers are thicker. This map can be used as a general guide to those areas where greatest amounts of water are stored in the aquifer, and where yields to wells may be greater. Local variations in the ability of saturated deposits to transmit water can alter the general relationship between aquifer thickness and yield of wells.The thickness of saturated Quaternary deposits within the area of the Sugar Horse quadrangle ranges from zero to about 650 feet, as shown on the map. The thickest section of these deposits is near the southwestern corner of the quadrangle, and the thinnest section is along the mountain front adjacent to the approximate eastern limit of saturated Quaternary deposits.The thickness of saturated Quaternary deposits shown on this map is based on drillers’ logs for 55 deep wells (which show the thickness of the Quaternary deposits) and on water-level measurements made in February 1972 in wells in unconfined shallow aquifers.Reports in the following list of selected references contain other information about the saturated Quaternary deposits in this and adjacent parts of Jordan Valley, Utah. The basic-data reports and releases contain well logs, water-level measurements, and other types of basic ground-water data. The interpretive repots contain discussions of the occurrence of ground water, tests to determine hydraulic properties of the aquifer, and related information. Ground-water terms used in this report have been defined by Lohman and others (1972).

A major change in precipitation gradient on the Chinese Loess Plateau at the Pliocene-Quaternary boundary

NASA Astrophysics Data System (ADS)

Peng, Wenbin; Nie, Junsheng; Wang, Zhao; Qiang, Xiaoke; Garzanti, Eduardo; Pfaff, Katharina; Song, Yougui; Stevens, Thomas

2018-04-01

Spatiotemporal variations in East Asian Monsoon (EAM) precipitation during the Quaternary have been intensively studied. However, spatial variations in pre-Quaternary EAM precipitation remain largely uninvestigated, preventing a clear understanding of monsoon dynamics during a warmer climatic period. Here we compare the spatial differences in heavy mineral assemblages between Quaternary loess and pre-Quaternary Red Clay on the Chinese Loess Plateau (CLP) to analyze spatial patterns in weathering. Prior studies have revealed that unstable hornblende is the dominant (∼50%) heavy mineral in Chinese loess deposited over the past 500 ka, whereas hornblende content decreases to <10% in strata older than ∼1 Ma in the central CLP because of diagenesis. In the present study we found that hornblende is the dominant heavy mineral in 2-2.7 Ma loess on the northeastern CLP (at Jiaxian), which today receives little precipitation. Conversely, hornblende content in the upper Miocene-Pliocene Red Clay at Jiaxian is <10%, as in the central CLP. The early Quaternary abundance of hornblende at Jiaxian indicates that the current northwestward-decreasing precipitation pattern and consequent dry climate at Jiaxian must have been initiated since ∼2.7 Ma, preventing hornblende dissolution to amounts <10% as observed in the central CLP. By contrast, the 7 Ma and 3 Ma Jiaxian Red Clay hornblende content is significantly less than that of the Xifeng samples, despite the fact that today Xifeng receives more precipitation than Jiaxian, with expected enhanced hornblende weathering. This suggests that the northeastern CLP received more precipitation during the Late Miocene-Pliocene than at Xifeng, indicating that the precipitation gradient on the CLP was more east-west during the Late Miocene-Pliocene rather than northwest-southeast as it was in the Quaternary. A comparison of magnetic susceptibility records for these sections confirms this inference. We attribute this major change in climatic patterns at ∼2.7 Ma to decreased northward moisture transportation associated with Northern Hemisphere glaciation and cooling in the Quaternary. This study therefore demonstrates the potential usefulness of employing heavy mineral analysis in both paleoclimatic and paleooceanographic reconstructions.

Prevalence of IgE against neuromuscular blocking agents in hairdressers and bakers.

PubMed

Dong, S; Acouetey, D S; Guéant-Rodriguez, R-M; Zmirou-Navier, D; Rémen, T; Blanca, M; Mertes, P M; Guéant, J-L

2013-11-01

Allergic IgE-mediated reactions to neuromuscular blocking agents (NMBAs) are the main cause of immediate hypersensitivity reactions in anaesthesia; their predominant occurrence in the absence of previous exposure to NMBAs suggests a risk related to environmental exposure. To investigate the prevalence of specific IgE to quaternary ammonium ions in two populations professionally exposed to quaternary ammonium compounds, in the north-eastern France. The study had a retrospective follow-up design whereby apprentices were assessed after their 2-year training period as apprentices. The professionally exposed hairdresser populations (n = 128) were compared with baker/pastry makers (n = 108) and 'non-exposed' matched control subjects (n = 379). We observed a 4.6-fold higher frequency of positive IgE against quaternary ammonium ions in hairdressers (HD), compared with baker/pastry makers (BP) and control (C) groups. The competitive inhibition of quaternary ammonium Sepharose radioimmunoassay (QAS-IgE RIA) with succinylcholine was significantly higher in HD, compared with BP and C groups, with inhibition percentage of 66.2 ± 7.4, 39.7 ± 6.0 and 43.8 ± 9.9, respectively (P < 0.001). The specific IgE against quaternary ammonium ions recognized also two compounds widely used by hairdressers, benzalkonium chloride and polyquaternium-10, in competitive inhibition of IgE RIA. When considering the whole study population, hairdresser professional exposure and total IgE > 100 kU/L were the two significant predictors of IgE-sensitization against quaternary ammonium ions in the multivariate analysis of a model that included age, sex, professional exposure, increased concentration of total IgE (IgE > 100 kU/L) and positive IgE against prevalent allergens (Phadiatop(®) ; P = 0.019 and P = 0.001, respectively). The exposure to hairdressing professional occupational factors increases IgE-sensitization to NMBAs and quaternary ammonium ion compounds used in hairdressing. Besides the pholcodine hypothesis, our study suggests that repetitive exposure to quaternary ammonium compounds used in hairdressing is a risk factor for NMBAs sensitization. © 2013 John Wiley & Sons Ltd.

On-line Ammonia Sensor and Invisible Security Ink by Fluorescent Zwitterionic Spirocyclic Meisenheimer Complex

PubMed Central

Das, Tanmay; Pramanik, Apurba; Haldar, Debasish

2017-01-01

Ammonia is not only a highly important gas for civilization but also contribute significantly for climate change and human health hazard. Highly sensitive ammonia sensor has been developed from a fluorescent zwitterionic spirocyclic Meisenheimer complex. Moreover, formation of this Meisenheimer complex can also be utilized for selective as well as naked eye instant detection of nitro aromatic explosive picric acid. The presence of a quaternary nitrogen atom directly attached to the spiro carbon is the unique feature of this Meisenheimer complex. This excellent photoluminescent (PL) Meisenheimer complex has two distinct stimuli responsive sites. One is sensitive towards acid while the other one is towards the base. These two positions can be modulated by adding one equivalent acid and one equivalent base to result two new products which are non fluorescent. One of these two non fluorescent species was found very exciting because of its UV/Vis transparency. Utilizing this concept we have fabricated an on-line sensor for measuring ammonia in dry or humid and condensing sewer air. The sensor was robust against ambient temperature and humidity variation. We have also developed an invisible ink from this Meisenheimer complex, with potential application for security purpose. PMID:28091542

On-line Ammonia Sensor and Invisible Security Ink by Fluorescent Zwitterionic Spirocyclic Meisenheimer Complex.

PubMed

Das, Tanmay; Pramanik, Apurba; Haldar, Debasish

2017-01-16

Ammonia is not only a highly important gas for civilization but also contribute significantly for climate change and human health hazard. Highly sensitive ammonia sensor has been developed from a fluorescent zwitterionic spirocyclic Meisenheimer complex. Moreover, formation of this Meisenheimer complex can also be utilized for selective as well as naked eye instant detection of nitro aromatic explosive picric acid. The presence of a quaternary nitrogen atom directly attached to the spiro carbon is the unique feature of this Meisenheimer complex. This excellent photoluminescent (PL) Meisenheimer complex has two distinct stimuli responsive sites. One is sensitive towards acid while the other one is towards the base. These two positions can be modulated by adding one equivalent acid and one equivalent base to result two new products which are non fluorescent. One of these two non fluorescent species was found very exciting because of its UV/Vis transparency. Utilizing this concept we have fabricated an on-line sensor for measuring ammonia in dry or humid and condensing sewer air. The sensor was robust against ambient temperature and humidity variation. We have also developed an invisible ink from this Meisenheimer complex, with potential application for security purpose.

On-line Ammonia Sensor and Invisible Security Ink by Fluorescent Zwitterionic Spirocyclic Meisenheimer Complex

NASA Astrophysics Data System (ADS)

Das, Tanmay; Pramanik, Apurba; Haldar, Debasish

2017-01-01

Ammonia is not only a highly important gas for civilization but also contribute significantly for climate change and human health hazard. Highly sensitive ammonia sensor has been developed from a fluorescent zwitterionic spirocyclic Meisenheimer complex. Moreover, formation of this Meisenheimer complex can also be utilized for selective as well as naked eye instant detection of nitro aromatic explosive picric acid. The presence of a quaternary nitrogen atom directly attached to the spiro carbon is the unique feature of this Meisenheimer complex. This excellent photoluminescent (PL) Meisenheimer complex has two distinct stimuli responsive sites. One is sensitive towards acid while the other one is towards the base. These two positions can be modulated by adding one equivalent acid and one equivalent base to result two new products which are non fluorescent. One of these two non fluorescent species was found very exciting because of its UV/Vis transparency. Utilizing this concept we have fabricated an on-line sensor for measuring ammonia in dry or humid and condensing sewer air. The sensor was robust against ambient temperature and humidity variation. We have also developed an invisible ink from this Meisenheimer complex, with potential application for security purpose.

Geologic map of the Wildcat Lake 7.5' quadrangle: Kitsap and Mason counties, Washington

USGS Publications Warehouse

Haeussler, Peter J.; Clark, Kenneth P.

2000-01-01

The Wildcat Lake quadrangle lies in the forearc of the Cascadia subduction zone, about 20-km east of the Cascadia accretionary complex exposed in the Olympic Mountains (Tabor and Cady, 1978),and about 100-km west of the axis of the Cascades volcanic arc. The quadrangle lies near the middle of the Puget Lowland, which typically has elevations less than 600 feet (183 m), but on Gold Mountain, in the center of the quadrangle, the elevation rises to 1761 feet (537 m). This anomalously high topography also provides a glimpse of the deeper crust beneath the Lowland. Exposed on Green and Gold Mountains are rocks related to the Coast Range basalt terrane. This terrane consists of Eocene submarine and subaerial tholeiitic basalt of the Crescent Formation, which probably accreted to the continental margin in Eocene time (Snavely and others, 1968). The Coast Range basalt terrane may have originated as an oceanic plateau or by oblique marginal rifting (Babcock and others, 1992), but its subsequent emplacement history is complex (Wells and others, 1984). In southern Oregon, onlapping strata constrain the suturing to have occured by 50 Ma; but on southern Vancouver Island where the terrane-bounding Leech River fault is exposed, Brandon and Vance (1992) concluded suturing to North America occurred in the broad interval between 42 and 24 Ma. After emplacement of the Coast Range basalt terrane, the Cascadia accretionary complex,exposed in the Olympic Mountains west of the quadrangle,developed by frontal accretion and underplating (e.g., Clowes and others, 1987). The Seattle basin, part of which lies to the north of Green Mountain, also began to develop in late Eocene time due to forced flexural subsidence along the Seattle fault zone (Johnson and others, 1994). Domal uplift of the accretionary complex beneath the Olympic Mountains occurred after approximately 18 million years ago (Brandon and others, 1998). Ice-sheet glaciation during Quaternary time reshaped the topography of the quadrangle, and approximately two-thirds of the map area is covered with Quaternary deposits related to the last glaciation. Geophysical studies and regional mapping indicate the Seattle fault lies north of Green Mountain. This fault produced a large earthquake about 1000 years ago and may pose a significant earthquake hazard (Bucknam and others, 1992; Atwater and Moore, 1992; Karlin and Abella,1992; Schuster and others, 1992; Jacoby and others, 1992). We found no evidence of Holocene faulting in the Wildcat Lake quadrangle. Geologic mapping within and marginal to the quadrangle began with Willis (1898), who described glacial deposits in Puget Sound. Weaver (1937) correlated volcanic rocks in the quadrangle to the Eocene Metchosin Volcanics on Vancouver Island. Sceva (1957), Garling and Moleenar (1965), and Deeter (1978) all focused on mapping and understanding the Quaternary stratigraphy of the Kitsap Peninsula, but they also examined bedrock in the quadrangle. Reeve (1979) was the first to examine the igneous rocks on Green and Gold Mountains in some detail, and Clark (1989) significantly improved Reeve's (1979) mapping. Clark's (1989) mapping was conducted soon after extensive logging on the mountains. A surficial geologic map of the Seattle 1:100,000-scale quadrangle, which includes the Wildcat Lake 1:24,000-scale quadrangle, was published by Yount and others (1993). Yount and Gower (1991) also published a bedrock geologic map of the Seattle quadrangle. Geologic mapping for this report was conducted by Haeussler in the spring and summer of 1998 and in the winter of 1999. We could not substantially improve upon the bedrock mapping of Clark (1989) and thus it is incorporated into this map. Well data in the southeastern corner of the map area also helped to constrain the surficial mapping (Geomatrix Consultants, 1997). In addition, 1995 vintage 1:12,000-scale aerial photographs were used in mapping Quaternary deposits. Geologic time scale is that of Berggeren and others (1995).

Incipient Evolution of the Eastern California Shear Zone through a Transpressional Zone along the San Andreas Fault in the San Bernardino Mountains, California

NASA Astrophysics Data System (ADS)

Cochran, W. J.; Spotila, J. A.

2017-12-01

Measuring long-term accumulation of strike-slip displacements and transpressional uplift is difficult where strain is accommodated across wide shear zones, as opposed to a single major fault. The Eastern California Shear Zone (ECSZ) in southern California accommodates dextral shear across several strike-slip faults, and is potentially migrating and cutting through a formerly convergent zone of the San Bernardino Mountains (SBM). The advection of crust along the San Andreas fault to the SE has forced these two tectonic regimes into creating a nexus of interacting strike-slip faults north of San Gorgonio Pass. These elements make this region ideal for studying complex fault interactions, evolving fault geometries, and deformational overprinting within a wide shear zone. Using high-resolution topography and field mapping, this study aims to test whether diffuse, poorly formed strike-slip faults within the uplifted SBM block are nascent elements of the ECSZ. Topographic resolution of ≤ 1m was achieved using both lidar and UAV surveys along two Quaternary strike-slip faults, namely the Lake Peak fault and Lone Valley faults. Although the Lone Valley fault cuts across Quaternary alluvium, the geomorphic expression is obscured, and may be the result of slow slip rates. In contrast, the Lake Peak fault is located high elevations north of San Gorgonio Peak in the SBM, and displaces Quaternary glacial deposits. The deposition of large boulders along the escarpment also obscures the apparent magnitude of slip along the fault. Although determining fault offset is difficult, the Lake Peak fault does display evidence for minor right-lateral displacement, where the magnitude of slip would be consistent with individual faults within the ECSZ (i.e. ≤ 1 mm/yr). Compared to the preservation of displacement along strike-slip faults located within the Mojave Desert, the upland region of the SBM adds complexity for measuring fault offset. The distribution of strain across the entire SBM block, the slow rates of slip, and the geomorphic expression of these faults add difficulty for assessing fault-slip evolution. Although evidence for diffuse dextral faulting exists within the formerly uplifted SBM block, future work is needed along these faults to determine if the ECSZ is migrating west.

Mammoth Mountain and its mafic periphery—A late Quaternary volcanic field in eastern California

USGS Publications Warehouse

Hildreth, Wes; Fierstein, Judith; Champion, Duane E.; Calvert, Andrew T.

2014-01-01

The trachydacite complex of Mammoth Mountain and an array of contemporaneous mafic volcanoes in its periphery together form a discrete late Pleistocene magmatic system that is thermally and compositionally independent of the adjacent subalkaline Long Valley system (California, USA). The Mammoth system first erupted ca. 230 ka, last erupted ca. 8 ka, and remains restless and potentially active. Magmas of the Mammoth system extruded through Mesozoic plutonic rocks of the Sierra Nevada batholith and extensive remnants of its prebatholith wall rocks. All of the many mafic and silicic vents of the Mammoth system are west or southwest of the structural boundary of Long Valley caldera; none is inboard of the caldera’s buried ring-fault zone, and only one Mammoth-related vent is within the zone. Mammoth Mountain has sometimes been called part of the Inyo volcanic chain, an ascription we regard inappropriate and misleading. The scattered vent array of the Mammoth system, 10 × 20 km wide, is unrelated to the range-front fault zone, and its broad nonlinear footprint ignores both Long Valley caldera and the younger Mono-Inyo range-front vent alignment. Moreover, the Mammoth Mountain dome complex (63%–71% SiO2; 8.0%–10.5% alkalies) ended its period of eruptive activity (100–50 ka) long before Holocene inception of Inyo volcanism. Here we describe 25 silicic eruptive units that built Mammoth Mountain and 37 peripheral units, which include 13 basalts, 15 mafic andesites, 6 andesites, and 3 dacites. Chemical data are appended for nearly 900 samples, as are paleomagnetic data for ∼150 sites drilled. The 40Ar/39Ar dates (230–16 ka) are given for most units, and all exposed units are younger than ca. 190 ka. Nearly all are mildly alkaline, in contrast to the voluminous subalkaline rhyolites of the contiguous long-lived Long Valley magma system. Glaciated remnants of Neogene mafic and trachydacitic lavas (9.1–2.6 Ma) are scattered near Mammoth Mountain, but Quaternary equivalents older than ca. 230 ka are absent. The wide area of late Quaternary Mammoth magmatism remained amagmatic during the long interval (2.2–0.3 Ma) of nearby Long Valley rhyolitic eruptions.

Glacial evolution of the Ampato Volcanic Complex (Peru)

NASA Astrophysics Data System (ADS)

Alcalá, J.; Palacios, D.; Zamorano, J. J.; Vázquez, L.

2009-04-01

Ice masses on the Western range of the Central Andes are a main source of water resources and act as a geoindicator of variations in the climate of the tropics (Mark, 2008). The study of their evolution is of particular interest since they are situated in the transition zone between the tropical and mid-latitude circulation areas of the atmosphere (Zech et al., 2007). The function of this transition area is currently under debate, and understanding it is essential for the development of global climate models (Kull et al, 2008; Mark, 2008). However our understanding of the evolution of glaciers and their paleoclimatic factors for this sector of the Central Andes is still at a very basic level. This paper presents initial results of a study on the glacial evolution of the Ampato volcanic complex (15°24´- 15° 51´ S, 71° 51´ - 73° W; 6288 m a.s.l.) located in the Western Range of the Central Andes in Southern Peru, 70 km NW of the city of Arequipa. The main objectives are to identify the number of glacial phases the complex has undergone using geomorphological criteria to define a time frame for each phase, based on cosmogenic 36Cl dating of a sequence of moraine deposits; and to estimate the glacier Equilibrium Line Altitude (ELA) of each phase. The Ampato volcanic complex is formed by 3 great andesitic stratovolcanoes, the Nevados HualcaHualca-Sabancaya-Ampato, which started forming between the late Miocene and early Quaternary (Bulmer et al., 1999), aligned N-S and with summits covered with glaciers. The Sabancaya volcano is fully active, with its latest eruption occurring in 2001. Glacial landforms were identified and mapped using photointerpretation of vertical aerial photographs from 1955 (1:35,000 scale, National Geographic Institute of Peru), oblique photographs from 1943 (Aerophotographical Service of Peru), and a geo-referenced high-resolution Mrsid satellite image from 2000 (NASA). This cartography was corrected and improved through fieldwork. It was then digitized in a Geographical Information System (GIS) using the existing 1:100,000 maps (National Geographical Institute of Peru) as a topographical base. Once the geomorphological maps had been analyzed, we decided to focus on the glacial evolution of a representative section of the Ampato Complex, specifically the Huayuray valley, located north of the HualcaHualca volcano. According to the altitudinal position and the degree of conservation of the moraines along the Quebrada, glacial phases of the Last Glacial Maximum (LGM), the Neoglacial and the Little Ice Age (LIA) were identified. The GIS was then used to delimit and calculate the ice surface area of each one. The same was also done for the years 1955 and 2000 AD, based on the interpretation of aerial photographs and satellite images from those years. Next, the ELA was calculated using the Altitude Area (AA) method (Osmaston, 2005) using GIS and the glacier paleotopography was reconstructed using geomorphological evidence (Carr, S & Coleman, C, 2007). To obtain numerical ages of moraine boulders and glacially abraded bedrock we applied cosmogenic36Cl surface exposure dating (Gosse & Phillips, 2001), which is the best method for volcanic rocks with no quartz content. Samples were collected from stable boulders located at the crests of moraine ridges and over 1 m in height. They were analyzed following procedures by Zreda et al. (1999) and Phillips (2003); physical analyses were undertaken at Universidad Complutense in Spain and physic-chemical analyses at the PRIME laboratory (Purdue University). LGM moraine forms always occupy the lowest altitude position, forming well-defined moraine arcs and ridges, with large dimensions and well preserved. During this phase, the climate was colder and damper than is currently the case in the Central Andes. Calculations show mean temperature during this period to have been 4 - 6°C below present values, and with more abundant precipitation (Seltzer et al., 2002). Under these climatic conditions, glaciers expanded and their fronts descended to a minimum altitude of 3900 m a.s.l. in the Huayuray valley. The ELA was at 4980 m a.s.l., implying an ELA depression of 900 m compared to the situation in 2000 AD. The age obtained for the Ampato Volcanic Complex using cosmogenic methods is 16,500 ± 0.37 y. AP, similar to the dates proposed by Clapperton (1993) - around 18,800 y. BP-, and far away from those proposed by Seltzer (2002) -30,000 y. BP- or by Smith et al. (2005) -21,000 y. BP-, although there is no certainty that the samples represent the oldest ridges of this period. Several records exist of Neoglacial advances, mainly well preserved moraines located in the glacial valleys immediately behind LGM moraines. One of these reached a minimum altitude of 4300 m a.s.l., with the ELA at 5240 m a.s.l., which implies an ELA depression of 560 m compared to the 2000 AD situation. 36Cl dating indicates that this Neoglacial advance occurred in 11,400 ± 0.21 y. BP. Two main glacial readvancement events due to climatic conditions have been noted in the Central Andes: The first between 15,000 and 13,000 yr. BP and the second at 12,000-10,000 yr. BP (Clapperton, 1993; Zech, et al., 2007). The latter has been dated with sufficient precision on the Chimborazo (Ecuador), the Junin Plains (Peru), and the Quelccaya Glacier (Peru) (Clapperton, 1993; Seltzer, 1990 and Smith et al. 2005) and corresponds to the described event in the Ampato Complex. There is limited data on the Little Ice Age for the Central Andes. This phase is represented by small moraines, located at high altitudes, very near the current glacial fronts. Ice cores extracted from some Central Andean glaciers, such as the Quelccaya Glacier (Peru), show a cooling episode between 1500 and 1820 AD, which corresponds to the LIA (Seltzer, 1990). During this recent global cold event, the minimum altitude of glaciers on the Ampato Volcanic Complex reached 5400 m a.s.l., 250 m below their 2000 position. The ELA is estimated at 5770 m a.s.l., with a depression of 110 m compared to 2000 AD. Existing ice masses on the Ampato are currently experiencing a substantial retreat. In 1955 the surface area they covered in the Huayuray valley was 2.45 km2, with an estimated ELA of 5800 m a.s.l., whereas by 2000 the area had been reduced to 1.45 km2 and the ELA climbed to 5887 m a.s.l.. In only 45 years, the glaciers have shrunk ~1 km2 and the ELA has raised 90 m. If the current trend continues, glaciers will have disappeared from this tropical mountain in approximately 65 years time. REFERENCES Bulmer, M.; Johnston, A. & Engle, F. (1999): Analysis of Sabancaya volcano, souther Peru using Radarsat and Landsat TM data. Application Development and Research Opportunity (ADRO), 10 pp. Carr, S & Coleman, C. (2007): An improved technique for the reconstruction of former glacier mass-balance and dynamics. Geomorphology, 92: 76-90. Clapperton, C. M. (1993). Quaternary Geology and Geomorphology of South America. Elservier, Amsterdam, 779 pp. Gosse, J.C.; y Phillips, F. M. (2001): Terrestrial in situ cosmogenic nuclides: theory and application. Quaternary Science Reviews 20: 1475-560. Mark, B. (2008): Tracing tropical Andean glaciers over space and time: Some lessons and transdisciplinary implications. Global and Planetary Change, 60: 101-114. Osmaston, H. (2005): Estimates of glacier equilibrium line altitudes by the Area Ã- Altitude, the Area Ã- Altitude Balance Ratio and the Area Ã- Altitude Balance Index Methods and their validation. Quaternary International, 138-139: 22-31. Phillips, F. M. (2003): Cosmogenic Cl36 ages of Quaternary basalt flows in the Mojave Desert, California, USA. Geomorphology, 53: 199-208. Kull, C.; Imhof, S.; Grosjean, M. y Veit, H. (2008): Late Pleistocene glaciations in the Central Andes: Temperature versus humidity control - A case study from the eastern Bolivian Andes (17° S) and regional synthesis. Global and Planetary Change (en prensa). Seltzer, G.O. (1990): Recent glacial history and paleoclimate of the Peruvian - Bolivian Andes. Quaternary Science Reviews, 9: 137-152. Seltzer, G. O.; Rodbell, D. T; Baker, P. A.; Fritz, S. C.; Tapia, P. M.; Rowe, H.D.; y Dunbar, R. B. (2002): Early warming of Tropical South America at the Last Glacial-Interglacial Transition. Science, 296: 1.685-1.686. Smith, J. A.; Seltzer, G.O.; Rodbell, R.T.; y Klein, A.R. (2005): Regional synthesis of last glacial maximum snowlines in the tropical Andes, South America. Quaternary International, 138: 145 -167. Zech, R.; Kull, CH.; Kubik, P. W. y Veit, H. (2007): Exposure dating of Late Glacial and pre-LGM moraines in the Cordon de Doña Rosa, Northern/Central Chile (31° S). Climate of the Past, 3: 1-14. Zech, R.; Kull, CH.; Kubik, P. W. y Veit, H. (2007): LGM and Late Glacial glacier advances in the Cordillera Real and Cochabamba (Bolivia) deduced from 10Be surface exposure dating. Climate of the Past, 3: 623-635. Zreda, M., J. England, F. Phillips, D. Elmore, and P. Sharma, (1999): Unblocking the Nares Strait by Greenland and Ellesmere ice-sheet retreat 10,000 years ago, Nature, 398: 139-142.

Cenozoic stratigraphy and geologic history of the Tucson Basin, Pima County, Arizona

USGS Publications Warehouse

Anderson, S.R.

1987-01-01

This report was prepared as part of a geohydrologic study of the Tucson basin conducted by the U.S. Geological Survey in cooperation with the city of Tucson. Geologic data from more than 500 water supply and test wells were analyzed to define characteristics of the basin sediments that may affect the potential for land subsidence induced by groundwater withdrawal. The Tucson basin is a structural depression within the Basin and Range physiographic province. The basin is 1,000 sq mi in units area and trends north to northwest. Three Cenozoic stratigraphic unit--the Pantano Formation of Oligocene age, the Tinaja beds (informal usage) of Miocene and Pliocene age, and the Fort Lowell Formation of Pleistocene age--fill the basin. The Tinaja beds include lower, middle, and upper unconformable units. A thin veneer of stream alluvium of late Quaternary age overlies the Fort Lowell Formation. The Pantano Formation and the lower Tinaja beds accumulated during a time of widespread continental sedimentation, volcanism, plutonism, uplift, and complex faulting and tilting of rock units that began during the Oligocene and continued until the middle Miocene. Overlying sediments of the middle and upper Tinaja beds were deposited in response to two subsequent episodes of post-12-million-year block faulting, the latter of which was accompanied by renewed uplift. The Fort Lowell Formation accumulated during the Quaternary development of modern through-flowing the maturation of the drainage. The composite Cenozoic stratigraphic section of the Tucson basin is at least 20,000 ft thick. The steeply tilted to flat-lying section is composed of indurated to unconsolidated clastic sediments, evaporites, and volcanic rocks that are lithologically and structurally complex. The lithology and structures of the section was greatly affected by the uplift and exhumation of adjacent metamorphic core-complex rocks. Similar Cenozoic geologic relations have been identified in other parts of southern Arizona. (Author 's abstract)

Electrostatic occlusion and quaternary structural ion pairing are key determinants of Cu(I)-mediated allostery in the copper-sensing operon repressor (CsoR).

PubMed

Chang, Feng-Ming James; Martin, Julia E; Giedroc, David P

2015-04-21

The copper-sensing operon repressor (CsoR) is an all-α-helical disc-shaped D2-symmetric homotetramer that forms a 2:1 tetramer/DNA operator complex and represses the expression of copper-resistance genes in a number of bacteria. A previous bioinformatics analysis of CsoR-family repressors distributes Cu(I)-sensing CsoRs in four of seven distinct clades on the basis of global sequence similarity. In this work, we define energetically important determinants of DNA binding in the apo-state (ΔΔGbind), and for allosteric negative coupling of Cu(I) binding to DNA binding (ΔΔGc) in a model clade IV CsoR from Geobacillus thermodenitrificans (Gt) of known structure, by selectively targeting for mutagenesis those charged residues uniquely conserved in clade IV CsoRs. These include a folded N-terminal "tail" and a number of Cu(I)-sensor and clade-specific residues that when mapped onto a model of Cu(I)-bound Gt CsoR define a path across one face of the tetramer. We find that Cu(I)-binding prevents formation of the 2:1 "sandwich" complex rather than DNA binding altogether. Folding of the N-terminal tail (residues R18, E22, R74) upon Cu-binding to the periphery of the tetramer inhibits assembly of the 2:1 apoprotein-DNA complex. In contrast, Ala substitution of residues that surround the central "hole" (R65, K101) in the tetramer, as well R48, impact DNA binding. We also identify a quaternary structural ion-pair, E73-K101″, that crosses the tetramer interface, charge-reversal of which restores DNA binding activity, allosteric regulation by Cu(I), and transcriptional derepression by Cu(I) in cells. These findings suggest an "electrostatic occlusion" model, in which basic residues important for DNA binding and/or allostery become sequestered via ion-pairing specifically in the Cu(I)-bound state, and this aids in copper-dependent disassembly of a repression complex.

Efficient Red-Emitting Platinum Complex with Long Operational Stability.

PubMed

Fleetham, Tyler; Li, Guijie; Li, Jian

2015-08-05

A tetradentate cyclometalated Pt(II) complex, PtN3N-ptb, was developed as an emissive dopant for stable and efficient red phosphorescent OLEDs. Devices employing PtN3N-ptb in electrochemically stable device architectures achieved long operational lifetimes with estimated LT97, of over 600 h at luminances of 1000 cd/m(2). Such long operational lifetimes were achieved utilizing only literature reported host, transporting and blocking materials with known molecular structures. Additionally, a thorough study of the effects of various host and transport materials on the efficiency, turn on voltage, and stability of the devices was carried out. Ultimately, maximum forward viewing EQEs as high as 21.5% were achieved, demonstrating that Pt(II) complexes can act as stable and efficient dopants with operational lifetimes comparable or superior to those of the best literature-reported Ir(III) complexes.

Compression behavior of quaternary and higher order solid-solution L1(2) trialuminides

NASA Technical Reports Server (NTRS)

Kumar, K. S.; Brown, S. A.

1992-01-01

Results from preliminary studies undertaken to evaluate the existence of single-phase L1(2) solid solutions between pairs of ternary L1(2) trialuminides are presented. Two-kilogram ingots of selected quaternary compositions were cast, homogenized and forged into pancakes; compression specimens were machined from the forgings and tested as a function of temperature. The results are compared against existing data for the ternary alloys. The ternary L1(2) trialuminides Al66Ti25Mn9, Al67Ti25Cr8, and Al22Ti8Fe3 were found to exhibit continuous solubility in one another. The quaternary Cr-Mn composition does not indicate any strength advantage over its ternary counterparts. The continuous replacement of Mn with Fe enhances the strength of the quaternary compound over the ternary Al66Ti25 Mn9.

Sex allocation and functional bias of quaternary and quinary flowers on same inflorescence in the hermaphrodite Ruta graveolens

NASA Astrophysics Data System (ADS)

Tang, Jing-Yu; Ren, Ming-Xun

2011-09-01

Intra-inflorescence variation in floral traits is important to understand the pollination function of an inflorescence and the real reproductive outputs of a plant. Ruta graveolens (Rutaceae) produce both quaternary (four petals and eight stamens) and quinary (five petals and ten stamens) flowers on the same cymes, while their pollination roles and the effects on the reproductive success remained unexplored. We experimentally examined the biomass of female versus male organs and pollen viability and stigma receptivity to explore the sex allocation patterns between the flowers. The breeding systems and reproductive outputs through either female function (seed set) or male function (pollen dispersal) were also studied for quinary and quaternary flowers to determine whether there was functional bias. The results showed that R. graveolens was protandrous, with a mixed mating system. Its stamens could slowly move one by one and only dehisce when positioning at the flower center, which could greatly enhance pollen dispersal. The first-opened quinary flower allocated significantly higher resources (dry biomass) in female organs while quaternary flowers allocated more resource in male organs. The quaternary flowers experienced higher pollen limitation in seed production but were more successful in pollen dispersal and the quinary flowers reproduced both through female and male functions. Our data suggested that quinary and quaternary flower on same inflorescence in R. graveolens functioned mainly as the sex role that most resources were allocated, which probably reflect an adaptation for floral phenology and pollination process in this plant.

Study of base pair mutations in proline-rich homeodomain (PRH)-DNA complexes using molecular dynamics.

PubMed

Jalili, Seifollah; Karami, Leila; Schofield, Jeremy

2013-06-01

Proline-rich homeodomain (PRH) is a regulatory protein controlling transcription and gene expression processes by binding to the specific sequence of DNA, especially to the sequence 5'-TAATNN-3'. The impact of base pair mutations on the binding between the PRH protein and DNA is investigated using molecular dynamics and free energy simulations to identify DNA sequences that form stable complexes with PRH. Three 20-ns molecular dynamics simulations (PRH-TAATTG, PRH-TAATTA and PRH-TAATGG complexes) in explicit solvent water were performed to investigate three complexes structurally. Structural analysis shows that the native TAATTG sequence forms a complex that is more stable than complexes with base pair mutations. It is also observed that upon mutation, the number and occupancy of the direct and water-mediated hydrogen bonds decrease. Free energy calculations performed with the thermodynamic integration method predict relative binding free energies of 0.64 and 2 kcal/mol for GC to AT and TA to GC mutations, respectively, suggesting that among the three DNA sequences, the PRH-TAATTG complex is more stable than the two mutated complexes. In addition, it is demonstrated that the stability of the PRH-TAATTA complex is greater than that of the PRH-TAATGG complex.

Characterizing Cretaceous Glaciation Events: K-Ar Ages of Southern Ocean Sediments

NASA Astrophysics Data System (ADS)

Wright, M. A.; Hemming, S. R.; Barbeau, D. L.; Torfstein, A.; Pierce, E. L.; Williams, T.; McManus, J. F.; Gombiner, J.

2012-12-01

Evidence from paleosols and carbonate weathering models suggest that the Late Cretaceous had a supergreenhouse climate due to atmospheric CO2 concentrations two to four times greater than modern levels, tropical sea surface temperatures exceeding 35°C, and high-latitude temperatures exceeding 20°C. Despite this warmth, the Late Cretaceous was apparently punctuated by large (>25 m) and rapid (<<1 million year) sea-level changes, as recorded by marginal marine stratigraphic architectures and pelagic stable isotope compositions. The magnitude and tempo of these changes suggest a glacio-eustatic control, presumably from the growth and decay of continental ice sheets on Antarctica. Because continental glaciation tends to increase the weathering of bedrock and production of sediment delivered to the oceans, circum-Antarctic marine sediment flux would be expected to increase during periods of glaciation. In order to identify a Late Cretaceous glaciation signal from such marine records, we must first constrain the compositional signal of continental detritus in marine sediments. Here we report the results of downcore K-Ar analysis of the terrigenous sediments of Quaternary Weddell Sea cores PS1170-1 and PS1388-3 in order to identify the compositional signature of continent-derived detritus deposited in the Weddell Sea during a known glacial period. Further, we use our K-Ar analyses of circum-Antarctic Quaternary sediment cores to pinpoint potential sediment source areas. Having constrained this glaciation signal, we also present preliminary K-Ar and Sm-Nd analysis of the Campanian-Maastrictian boundary event (69 Ma) at Ocean Drilling Project site 690C to assess the controversial hypothesis of Late Cretaceous glaciation of Antarctica.

Comparing effectiveness of rhamnolipid biosurfactant with a quaternary ammonium salt surfactant for hydrate anti-agglomeration.

PubMed

York, J Dalton; Firoozabadi, Abbas

2008-01-24

Natural gas is projected to be the premium fuel of the 21st century because of availability, as well as economical and environmental considerations. Natural gas is coproduced with water from the subsurface forming gas hydrates. Hydrate formation may result in shutdown of onshore and offshore operations. Industry practice has been usage of alcohols--which have undesirable environmental impacts--to affect bulk-phase properties and inhibit hydrate formation. An alternative to alcohols is changing the surface properties through usage of polymers and surfactants, effective at 0.5-3 wt % of coproduced water. One group of low-dosage hydrate inhibitors (LDHI) are kinetic inhibitors, which affect nucleation rate and growth. A second group of LDHI are anti-agglomerants, which prevent agglomeration of small hydrate crystallites. Despite great potential, reported work on hydrate anti-agglomeration is very limited. In this paper, our focus is on the use of two vastly different surfactants as anti-agglomerants. We use a model oil, water, and tetrahydrofuran as a hydrate-forming species. We examine the effectiveness of a quaternary ammonium salt (i.e., quat). Visual observation measurements show that a small concentration of the quat (0.01%) can prevent agglomeration. However, a quat is not a green chemical and therefore may be undesirable. We show that a rhamnolipid biosurfactant can be effective to a concentration of 0.05 wt %. One difference between the two surfactants is the stability of the water-in-oil emulsions created. The biosurfactant forms a less stable emulsion, which makes it very desirable for hydrate application.

Structure of Respiratory Syncytial Virus Fusion Glycoprotein in the Postfusion Conformation Reveals Preservation of Neutralizing Epitopes

DOE Office of Scientific and Technical Information (OSTI.GOV)

McLellan, Jason S.; Yang, Yongping; Graham, Barney S.

2011-09-16

Respiratory syncytial virus (RSV) invades host cells via a type I fusion (F) glycoprotein that undergoes dramatic structural rearrangements during the fusion process. Neutralizing monoclonal antibodies, such as 101F, palivizumab, and motavizumab, target two major antigenic sites on the RSV F glycoprotein. The structures of these sites as peptide complexes with motavizumab and 101F have been previously determined, but a structure for the trimeric RSV F glycoprotein ectodomain has remained elusive. To address this issue, we undertook structural and biophysical studies on stable ectodomain constructs. Here, we present the 2.8-{angstrom} crystal structure of the trimeric RSV F ectodomain in itsmore » postfusion conformation. The structure revealed that the 101F and motavizumab epitopes are present in the postfusion state and that their conformations are similar to those observed in the antibody-bound peptide structures. Both antibodies bound the postfusion F glycoprotein with high affinity in surface plasmon resonance experiments. Modeling of the antibodies bound to the F glycoprotein predicts that the 101F epitope is larger than the linear peptide and restricted to a single protomer in the trimer, whereas motavizumab likely contacts residues on two protomers, indicating a quaternary epitope. Mechanistically, these results suggest that 101F and motavizumab can bind to multiple conformations of the fusion glycoprotein and can neutralize late in the entry process. The structural preservation of neutralizing epitopes in the postfusion state suggests that this conformation can elicit neutralizing antibodies and serve as a useful vaccine antigen.« less

Thermostable and highly specific L-aspartate oxidase from Thermococcus litoralis DSM 5473: cloning, overexpression, and enzymological properties.

PubMed

Washio, Tsubasa; Oikawa, Tadao

2018-01-01

We successfully expressed the L-aspartate oxidase homolog gene (accession no: OCC_06611) of Thermococcus litoralis DSM 5473 in the soluble fraction of Escherichia coli BL21 (DE3) using a pET21b vector with 6X His tag at its C-terminus. The gene product (Tl-LASPO) showed L-aspartate oxidase activity in the presence of FAD in vitro, and this report is the first that details an L-aspartate oxidase derived from a Thermococcus species. The homologs of Tl-LASPO existed mainly in archaea, especially in the genus of Thermococcus, Pyrococcus, Sulfolobus, and Halobacteria. The quaternary structure of Tl-LASPO was homotrimeric with a subunit molecular mass of 52 kDa. The enzyme activity of Tl-LASPO increased with temperature up to 70 °C. Tl-LASPO was active from pH 6.0 to 9.0, and its highest activity was at pH 8.0. Tl-LASPO was stable at 80 °C for 1 h. The highest k cat /K m value was observed in assays at 70 °C. Tl-LASPO was highly specific for L-aspartic acid. Tl-LASPO utilized fumaric acid, 2,6-dichlorophenolindophenol, and ferricyanide in addition to FAD as a cofactor under anaerobic conditions. The absorption spectrum of holo-Tl-LASPO exhibited maxima at 380 and 450 nm. The FAD dissociation constant, K d , of the FAD-Tl-LASPO complex was determined to be 5.9 × 10 -9 M.

Contrasting patterns of population history and seed-mediated gene flow in two endemic Costa Rican oak species.

PubMed

Rodríguez-Correa, Hernando; Oyama, Ken; Quesada, Mauricio; Fuchs, Eric J; González-Rodríguez, Antonio

2018-03-02

Lower Central America is an important area to study recent population history and diversification of Neotropical species due to its complex and dynamic geology and climate. Phylogeographic studies in this region are few in comparison with other regions and even less for tree species. The aim of the present study was to characterize the phylogeographic structure in two partially co-distributed endemic oak species (Quercus costaricensis and Q. bumelioides) of the Costa Rican mountains using chloroplast short sequence repeats (cpSSRs), and to test for the effect of geological and palaeoclimatic processes on their population history. Genetic diversity and structure, haplotype networks, patterns of seed-mediated gene flow and historical demography were estimated for both species. Results suggested contrasting patterns. Quercus costaricensis exhibited high values of genetic diversity, a marked phylogeographic structure, a north-to-south genetic diversity gradient and evidence of a demographic expansion during the Quaternary. Quercus bumelioides did not show significant genetic structure and the haplotype network and historical demography estimates suggested a recent population expansion probably during the Pleistocene-Holocene transition. Phylogeographic structure of Q. costaricensis seems to be related to Pleistocene altitudinal migration due to its higher altitudinal distribution. Meanwhile, historical seed-mediated gene flow through the lower altitudinal distribution of Q. bumelioides may have promoted the homogenization of genetic variation. Population expansion and stable availability of suitable climatic areas in both species probably indicate that palaeoclimatic changes promoted downwards altitudinal migration and formation of continuous forests allowing oak species to expand their distribution into the Panamanian mountains during glacial stages.

Boundary current-controlled turbidite deposition: A sedimentation model for the Southern Nares Abyssal Plain, Western North Atlantic

NASA Astrophysics Data System (ADS)

Kuijpers, A.; Duin, E. J. Th.

1986-03-01

Examination of 38 sediment cores, bottom photographs, 7,000 km of 3.5 kHz reflection profiles and other seismic data from the southern part of the Nares Abyssal Plain suggests that complex sedimentary patterns and high sedimentation rates can be largely attributed to effects of a deep boundary current flowing eastward along the north flank of the Greater Antilles Outer Ridge. It is concluded that the areal dispersal pattern of turbidites on the plain results mainly from Quaternary climatically-induced fluctuations of the boundary current intensity.

Novel Optical Fiber Materials With Engineered Brillouin Gain Coefficients SSL 1: Novel Fiber Lasers

DTIC Science & Technology

2015-12-29

strontium aluminosilicate glasses . A zero-p12 composition is calculated to be at a SiO2 content of about 41.5 mol%, SrO content of about 22.5 mol...ternary, glasses that are needed for this program. These include the BaO- SiO2 system as an example binary glass , and the MgO-Al2O3- SiO2 and BaO-Al2O3... SiO2 systems as example ternary glasses (with the addition of a rare earth 16 resulting in a quaternary glass ). Complex ternary compositions were

SEPARATION OF INORGANIC SALTS FROM ORGANIC SOLUTIONS

DOEpatents

Katzin, L.I.; Sullivan, J.C.

1958-06-24

A process is described for recovering the nitrates of uranium and plutonium from solution in oxygen-containing organic solvents such as ketones or ethers. The solution of such salts dissolved in an oxygen-containing organic compound is contacted with an ion exchange resin whereby sorption of the entire salt on the resin takes place and then the salt-depleted liquid and the resin are separated from each other. The reaction seems to be based on an anion formation of the entire salt by complexing with the anion of the resin. Strong base or quaternary ammonium type resins can be used successfully in this process.

Minimal erosion of Arctic alpine topography during late Quaternary glaciation

NASA Astrophysics Data System (ADS)

Gjermundsen, Endre F.; Briner, Jason P.; Akçar, Naki; Foros, Jørn; Kubik, Peter W.; Salvigsen, Otto; Hormes, Anne

2015-10-01

The alpine topography observed in many mountainous regions is thought to have formed during repeated glaciations of the Quaternary period. Before this time, landscapes had much less relief. However, the spatial patterns and rates of Quaternary exhumation at high latitudes--where cold-based glaciers may protect rather than erode landscapes--are not fully quantified. Here we determine the exposure and burial histories of rock samples from eight summits of steep alpine peaks in northwestern Svalbard (79.5° N) using analyses of 10Be and 26Al concentrations. We find that the summits have been preserved for at least the past one million years. The antiquity of Svalbard’s alpine landscape is supported by the preservation of sediments older than one million years along a fjord valley, which suggests that both mountain summits and low-elevation landscapes experienced very low erosion rates over the past million years. Our findings support the establishment of northwestern Svalbard’s alpine topography during the early Quaternary. We suggest that, as the Quaternary ice age progressed, glacial erosion in the Arctic became inefficient and confined to ice streams, and high-relief alpine landscapes were preserved by minimally erosive glacier armour.

The influence of climate on species distribution over time and space during the late Quaternary

NASA Astrophysics Data System (ADS)

Carotenuto, F.; Di Febbraro, M.; Melchionna, M.; Castiglione, S.; Saggese, F.; Serio, C.; Mondanaro, A.; Passaro, F.; Loy, A.; Raia, P.

2016-10-01

Understanding the effect of climate on the composition of communities and its change over time and space is one of the major aims in ecology and paleoecology. Herein, we tackled on this issue by studying late Quaternary large mammal paleocommunities of Eurasia. The late Quaternary was a period of strong environmental instability, especially characterized by the occurrence of the last glacial maximum (LGM). We used community phylogenetics and joint species distribution models in order to understand the factors determining paleocommunity composition in the late Quaternary. Our results support the existence of strong climatic selection operating on the LGM fauna, both through the disappearance of warm-adapted species such as Elephas antiquus, Hippopothamus amphibious, and Stephanorhinus hemitoechus, and by setting the stage for the existence of a community characterized by cold-adapted large mammals. Patterns of abundance in the fossil record, co-occurrence between species pairs, and the extent of climatic forcing on faunal composition, differ between paleocommunities, but not between extinct and extant species, which is consistent with the idea that climate change, rather than the presence of humans, exerted a major effect on the survival of the late Quaternary megafauna.

Analysis of residual products in triethylbenzylammonium chloride by HPLC. Study of the retention mechanism.

PubMed

Prieto-Blanco, M C; López-Mahía, P; Prada-Rodríguez, D

2006-04-01

The control of industrial products for minimization of their impact on the environment and human health requires the development of specific analysis methods. Information provided by these methods about toxic components, by-products, and other derivatives may also be useful to reduce the possible impact of industrial products. The studied compound in this paper, triethylbenzylammonium chloride (TEBA), is mainly used in industrial synthesis. This quaternary compound and its residual products coming from quaternization reaction (benzyl chloride, benzaldehyde, and benzyl alcohol) are analyzed by HPLC. The separation is based on control of the silanophilic contribution to TEBA retention because of the quaternary nature of this compound. The effect of the three buffers (sodium acetate, ammonium acetate, and sodium formate) and their concentrations in the chromatographic behavior of the quaternary compound is examined. The buffer cation and anion regulate TEBA retention. Also, the concentration of the quaternary compound is another parameter that had influence in some aspects of its chromatographic behavior (e.g., retention and symmetry). The proposed method is applied to TEBA synthesis along, with the formation and removal of impurities with the results compared with those obtained for the quaternary compound benzalkonium chloride.

A Systematic Investigation of Quaternary Ammonium Ions as Asymmetric Phase Transfer Catalysts. Synthesis of Catalyst Libraries and Evaluation of Catalyst Activity

PubMed Central

Denmark, Scott E.; Gould, Nathan D.; Wolf, Larry M.

2011-01-01

Despite over three decades of research into asymmetric phase transfer catalysis (APTC), a fundamental understanding of the factors that affect the rate and stereoselectivity of this important process are still obscure. This paper describes the initial stages of a long-term program aimed at elucidating the physical organic foundations of APTC employing a chemoinformatic analysis of the alkylation of a protected glycine imine with a libraries of enantiomerically enriched quaternary ammonium ions. The synthesis of the quaternary ammonium ions follows a diversity oriented approach wherein the tandem inter[4+2]/intra[3+2] cycloaddition of nitroalkenes serves as the key transformation. A two part synthetic strategy comprised of: (1) preparation of enantioenriched scaffolds and (2) development of parallel synthesis procedures is described. The strategy allows for the facile introduction of four variable groups in the vicinity of a stereogenic quaternary ammonium ion. The quaternary ammonium ions exhibited a wide range of activity and to a lesser degree enantioselectivity. Catalyst activity and selectivity are rationalized in a qualitative way based on the effective positive potential of the ammonium ion. PMID:21446721

Bactericidal Specificity and Resistance Profile of Poly(Quaternary Ammonium) Polymers and Protein-Poly(Quaternary Ammonium) Conjugates.

PubMed

Ji, Weihang; Koepsel, Richard R; Murata, Hironobu; Zadan, Sawyer; Campbell, Alan S; Russell, Alan J

2017-08-14

Antibacterial polymers are potentially powerful biocides that can destroy bacteria on contact. Debate in the literature has surrounded the mechanism of action of polymeric biocides and the propensity for bacteria to develop resistance to them. There has been particular interest in whether surfaces with covalently coupled polymeric biocides have the same mechanism of action and resistance profile as similar soluble polymeric biocides. We designed and synthesized a series of poly(quaternary ammonium) polymers, with tailorable molecular structures and architectures, to engineer their antibacterial specificity and their ability to delay the development of bacterial resistance. These linear poly(quaternary ammonium) homopolymers and block copolymers, generated using atom transfer radical polymerization, had structure-dependent antibacterial specificity toward Gram positive and negative bacterial species. When single block copolymers contained two polymer segments of differing antibacterial specificity, the polymer combined the specificities of its two components. Nanoparticulate human serum albumin-poly(quaternary ammonium) conjugates of these same polymers, synthesized via "grafting from" atom transfer radical polymerization, were strongly biocidal and also exhibited a marked decrease in the rate of bacterial resistance development relative to linear polymers. These protein-biocide conjugates mimicked the behavior of surface-presented polycationic biocides rather than their nonproteinaceous counterparts.

Latest Pannonian and Quaternary evolution at the transition between Eastern Alps and Pannonian Basin: new insights from geophysical, sedimentological and geochronological data

NASA Astrophysics Data System (ADS)

Zámolyi, A.; Salcher, B.; Draganits, E.; Exner, U.; Wagreich, M.; Gier, S.; Fiebig, M.; Lomax, J.; Surányi, G.; Diel, M.; Zámolyi, F.

2017-07-01

The transition zone between Eastern Alps and Pannonian Basin is a key area for the investigation of the interplay between regional uplift, local tectonic subsidence and depositional environment. Our study area, the western margin of the Little Hungarian Plain, is characterized by gentle hills, plateaus and depressions, of which several are filled by lakes—including one of Austria's largest and shallowest lakes, Lake Neusiedl. Geological investigation is hampered by the scarcity of outcrops, and thus direct observation of sedimentological or structural features is difficult. Despite a long research history in the area, a consistent landscape evolution model considering all relevant constraints is lacking so far. In this study, we apply multidisciplinary methods to decipher the complex tectonic and fluvial depositional evolution of the region. Local data from shallow-lake drilling and seismic investigation are combined with regional data from industrial seismics and core data to gain new insights into the latest Pannonian (Late Miocene) and Quaternary evolution. Shallow-lake seismic data show the erosionally truncated Pannonian sediments dipping and thickening toward southeast, toward the modern depocenter of the Little Hungarian Plain. Overlying Quaternary fluvial sediments show a very similar thickening trend except for the area on the plateau north of the lake indicating ongoing subsidence in major parts of the basin. Drill cores from locations along the lake seismic lines were analyzed concerning their age, mineralogy and heavy minerals and compared with outcrop samples from the surrounding plains and the plateau to derive indications on sediment provenance. A key observation is the apparent lack of a significant gravel layer on top of the tilted Pannonian sediments beneath Lake Neusiedl. Small-scale faults can be observed in the lake seismic sections along with key sedimentary features. Significant differences of the current elevation of the top Pannonian between the surrounding plains and the plateau indicate post-Pannonian normal faulting, which is a key process in shaping the present-day morphology of the region. Luminescence ages of samples from the Quaternary fluvial gravels on top of the Pannonian sediments are a significantly higher (>300 ka) compared to the gravels in the plain (102 ± 11 and 76 ± 8 ka), suggesting ongoing tectonic subsidence.

Micropaleontologic record of late Pliocene and Quaternary paleoenvironments in the northern Albemarle Embayment, North Carolina, U.S.A.

USGS Publications Warehouse

Culver, S.J.; Farrell, K.M.; Mallinson, D.J.; Horton, B.P.; Willard, D.A.; Thieler, E.R.; Riggs, S.R.; Snyder, S.W.; Wehmiller, J.F.; Bernhardt, C.E.; Hillier, C.

2008-01-01

Micropaleontological data provide a strong actualistic basis for detailed interpretations of Quaternary paleoenvironmental change. The 90??m-thick Quaternary record of the Albemarle Embayment in the mid-Atlantic coastal plain of the USA provides an excellent opportunity to use such an approach in a region where the details of Quaternary environmental change are poorly known. The foraminiferal record in nine cores from the northern Outer Banks, east of Albemarle Sound, North Carolina, indicates the deposition of subhorizontal, mostly open-marine early to late Pleistocene units unconformably upon a basement of late Pliocene reduced-oxygen, fine-grained, shelf-basin deposits. Pollen data record several warm-cool fluctuations within the early to mid-Pleistocene deposits. Diatom data indicate that some fresh and brackish-water units occur within the generally open-marine Pleistocene succession. A channel cut by the paleo-Roanoke River during the last glacial sea-level lowstand occurs in the northern part of the study area. Pollen indicates that the basal fluvial valley fill accumulated in cooler than modern climate conditions in the latest Pleistocene. Overlying silts and muds accumulated under cool climatic, estuarine conditions according to diatom and pollen data. Radiocarbon ages from the estuarine deposits indicate that the bulk of these sediments accumulated during the latest Pleistocene. The estuarine channel-fill deposits are overlain by Holocene open-marine sands deposited as the rising sea transgressed into the estuary approximately 8.5 to 9.0??kyr BP. Within the barrier island drill cores of this study, fully marine sedimentation occurred throughout the Holocene. However, immediately west of the present barrier island, mid- to late Holocene estuarine deposits underlie the modern Albemarle Sound. The islands that currently form a continuous barrier across the mouth of Albemarle Sound have a complex history of Holocene construction and destruction and large portions of them may be less than 3??kyr old. The barrier island sands overlie open-marine sands of Colington Shoal in the north and to the south overlie fluvial and marine sand filling paleo-Roanoke tributary valleys. The Pleistocene sediments underlying the northern Outer Banks study area are mainly of open inner to mid-shelf origin. If, as is likely, sea level continues to rise, a return to such environmental conditions is likely in the near future. ?? 2008 Elsevier B.V.

Quantum chemical studies on hypothetical Fischer type Mo(CO)5[C(OEt)Me] and Mo(CO)5[C(OMe)Et] carbene complexes

NASA Astrophysics Data System (ADS)

Gövdeli, Nezafet; Karakaş, Duran

2018-07-01

Quantum chemical calculations at B3LYP/LANL2DZ/6-31G(d) level were made on anti-eclipsed, anti-staggered, syn-eclipsed, syn-staggered conformers of hypothetical Fischer type Mo(CO)5[C(OEt)Me] and Mo(CO)5[C(OMe)Et] carbene complexes in the gas phase. The most stable conformer of the complexes was found to be anti-staggered according to the total energy values calculated at given level. Structural parameters, vibration spectra, charge distributions, molecular orbital energy diagrams, contour diagrams of frontier orbitals, molecular electrostatic potential maps and some electronic structure descriptors were obtained for the most stable conformers. NMR spectra of the most stable conformers were calculated at GIAO/B3LYP/LANL2DZ level. The most stable conformer geometry was found to be distorted octahedral. IR and NMR spectra of the complexes are consistent with their geometry. HOMOs of the complexes were found to be center-atomic character and LUMOs were carbene-carbon character. From the calculated charge analysis and molecular electrostatic potential maps, it is found that carbene-carbon acts as electrofil and metal center nucleophile. It is suggested that the catalytic properties of the carbene complexes may be due to the fact that the carbene-carbon behave as electrophile and metal center nucleophile. Some electronic structure descriptors of the complexes were calculated and the molecular properties were estimated.

Binding of 3O2 and 1O2 to dyes used in photodynamic therapy in gas phase and aqueous media

NASA Astrophysics Data System (ADS)

Kushwaha, P. S.; Mishra, P. C.

Density functional theory (DFT) was employed at the B3LYP/6-31+G* level to study complexes of 1O2 and 3O2 with the dye molecules proflavine, methylene blue, and acridine orange, which are useful in photodynamic therapy. It was found that the most stable complex between 1O2 and proflavine are formed when 1O2 is located above the central ring, while the most stable complex between 1O2 and methylene blue is formed when 1O2 is located above the molecular plane, but not above any of the rings, near the sulfur atom. 1O2 can make a stable complex with acridine orange, as it is located above the outer ring of the dye. The binding energies of the complexes of 1O2 with all three dyes are enhanced considerably in going from gas phase to aqueous media. The complexes of 3O2 with the dyes will be unstable in all cases, while those of 1O2 with the same will be quite stable and will not be dissociated due to thermal fluctuations at room temperature. In the complexes of 1O2 and 3O2 with the dyes, charge transfer occurs from the dyes to the O2 moiety, the amount of charge transfer being much more to 1O2 than to 3O2 in each case.

Catalytic Enantioselective Synthesis of Quaternary Carbon Stereocenters

PubMed Central

Quasdorf, Kyle W.; Overman, Larry E.

2015-01-01

Preface Quaternary carbon stereocenters–carbon atoms to which four distinct carbon substituents are attached–are common features of molecules found in nature. However, prior to recent advances in chemical catalysis, there were few methods available for constructing single stereoisomers of this important structural motif. Here we discuss the many catalytic enantioselective reactions developed during the past decade for synthesizing organic molecules containing such carbon atoms. This progress now makes it possible to selectively incorporate quaternary stereocenters in many high-value organic molecules for use in medicine, agriculture, and other areas. PMID:25503231

Thermodynamic Description of the Quaternary Ag-Bi-Cu-Sn System

NASA Astrophysics Data System (ADS)

Gierlotka, Wojciech

2018-01-01

Lead-free soldering is an important part of electronic devices production. New lead-free solders that replace classical Sn-37Pb solder are still under development. Thermodynamic modeling makes the development process faster, cheaper and more environmentally friendly due to predictions of phases stabilities and phases transformations. In this work, the thermodynamic description of quaternary Ag-Bi-Cu-Sn system is presented. The thermodynamic assessment of promising lead-free quaternary solder was prepared using the Calphad approach. A good agreement between available experimental data and calculation was found.

Quaternary ammonium promoted ultra selective and sensitive fluorescence detection of fluoride ion in water and living cells.

PubMed

Li, Long; Ji, Yuzhuo; Tang, Xinjing

2014-10-21

Highly selective and sensitive fluorescent probes with a quaternary ammonium moiety have been rationally designed and developed for fast and sensitive fluorescence detection of fluoride ion (F(-) from NaF, not TBAF) in aqueous solution and living cells. With the sequestration effect of quaternary ammonium, the detection time was less than 2 min and the detection limit of fluoride ion was as low as 0.57 ppm that is among the lowest detection limits in aqueous solutions of many fluoride fluorescence probes in the literature.

Phase behaviour and structure of stable complexes of oppositely charged polyelectrolytes

NASA Astrophysics Data System (ADS)

Mengarelli, V.; Auvray, L.; Zeghal, M.

2009-03-01

We study the formation and structure of stable electrostatic complexes between oppositely charged polyelectrolytes, a long polymethacrylic acid and a shorter polyethylenimine, at low pH, where the polyacid is weakly charged. We explore the phase diagram as a function of the charge and concentration ratio of the constituents. In agreement with theory, turbidity and ζ potential measurements show two distinct regimes of weak and strong complexation, which appear successively as the pH is increased and are separated by a well-defined limit. Weak complexes observed by neutron scattering and contrast matching have an open, non-compact structure, while strong complexes are condensed.

Spatiotemporal analysis of Quaternary normal faults in the Northern Rocky Mountains, USA

NASA Astrophysics Data System (ADS)

Davarpanah, A.; Babaie, H. A.; Reed, P.

2010-12-01

The mid-Tertiary Basin-and-Range extensional tectonic event developed most of the normal faults that bound the ranges in the northern Rocky Mountains within Montana, Wyoming, and Idaho. The interaction of the thermally induced stress field of the Yellowstone hot spot with the existing Basin-and-Range fault blocks, during the last 15 my, has produced a new, spatially and temporally variable system of normal faults in these areas. The orientation and spatial distribution of the trace of these hot-spot induced normal faults, relative to earlier Basin-and-Range faults, have significant implications for the effect of the temporally varying and spatially propagating thermal dome on the growth of new hot spot related normal faults and reactivation of existing Basin-and-Range faults. Digitally enhanced LANDSAT 7 Enhanced Thematic Mapper Plus (ETM+) and Landsat 4 and 5 Thematic Mapper (TM) bands, with spatial resolution of 30 m, combined with analytical GIS and geological techniques helped in determining and analyzing the lineaments and traces of the Quaternary, thermally-induced normal faults in the study area. Applying the color composite (CC) image enhancement technique, the combination of bands 3, 2 and 1 of the ETM+ and TM images was chosen as the best statistical choice to create a color composite for lineament identification. The spatiotemporal analysis of the Quaternary normal faults produces significant information on the structural style, timing, spatial variation, spatial density, and frequency of the faults. The seismic Quaternary normal faults, in the whole study area, are divided, based on their age, into four specific sets, which from oldest to youngest include: Quaternary (>1.6 Ma), middle and late Quaternary (>750 ka), latest Quaternary (>15 ka), and the last 150 years. A density map for the Quaternary faults reveals that most active faults are near the current Yellowstone National Park area (YNP), where most seismically active faults, in the past 1.6 my, are located. The GIS based autocorrelation method, applied to the trace orientation, length, frequency, and spatial distribution for each age-defined fault set, revealed spatial homogeneity for each specific set. The results of the method of Moran`sI and Geary`s C show no spatial autocorrelation among the trend of the fault traces and their location. Our results suggest that while lineaments of similar age define a clustered pattern in each domain, the overall distribution pattern of lineaments with different ages seems to be non-uniform (random). The directional distribution analysis reveals a distinct range of variation for fault traces of different ages (i.e., some displaying ellipsis behavior). Among the Quaternary normal fault sets, the youngest lineament set (i.e., last 150 years) defines the greatest ellipticity (eccentricity) and the least lineaments distribution variation. The frequency rose diagram for the entire Quaternary normal faults, shows four major modes (around 360o, 330o, 300o, and 270o), and two minor modes (around 235 and 205).

Coupling Geophysical, Geotechnical and Stratigraphic Data to Interpret the Genesis of Mega-Scale-Glacial-Lineations on the Yermak Plateau, Arctic Ocean

NASA Astrophysics Data System (ADS)

O'Regan, M. A.; Jakobsson, M.; Kirchner, N.; Dowdeswell, J. A.; Hogan, K.

2010-12-01

The recent collection and analysis of multi-beam bathymetry data has revealed Mega-Scale Glacial Lineations (MSGL) in up to 600 m present water depth on the Yermak Plateau (Dowdeswell et al., 2010; Jakobsson et al., 2010). This evidence for large-scale ice grounding in the region supports previous interpretations from side-scan sonar, high-resolution subbottom and multi-channel seismic data. Detailed integration with regional subbottom data illustrates that the formation of the MSGL occurred in the late Quaternary, around MIS6. This event is distinct from a middle Quaternary ice grounding in the same region, that was first recognized by the transition into heavily overconsolidated sediments at ~20 mbsf at Ocean Drilling Program Site 910. While the middle Quaternary ice grounding left an easily recognizable imprint on the geotechnical properties of the sediments, the imprint from the late Quaternary event is far subtler, and not formerly recognized by analysis of sediments from Site 910. Furthermore, stratigraphic information indicates that neither event was associated with significant erosion, implying that the observed stress state of the sediments arose from ice-loading. Coupled with the orientation of the late Quaternary MSGL, the available evidence argues against an active ice-stream being responsible for their formation, and that they were more likely formed by a very large tabular iceberg traversing the ridge. This lends considerable support to the argument that MSGL-like features are not exclusively associated with fast flowing ice-streams. References Jakobsson, M., et al., An Arctic Ocean iceshelf during MIS 6 constrained by new geophysical and geological data. Quaternary Science Reviews (2010), doi:10.1016/j.quascirev.2010.03.015. Dowdeswell, J. A., et al., High-resolution geophysical observations of the Yermak Plateau and northern Svalbard margin: implications for ice-sheet grounding and deep-keeled icebergs. Quaternary Science Reviews (2010), doi:10.1016/j.quascirev.2010.06.002

Atomic structure of an alphabeta T cell receptor (TCR) heterodimer in complex with an anti-TCR fab fragment derived from a mitogenic antibody.

PubMed Central

Wang, J; Lim, K; Smolyar, A; Teng, M; Liu, J; Tse, A G; Liu, J; Hussey, R E; Chishti, Y; Thomson, C T; Sweet, R M; Nathenson, S G; Chang, H C; Sacchettini, J C; Reinherz, E L

1998-01-01

Each T cell receptor (TCR) recognizes a peptide antigen bound to a major histocompatibility complex (MHC) molecule via a clonotypic alphabeta heterodimeric structure (Ti) non-covalently associated with the monomorphic CD3 signaling components. A crystal structure of an alphabeta TCR-anti-TCR Fab complex shows an Fab fragment derived from the H57 monoclonal antibody (mAb), interacting with the elongated FG loop of the Cbeta domain, situated beneath the Vbeta domain. This loop, along with the partially exposed ABED beta sheet of Cbeta, and glycans attached to both Cbeta and Calpha domains, forms a cavity of sufficient size to accommodate a single non-glycosylated Ig domain such as the CD3epsilon ectodomain. That this asymmetrically localized site is embedded within the rigid constant domain module has implications for the mechanism of signal transduction in both TCR and pre-TCR complexes. Furthermore, quaternary structures of TCRs vary significantly even when they bind the same MHC molecule, as manifested by a unique twisting of the V module relative to the C module. PMID:9427737

Quantifying the assembly of multicomponent molecular machines by single-molecule total internal reflection fluorescence microscopy

PubMed Central

Boehm, Elizabeth M.; Subramanyam, Shyamal; Ghoneim, Mohamed; Washington, M. Todd; Spies, Maria

2016-01-01

Large, dynamic macromolecular complexes play essential roles in many cellular processes. Knowing how the components of these complexes associate with one another and undergo structural rearrangements is critical to understanding how they function. Single-molecule total internal reflection fluorescence (TIRF) microscopy is a powerful approach for addressing these fundamental issues. In this article, we first discuss single-molecule TIRF microscopes and strategies to immobilize and fluorescently label macromolecules. We then review the use of single-molecule TIRF microscopy to study the formation of binary macromolecular complexes using one-color imaging and inhibitors. We conclude with a discussion of the use of TIRF microscopy to examine the formation of higher-order (i.e., ternary, quaternary, etc.) complexes using multi-color setups. The focus throughout this article is on experimental design, controls, data acquisition, and data analysis. We hope that single-molecule TIRF microscopy, which has largely been the province of specialists, will soon become as common in the tool box of biophysicists and biochemists as structural approaches has become today. PMID:27793278

Adding Complex Terrain and Stable Atmospheric Condition Capability to the OpenFOAM-based Flow Solver of the Simulator for On/Offshore Wind Farm Applications (SOWFA): Preprint

DOE Office of Scientific and Technical Information (OSTI.GOV)

Churchfield, M. J.; Sang, L.; Moriarty, P. J.

This paper describes changes made to NREL's OpenFOAM-based wind plant aerodynamics solver such that it can compute the stably stratified atmospheric boundary layer and flow over terrain. Background about the flow solver, the Simulator for Off/Onshore Wind Farm Applications (SOWFA) is given, followed by details of the stable stratification/complex terrain modifications to SOWFA, along with somepreliminary results calculations of a stable atmospheric boundary layer and flow over a simply set of hills.

Adding Complex Terrain and Stable Atmospheric Condition Capability to the Simulator for On/Offshore Wind Farm Applications (SOWFA) (Presentation)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Churchfield, M. J.

This presentation describes changes made to NREL's OpenFOAM-based wind plant aerodynamics solver so that it can compute the stably stratified atmospheric boundary layer and flow over terrain. Background about the flow solver, the Simulator for Off/Onshore Wind Farm Applications (SOWFA) is given, followed by details of the stable stratification/complex terrain modifications to SOWFA, along with some preliminary results calculations of a stable atmospheric boundary layer and flow over a simple set of hills.

Map and data for Quaternary faults and folds in Washington state

USGS Publications Warehouse

Lidke, David J.; Johnson, Samuel Y.; McCrory, Patricia A.; Personius, Stephen F.; Nelson, Alan R.; Dart, Richard L.; Bradley, Lee-Ann; Haller, Kathleen M.; Machette, Michael N.

2004-01-01

The map shows faults and folds in Washington State that exhibit evidence of Quaternary deformation and includes data on timing of most recent movement, sense of movement, slip rate, and continuity of surface expression.

A solution-processed quaternary oxide system obtained at low-temperature using a vertical diffusion technique

PubMed Central

Yoon, Seokhyun; Kim, Si Joon; Tak, Young Jun; Kim, Hyun Jae

2017-01-01

We report a method for fabricating solution-processed quaternary In-Ga-Zn-O (IGZO) thin-film transistors (TFTs) at low annealing temperatures using a vertical diffusion technique (VDT). The VDT is a deposition process for spin-coating binary and ternary oxide layers consecutively and annealing at once. With the VDT, uniform and dense quaternary oxide layers were fabricated at lower temperatures (280 °C). Compared to conventional IGZO and ternary In-Zn-O (IZO) thin films, VDT IGZO thin film had higher density of the metal-oxide bonds and lower density of the oxygen vacancies. The field-effect mobility of VDT IGZO TFT increased three times with an improved stability under positive bias stress than IZO TFT due to the reduction in oxygen vacancies. Therefore, the VDT process is a simple method that reduces the processing temperature without any additional treatment for quaternary oxide semiconductors with uniform layers. PMID:28230088

A solution-processed quaternary oxide system obtained at low-temperature using a vertical diffusion technique

NASA Astrophysics Data System (ADS)

Yoon, Seokhyun; Kim, Si Joon; Tak, Young Jun; Kim, Hyun Jae

2017-02-01

We report a method for fabricating solution-processed quaternary In-Ga-Zn-O (IGZO) thin-film transistors (TFTs) at low annealing temperatures using a vertical diffusion technique (VDT). The VDT is a deposition process for spin-coating binary and ternary oxide layers consecutively and annealing at once. With the VDT, uniform and dense quaternary oxide layers were fabricated at lower temperatures (280 °C). Compared to conventional IGZO and ternary In-Zn-O (IZO) thin films, VDT IGZO thin film had higher density of the metal-oxide bonds and lower density of the oxygen vacancies. The field-effect mobility of VDT IGZO TFT increased three times with an improved stability under positive bias stress than IZO TFT due to the reduction in oxygen vacancies. Therefore, the VDT process is a simple method that reduces the processing temperature without any additional treatment for quaternary oxide semiconductors with uniform layers.

Mössbauer and XRD study of novel quaternary Sn-Fe-Co-Ni electroplated alloy

NASA Astrophysics Data System (ADS)

Kuzmann, E.; Sziráki, L.; Stichleutner, S.; Homonnay, Z.; Lak, G. B.; El-Sharif, M.; Chisholm, C. U.

2017-11-01

Constant current electrochemical deposition technique was used to obtain quaternary alloys of Sn-Fe-Co-Ni from a gluconate electrolyte, which to date have not been reported in the literature. For the characterization of electroplated alloys, 57Fe and 119Sn Conversion Electron Mössbauer Spectroscopy (CEMS), XRD and SEM/EDAX were used. XRD revealed the amorphous character of the novel Sn-Fe-Co-Ni electrodeposited alloys. 57Fe Mössbauer spectrum of quaternary deposit with composition of 37.0 at% Sn, 38.8 at% Fe, 16.8 at% Co and 7.4 at% Ni displayed a magnetically split sextet (B = 28.9T) with broad lines typical of iron bearing ferromagnetic amorphous alloys. Magnetically split 119Sn spectra reflecting a transferred hyperfine field (B = 2.3T) were also observed. New quaternary Sn-Fe-Co-Ni alloys were successfully prepared.

A solution-processed quaternary oxide system obtained at low-temperature using a vertical diffusion technique.

PubMed

Yoon, Seokhyun; Kim, Si Joon; Tak, Young Jun; Kim, Hyun Jae

2017-02-23

We report a method for fabricating solution-processed quaternary In-Ga-Zn-O (IGZO) thin-film transistors (TFTs) at low annealing temperatures using a vertical diffusion technique (VDT). The VDT is a deposition process for spin-coating binary and ternary oxide layers consecutively and annealing at once. With the VDT, uniform and dense quaternary oxide layers were fabricated at lower temperatures (280 °C). Compared to conventional IGZO and ternary In-Zn-O (IZO) thin films, VDT IGZO thin film had higher density of the metal-oxide bonds and lower density of the oxygen vacancies. The field-effect mobility of VDT IGZO TFT increased three times with an improved stability under positive bias stress than IZO TFT due to the reduction in oxygen vacancies. Therefore, the VDT process is a simple method that reduces the processing temperature without any additional treatment for quaternary oxide semiconductors with uniform layers.

Tertiary and Quaternary Research with Remote Sensing Methods

NASA Technical Reports Server (NTRS)

Conel, J. E.

1985-01-01

Problems encountered in mapping the Quaternary section of the Wind River Region using remote sensing methods are discussed. Analysis of the stratigraphic section is a fundamental aspect of the geologic study of sedimentary basins. Stratigraphic analysis of post-Cretaceous rocks in the Wind River Basin encounters problems of a distinctly different character from those involved in studying the pre-Cretaceous section. The interior of the basin is predominantly covered by Tertiary and Quaternary sediments. These rocks, except on the basin margin to the north, are mostly flat lying or gently dipping. The Tertiary section consists of sandstones, siltstones, and tuffaceous sediments, some variegated, but in general poorly bedded and of great lithologic similarity. The Quaternary sediments consist of terrace, fan, and debris tongue deposits, unconsolidated alluvium occupying the bottoms of modern watercourses, deposits of eolian origin and tufa. Terrace and fan deposits are compositionally diverse and reflect the lithologic diversity of the source terranes.

Bottom-up construction of a superstructure in a porous uranium-organic crystal

NASA Astrophysics Data System (ADS)

Li, Peng; Vermeulen, Nicolaas A.; Malliakas, Christos D.; Gómez-Gualdrón, Diego A.; Howarth, Ashlee J.; Mehdi, B. Layla; Dohnalkova, Alice; Browning, Nigel D.; O'Keeffe, Michael; Farha, Omar K.

2017-05-01

Bottom-up construction of highly intricate structures from simple building blocks remains one of the most difficult challenges in chemistry. We report a structurally complex, mesoporous uranium-based metal-organic framework (MOF) made from simple starting components. The structure comprises 10 uranium nodes and seven tricarboxylate ligands (both crystallographically nonequivalent), resulting in a 173.3-angstrom cubic unit cell enclosing 816 uranium nodes and 816 organic linkers—the largest unit cell found to date for any nonbiological material. The cuboctahedra organize into pentagonal and hexagonal prismatic secondary structures, which then form tetrahedral and diamond quaternary topologies with unprecedented complexity. This packing results in the formation of colossal icosidodecahedral and rectified hexakaidecahedral cavities with internal diameters of 5.0 nanometers and 6.2 nanometers, respectively—ultimately giving rise to the lowest-density MOF reported to date.

Symmetric and Asymmetric Tendencies in Stable Complex Systems

PubMed Central

Tan, James P. L.

2016-01-01

A commonly used approach to study stability in a complex system is by analyzing the Jacobian matrix at an equilibrium point of a dynamical system. The equilibrium point is stable if all eigenvalues have negative real parts. Here, by obtaining eigenvalue bounds of the Jacobian, we show that stable complex systems will favor mutualistic and competitive relationships that are asymmetrical (non-reciprocative) and trophic relationships that are symmetrical (reciprocative). Additionally, we define a measure called the interdependence diversity that quantifies how distributed the dependencies are between the dynamical variables in the system. We find that increasing interdependence diversity has a destabilizing effect on the equilibrium point, and the effect is greater for trophic relationships than for mutualistic and competitive relationships. These predictions are consistent with empirical observations in ecology. More importantly, our findings suggest stabilization algorithms that can apply very generally to a variety of complex systems. PMID:27545722

Symmetric and Asymmetric Tendencies in Stable Complex Systems.

PubMed

Tan, James P L

2016-08-22

A commonly used approach to study stability in a complex system is by analyzing the Jacobian matrix at an equilibrium point of a dynamical system. The equilibrium point is stable if all eigenvalues have negative real parts. Here, by obtaining eigenvalue bounds of the Jacobian, we show that stable complex systems will favor mutualistic and competitive relationships that are asymmetrical (non-reciprocative) and trophic relationships that are symmetrical (reciprocative). Additionally, we define a measure called the interdependence diversity that quantifies how distributed the dependencies are between the dynamical variables in the system. We find that increasing interdependence diversity has a destabilizing effect on the equilibrium point, and the effect is greater for trophic relationships than for mutualistic and competitive relationships. These predictions are consistent with empirical observations in ecology. More importantly, our findings suggest stabilization algorithms that can apply very generally to a variety of complex systems.

Some modification of cellulose nanocrystals for functional Pickering emulsions

PubMed Central

Saidane, Dorra; Perrin, Emilie; Cherhal, Fanch; Guellec, Florian

2016-01-01

Cellulose nanocrystals (CNCs) are negatively charged colloidal particles well known to form highly stable surfactant-free Pickering emulsions. These particles can vary in surface charge density depending on their preparation by acid hydrolysis or applying post-treatments. CNCs with three different surface charge densities were prepared corresponding to 0.08, 0.16 and 0.64 e nm−2, respectively. Post-treatment might also increase the surface charge density. The well-known TEMPO-mediated oxidation substitutes C6-hydroxyl groups by C6-carboxyl groups on the surface. We report that these different modified CNCs lead to stable oil-in-water emulsions. TEMPO-oxidized CNC might be the basis of further modifications. It is shown that they can, for example, lead to hydrophobic CNCs with a simple method using quaternary ammonium salts that allow producing inverse water-in-oil emulsions. Different from CNC modification before emulsification, modification can be carried out on the droplets after emulsification. This way allows preparing functional capsules according to the layer-by-layer process. As a result, it is demonstrated here the large range of use of these biobased rod-like nanoparticles, extending therefore their potential use to highly sophisticated formulations. This article is part of the themed issue ‘Soft interfacial materials: from fundamentals to formulation’. PMID:27298429

River-damming, late-Quaternary rockslides in the Ötz Valley region (Tyrol, Austria)

NASA Astrophysics Data System (ADS)

Dufresne, A.; Ostermann, M.; Preusser, F.

2018-06-01

The Ötz Valley and adjacent regions in Tyrol (Austria) have been repeatedly affected by large rockslope failures following deglaciation. Six rockslides, each over 107 m3 in volume, were emplaced into the Ötz and Inn valleys, five of which formed persistent rockslide dams. Even though catastrophic rockslope failures are short-lived events (commonly minutes) they can have long-lasting impacts on the landscape. For example, large fans have built in the Ötz Valley and knickpoints persist at the former dam sites even though the Ötz River has eroded through the deposits during the past thousands of years; exact age-constraints of rockslide dam failure, however, are still scarce. Empirical, geomorphic stability indices from the literature successfully identified the least and the most stable dams of this group, whereas the rest remain inconclusive with some indices variably placing the dams in the stable, unstable, and uncertain categories. This shows (a) that further index calibrations and (b) better age constraints on dam formation and failure are needed, and (c) that the exact processes of dam failure are not always trivial to pinpoint for ancient (partially) breached dams. This study is a contribution towards better constraining the nature and landscape impact of dam formation following large rockslope failures.

Multi-functional magnetic water purifier for disinfection and removal of dyes and metal ions with superior reusability.

PubMed

Wu, Yao; Chen, Lei; Long, Xuwei; Zhang, Xiaolin; Pan, Bingcai; Qian, Jieshu

2018-04-05

It is of great practical importance but rarely reported to design a multifunctional scavenger for water purification. In this study, we describe a sophisticated preparation of an inorganic/organic composite sample for the simultaneous removal of anionic dyes and metal ions, as well as disinfection. The sample has a stable structure formed by the covalent connection between a magnetic silica (MS) core and a polyethylenimine derived quaternary ammonium compound (QAC) corona. We characterized the sample in details by SEM, TEM, EDX, FT-IR, XRD, TGA, VSM, and zeta potential. Our QAC-MS sample exhibited superior performance and reusability in the disinfection and adsorption experiments towards acid fuchsin and Cu 2+ . With the virtue of easy separation from solution, our sample should be an ideal candidate for water purification application. Copyright © 2017 Elsevier B.V. All rights reserved.

Matrix- and tensor-based recommender systems for the discovery of currently unknown inorganic compounds

NASA Astrophysics Data System (ADS)

Seko, Atsuto; Hayashi, Hiroyuki; Kashima, Hisashi; Tanaka, Isao

2018-01-01

Chemically relevant compositions (CRCs) and atomic arrangements of inorganic compounds have been collected as inorganic crystal structure databases. Machine learning is a unique approach to search for currently unknown CRCs from vast candidates. Herein we propose matrix- and tensor-based recommender system approaches to predict currently unknown CRCs from database entries of CRCs. Firstly, the performance of the recommender system approaches to discover currently unknown CRCs is examined. A Tucker decomposition recommender system shows the best discovery rate of CRCs as the majority of the top 100 recommended ternary and quaternary compositions correspond to CRCs. Secondly, systematic density functional theory (DFT) calculations are performed to investigate the phase stability of the recommended compositions. The phase stability of the 27 compositions reveals that 23 currently unknown compounds are newly found to be stable. These results indicate that the recommender system has great potential to accelerate the discovery of new compounds.

Effect of on-site Coulomb interaction on electronic and transport properties of 100% spin polarized CoMnVAs

NASA Astrophysics Data System (ADS)

Bhat, Tahir Mohiuddin; Gupta, Dinesh C.

2017-08-01

The structural, electronic, magnetic and transport properties of a new quaternary Heusler alloy CoMnVAs have been investigated by employing generalized gradient approximation (GGA), modified Becke-Johnson (mBJ) and GGA with Hubbard U correction (GGA + U). The alloy is energetically more stable in ferromagnetic Y1 type structure. Elastic parameters reveal high anisotropy and ductile nature of the material. CoMnVAs shows half-metallic ferromagnet character with 100% spin polarization at Fermi level with band gap of 0.55 eV in the minority spin state. The alloy also possesses high electrical conductivity and Seebeck coefficients with 15 μVK-1 at room temperature, achieving a figure of merit of 0.65 at high temperatures. The high degree of ductility, 100% spin polarization and large Seebeck coefficient, makes it an attractive candidate to be used in spin voltage generators and thermoelectric materials.

Crosslinked anion exchange membranes prepared from poly(phenylene oxide) (PPO) for non-aqueous redox flow batteries

NASA Astrophysics Data System (ADS)

Li, Yun; Sniekers, Jeroen; Malaquias, João C.; Van Goethem, Cedric; Binnemans, Koen; Fransaer, Jan; Vankelecom, Ivo F. J.

2018-02-01

A stable and eco-friendly anion-exchange membrane (AEM) was prepared and applied in a non-aqueous all-copper redox flow battery (RFB). The AEM was prepared via a simple procedure, leading to a cross-linked structure containing quaternary ammonium groups without involvement of harmful trimethylamine. A network was thus constructed which ensured both ion transport and solvent resistance. The ion exchange capacity (IEC) of the membrane was tuned from 0.49 to 1.03 meq g-1 by varying the content of the 4, 4‧-bipyridine crosslinking agent. The membrane showed a good anion conductivity and retention of copper ions. As a proof of principle, a RFB single cell with this crosslinked membrane yielded a coulombic efficiency of 89%, a voltage efficiency of 61% and an energy efficiency of 54% at 7.5 mA cm-2.

Limitations on Inferring 3D Architecture and Dynamics From Surface Velocities in the India-Eurasia Collision Zone

NASA Astrophysics Data System (ADS)

Flesch, L.; Bendick, R.; Bischoff, S.

2018-02-01

Surface velocities derived from Global Positioning System observations and Quaternary fault slip rates measured throughout an extended region of high topography in South Asia vary smoothly over thousands of kilometers and are broadly symmetrical, with components of both north-south shortening and east-west extension relative to stable Eurasia. The observed velocity field does not contain discontinuities or steep gradients attributable to along-strike differences in collision architecture, despite the well-documented presence of a lithospheric slab beneath the Pamir but not the Tibetan Plateau. We use a modified Akaike information criterion (AICc) to show that surface velocities do not efficiently constrain 3D rheology, geometry, or force balance. Therefore, although other geophysical and geological observations may indicate the presence of mechanical or dynamic heterogeneities within the Indian-Asian collision, the surface Global Positioning System velocities contain little or no usable information about them.

Designing cooperatively folded abiotic uni- and multimolecular helix bundles

NASA Astrophysics Data System (ADS)

de, Soumen; Chi, Bo; Granier, Thierry; Qi, Ting; Maurizot, Victor; Huc, Ivan

2018-01-01

Abiotic foldamers, that is foldamers that have backbones chemically remote from peptidic and nucleotidic skeletons, may give access to shapes and functions different to those of peptides and nucleotides. However, design methodologies towards abiotic tertiary and quaternary structures are yet to be developed. Here we report rationally designed interactional patterns to guide the folding and assembly of abiotic helix bundles. Computational design facilitated the introduction of hydrogen-bonding functionalities at defined locations on the aromatic amide backbones that promote cooperative folding into helix-turn-helix motifs in organic solvents. The hydrogen-bond-directed aggregation of helices not linked by a turn unit produced several thermodynamically and kinetically stable homochiral dimeric and trimeric bundles with structures that are distinct from the designed helix-turn-helix. Relative helix orientation within the bundles may be changed from parallel to tilted on subtle solvent variations. Altogether, these results prefigure the richness and uniqueness of abiotic tertiary structure behaviour.

{13C }/{12C } ratios of pleistocene mummified remains from beringia

NASA Astrophysics Data System (ADS)

Bombin, Miguel; Muehlenbachs, Karlis

1985-01-01

During the Quaternary glacial episodes, when sea level was considerably lower, Asia and North America were linked by large extensions of circumarctic land (Beringia), which remained unglaciated. This land mass served not only as a biogeographical bridge for plants, animals, and humans, but also supported a biome very different from present tundra or boreal coniferous forests, which was dominated by steppes and a rich mammalian megafauna. Carbon stable isotope ratios of Beringian late Pleistocene mummified remains of bison, equids, mammoth, caribou, musk-ox, moose, woolly rhino, and other undetermined species, found preserved in permafrost, indicate that these megaherbivores fed exclusively on C 3 plants, and that C 4 grasses were not differentially ingested by bison, as previously suggested. Paleoclimatic constraints probably prevented the formation of a warm-season (C 4) guild during the later part of the growing season in the steppes of Beringia during the last glaciation.

Missing in Action? Evaluating the Putative Absence of Impacts by Large Asteroids and Comets during the Quaternary Period

NASA Astrophysics Data System (ADS)

Masse, W.; Weaver, R.; Abbott, D.; Gusiakov, V.; Bryant, E.

The Quaternary period represents the interval of oscillating climatic extremes (glacial and interglacial periods) beginning about 2.6 million years ago to the present. Based on modeling by the Near Earth Object (NEO) community of planetary scientists, the known and validated record of Quaternary impact on Earth by comets and asteroids is seemingly depauperate in terms of larger impactors of 10,000+ Mt (roughly equal to or larger than about 500 m in diameter). Modeling suggests that an average of between 2-3 and perhaps as many as 5 globally catastrophic (ca. 1,000,000+ Mt) impacts by asteroids and comets could have occurred on Earth during this period of time, each having catastrophic regional environmental effects and moderate to severe continental and global effects. A slightly larger number of substantive but somewhat less than globally catastrophic impacts in the 10,000-100,000 Mt range would also be predicted to have occurred during the Quaternary. However, databases of validated impact structures on Earth, contain only two examples of Quaternary period impacts in the 10,000-100,000 Mt range (Zhamanshin, Bosumtwi), dating to around a million years ago, while no examples of Quaternary period globally catastrophic impact structures have been yet identified. In addition, all of the 27 validated Quaternary period impact structures are terrestrial--no Quaternary period oceanic impacts have been yet validated. Two likely globally catastrophic probable oceanic impacts events, Eltanin (ca. 1,000,000 Mt at around 2.5 mya), and that associated with the Australasian tektite strewn field (> 1,000,000 Mt at around 0.8 mya), are known due to their debris fields for which craters have not yet been identified and validated. These and the 8-km diameter Bolivian Iturralde candidate impact structure (ca. 10,000 Mt at around 20 kya) round out our list of likely large Quaternary impact structures. This suggests that one or more Quaternary period globally catastrophic impacts and several events in the 10,000-100,000 Mt range occurred in oceanic settings and have not yet been identified. At issue here is the default position of the NEO community that no large impacts have occurred during the past 15,000 years and that there is little evidence for human death by impacts during the past 5000 years of recorded history. This bias, deriving largely from reliance on stochastic models and by selectively ignoring physical, anthropological, and archaeological evidence in support of such impacts, is apparent in the messages being given to the media and general public, and in the general lack of grant support and other assistance to scientists and scholars wishing to conduct fieldwork on impacts that may date to the past 15,000 years. Such a position has a chilling effect on what should otherwise be an important arena of inquiry into the risks and effects of cosmic impact on human society. It potentially limits advancement in our understanding of the recent record and flux of cosmic impact, and diverts attention away from significant research questions such as the possible role of impact in Quaternary period climate change and biological and cultural evolution and process. LA-UR-07-2526.

Quaternary tectonic evolution of the Pamir-Tian Shan convergence zone, Northwest China

NASA Astrophysics Data System (ADS)

Thompson Jobe, Jessica Ann; Li, Tao; Chen, Jie; Burbank, Douglas W.; Bufe, Aaron

2017-12-01

The Pamir-Tian Shan collision zone in the western Tarim Basin, northwest China, formed from rapid and ongoing convergence in response to the Indo-Eurasian collision. The arid landscape preserves suites of fluvial terraces crossing structures active since the late Neogene that create fault and fold scarps recording Quaternary deformation. Using geologic and geomorphic mapping, differential GPS surveys of deformed terraces, and optically stimulated luminescence dating, we create a synthesis of the active structures that delineate the timing, rate, and migration of Quaternary deformation during ongoing convergence. New deformation rates on eight faults and folds, when combined with previous studies, highlight the spatial and temporal patterns of deformation within the Pamir-Tian Shan convergence zone during the Quaternary. Terraces spanning 130 to 8 ka record deformation rates between 0.1 and 5.6 mm/yr on individual structures. In the westernmost Tarim Basin, where the Pamir and Tian Shan are already juxtaposed, the fastest rates occur on actively deforming structures at the interface of the Pamir-Tian Shan orogens. Farther east, as the separation between the Pamir-Tian Shan orogens increases, the deformation has not been concentrated on a single structure, but rather has been concurrently distributed across a zone of faults and folds in the Kashi-Atushi fold-and-thrust belt and along the NE Pamir margin, where shortening rates vary on individual structures during the Quaternary. Although numerous structures accommodate the shortening and the locus of deformation shifts during the Quaternary, the total shortening across the western Tarim Basin has remained steady and approximately matches the current geodetic rate of 6-9 mm/yr.

Diversification dynamics, species sorting, and changes in the functional diversity of marine benthic gastropods during the Pliocene-Quaternary at temperate western South America.

PubMed

Rivadeneira, Marcelo M; Nielsen, Sven N

2017-01-01

Functional diversity based on species traits is a powerful tool to investigate how changes in species richness and composition affect ecosystem functioning. However, studies aimed at understanding changes in functional diversity over large temporal and spatial scales are still scant. Here we evaluate the combined effect of diversification and species sorting on functional diversity of fossil marine gastropods during the Pliocene-Quaternary transition in the Pacific coast of South America. We analyzed a total of 172 species in 29 Pliocene and 97 Quaternary sites. Each species was characterized according to six functional traits: body size, feeding type, mobility, attachment, life-habit, and larval mode. Functional diversity was estimated according to four indexes (functional richness, evenness, divergence and dispersion) based on functional traits measured. Extrapolated species richness showed a slight yet not significant decrease from the Pliocene to the Quaternary despite the fact that a large faunal turnover took place; furthermore, a large extinction of Pliocene species (61-76%) was followed by a high pulse of appearances (49-56%) during the Quaternary. Three out of four indices of functional diversity (evenness, divergence and dispersion) increased significantly towards the Quaternary which is more than expected under a random turnover of species. The increase in functional diversity is associated with a loss of large-sized carnivore forms, which tended to be replaced by small-sized grazers. Hence, this trait-selective species turnover, even in the absence of significant changes in species richness, likely had a large effect and has shaped the functional diversity of present-day assemblages.

Platinated DNA oligonucleotides: new probes forming ultrastable conjugates with graphene oxide

NASA Astrophysics Data System (ADS)

Wang, Feng; Liu, Juewen

2014-05-01

Metal containing polymers have expanded the property of polymers by involving covalently associated metal complexes. DNA is a special block copolymer. While metal ions are known to influence DNA, little is explored on its polymer property when strong metal complexes are associated. In this work, we study cisplatin modified DNA as a new polymer and probe. Out of the complexes formed between cisplatin-A15, HAuCl4-A15, Hg2+-T15 and Ag+-C15, only the cisplatin adduct is stable under the denaturing gel electrophoresis condition. Each Pt-nucleobase bond gives a positive charge and thus makes DNA a zwitterionic polymer. This allows ultrafast adsorption of DNA by graphene oxide (GO) and the adsorbed complex is highly stable. Non-specific DNA, protein, surfactants and thiolated compounds cannot displace platinated DNA from GO, while non-modified DNA is easily displaced in most cases. The stable GO/DNA conjugate is further tested for surface hybridization. This is the first demonstration of using metallated DNA as a polymeric material for interfacing with nanoscale materials.Metal containing polymers have expanded the property of polymers by involving covalently associated metal complexes. DNA is a special block copolymer. While metal ions are known to influence DNA, little is explored on its polymer property when strong metal complexes are associated. In this work, we study cisplatin modified DNA as a new polymer and probe. Out of the complexes formed between cisplatin-A15, HAuCl4-A15, Hg2+-T15 and Ag+-C15, only the cisplatin adduct is stable under the denaturing gel electrophoresis condition. Each Pt-nucleobase bond gives a positive charge and thus makes DNA a zwitterionic polymer. This allows ultrafast adsorption of DNA by graphene oxide (GO) and the adsorbed complex is highly stable. Non-specific DNA, protein, surfactants and thiolated compounds cannot displace platinated DNA from GO, while non-modified DNA is easily displaced in most cases. The stable GO/DNA conjugate is further tested for surface hybridization. This is the first demonstration of using metallated DNA as a polymeric material for interfacing with nanoscale materials. Electronic supplementary information (ESI) available: Methods, additional gels, kinetics, mass spectrum. See DOI: 10.1039/c4nr00867g

Variable near-surface deformation along the Commerce segment of the Commerce geophysical lineament, southeast Missouri to southern Illinois, USA

USGS Publications Warehouse

Odum, J.K.; Stephenson, W.J.; Williams, R.A.

2003-01-01

Recent studies have demonstrated a plausible link between surface and near-surface tectonic features and the vertical projection of the Commerce geophysical lineament (CGL). The CGL is a 5- to 10-km-wide zone of basement magnetic and gravity anomalies traceable for more than 600 km, extending from Arkansas through southeast Missouri and southern Illinois and into Indiana. Twelve kilometers of high-resolution seismic reflection data, collected at four sites along a 175-km segment of the CGL projection, are interpreted to show varying amounts of deformation involving Tertiary and some Quaternary sediments. Some of the locally anomalous geomorphic features in the northern Mississippi embayment region (i.e., paleoliquefaction features, anomalous directional changes in stream channels, and areas of linear bluff escarpments) overlying the CGL can be correlated with specific faults and/or narrow zones of deformed (faulted and folded) strata that are imaged on high-resolution seismic reflection data. There is an observable change in near-surface deformation style and complexity progressing from the southwest to the northeast along the trace of the CGL. The seismic reflection data collaborate mapping evidence which suggests that this region has undergone a complex history of deformation, some of which is documented to be as young as Quaternary, during multiple episodes of reactivation under varying stress fields. This work, along with that of other studies presented in this volume, points to the existence of at least one major crustal feature outside the currently defined zone of seismic activity (New Madrid Seismic Zone) that should be considered as a significant potential source zone for seismogenic activity within the midcontinent region of the United States. ?? 2003 Elsevier B.V. All rights reserved.

Evidences of Multiple Magma Injections in Quaternary Balerang and Rajabasa Volcanoes, Indonesia

NASA Astrophysics Data System (ADS)

Hasibuan, R. F.; Ohba, T.; Abdurrachman, M.

2016-12-01

Quaternary Balerang and Rajabasa volcanoes are situated along the nearly north-south lineament with a most explosive Krakatau volcanic complex in the south and effusive Sukadana basalt plateau in the north. Some studies have elucidated that Krakatau volcano has multiple magma storage regions beneath together with evidences of magma mixing process. By considering these circumstances, it is necessary to know lateral variations of magmas and to characterize volcanic rocks from Rajabasa volcanic complex which is located between these distinct magmatic systems, in terms of magmatic processes and evolution. Methodologies we used are X-ray fluorescence to determine the whole rock chemistry, K-Ar isotope dating to determine the lifespan of the volcano, as well as EPMA analysis to obtain the chemical composition of minerals. The rock chemistry or TAS plot shows a linear trend, ranging from basaltic (51 wt.%) to rhyolitic (75 wt.%), indicating a chemical heterogeneity of magma. When SiO2 contents are correlated with the relative ages, we found a broad tendency that SiO2 contents progressively decrease with age. The Rajabasa volcano lifespan is known formed at 0.31 Ma while one of the youngest lava is identified erupted at 0.12 Ma. Some plagioclase crystals exhibit disequilibrium textures, like highly sieved core and clear rim regions, also overgrowth rim on the plagioclase and pyroxene crystals whose composition more primitive than the core's composition, indicating magmatic recharge events. Reverse zoning and resorption textures associated with compositional step zoning or progressive zoning are quite common as well in clinopyroxene and plagioclase crystals. By considering these evidences, we conclude that injection of a hotter basaltic magma into colder and more felsic magma occurred beneath the volcanoes.

New seismo-stratigraphic and marine magnetic data of the Gulf of Pozzuoli (Naples Bay, Tyrrhenian Sea, Italy): inferences for the tectonic and magmatic events of the Phlegrean Fields volcanic complex (Campania)

NASA Astrophysics Data System (ADS)

Aiello, Gemma; Marsella, Ennio; Fiore, Vincenzo Di

2012-06-01

A detailed reconstruction of the stratigraphic and tectonic setting of the Gulf of Pozzuoli (Naples Bay) is provided on the basis of newly acquired single channel seismic profiles coupled with already recorded marine magnetics gathering the volcanic nature of some seismic units. Inferences for the tectonic and magmatic setting of the Phlegrean Fields volcanic complex, a volcanic district surrounding the western part of the Gulf of Naples, where volcanism has been active since at least 50 ka, are also discussed. The Gulf of Pozzuoli represents the submerged border of the Phlegrean caldera, resulting from the volcano-tectonic collapse induced from the pyroclastic flow deposits of the Campanian Ignimbrite (35 ka). Several morpho-depositional units have been identified, i.e., the inner continental shelf, the central basin, the submerged volcanic banks and the outer continental shelf. The stratigraphic relationships between the Quaternary volcanic units related to the offshore caldera border and the overlying deposits of the Late Quaternary depositional sequence in the Gulf of Pozzuoli have been highlighted. Fourteen main seismic units, both volcanic and sedimentary, tectonically controlled due to contemporaneous folding and normal faulting have been revealed by geological interpretation. Volcanic dykes, characterized by acoustically transparent sub-vertical bodies, locally bounded by normal faults, testify to the magma uprising in correspondence with extensional structures. A large field of tuff cones interlayered with marine deposits off the island of Nisida, on the western rim of the gulf, is related to the emplacement of the Neapolitan Yellow Tuff deposits. A thick volcanic unit, exposed over a large area off the Capo Miseno volcanic edifice is connected with the Bacoli-Isola Pennata-Capo Miseno yellow tuffs, cropping out in the northern Phlegrean Fields.

A novel L-ficolin/mannose-binding lectin chimeric molecule with enhanced activity against Ebola virus.

PubMed

Michelow, Ian C; Dong, Mingdong; Mungall, Bruce A; Yantosca, L Michael; Lear, Calli; Ji, Xin; Karpel, Marshall; Rootes, Christina L; Brudner, Matthew; Houen, Gunnar; Eisen, Damon P; Kinane, T Bernard; Takahashi, Kazue; Stahl, Gregory L; Olinger, Gene G; Spear, Gregory T; Ezekowitz, R Alan B; Schmidt, Emmett V

2010-08-06

Ebola viruses constitute a newly emerging public threat because they cause rapidly fatal hemorrhagic fevers for which no treatment exists, and they can be manipulated as bioweapons. We targeted conserved N-glycosylated carbohydrate ligands on viral envelope surfaces using novel immune therapies. Mannose-binding lectin (MBL) and L-ficolin (L-FCN) were selected because they function as opsonins and activate complement. Given that MBL has a complex quaternary structure unsuitable for large scale cost-effective production, we sought to develop a less complex chimeric fusion protein with similar ligand recognition and enhanced effector functions. We tested recombinant human MBL and three L-FCN/MBL variants that contained the MBL carbohydrate recognition domain and varying lengths of the L-FCN collagenous domain. Non-reduced chimeric proteins formed predominantly nona- and dodecameric oligomers, whereas recombinant human MBL formed octadecameric and larger oligomers. Surface plasmon resonance revealed that L-FCN/MBL76 had the highest binding affinities for N-acetylglucosamine-bovine serum albumin and mannan. The same chimeric protein displayed superior complement C4 cleavage and binding to calreticulin (cC1qR), a putative receptor for MBL. L-FCN/MBL76 reduced infection by wild type Ebola virus Zaire significantly greater than the other molecules. Tapping mode atomic force microscopy revealed that L-FCN/MBL76 was significantly less tall than the other molecules despite similar polypeptide lengths. We propose that alterations in the quaternary structure of L-FCN/MBL76 resulted in greater flexibility in the collagenous or neck region. Similarly, a more pliable molecule might enhance cooperativity between the carbohydrate recognition domains and their cognate ligands, complement activation, and calreticulin binding dynamics. L-FCN/MBL chimeric proteins should be considered as potential novel therapeutics.

Sand ramps as palaeoenvironmental archives: Integrating general principles and regional contexts through reanalysis of the Klipkraal Sands, South Africa

NASA Astrophysics Data System (ADS)

Rowell, Alexandra L. K.; Thomas, David S. G.; Bailey, Richard M.; Holmes, Peter J.

2018-06-01

Sand ramps occur on a continuum of topographically-controlled landforms, ranging from purely aeolian features (climbing/falling dunes) to talus cones and alluvial fans. Sand ramps have been identified as potentially important palaeoenvironmental archives in dryland regions that possess relatively few Quaternary proxy records. Their utility however requires not only good age control of depositional phases but clear identification of process regimes, determined through morphological and sedimentological analyses, with several recent studies indicating the complexities of palaeoenvironmental interpretations and the controls of ramp development (Bateman et al., 2012; Rowell et al., 2018). Klipkraal Sands is a sand ramp on the north-eastern margin of the semi-arid Karoo that has been important for inferences of the extent of southern African Late Quaternary aeolian activity (Thomas et al., 2002). We reanalyse this feature, in the light of both its significance and other recent studies that have inferred extensive southern African LGM aeolian activity (Telfer et al., 2012, 2014). New sedimentological data and twelve OSL dates indicate the Klipkraal Sands formed episodically between 100-0.14 ka, rather than accumulating rapidly, while sedimentological data question the aeolian affinities of the bulk of the feature. Therefore, Klipkraal is reinterpreted as showing no particular affinity to the LGM, with sediments locally sourced with a significant colluvial component. Only the upper historical sediments can be clearly interpreted as aeolian deposits. A complex interplay of processes is suggested, for which a meaningful palaeoenvironmental interpretation cannot be easily defined. This implies that the local geomorphic processes and controls operating on sand ramps need to be established before they can be fully utilised as palaeoenvironmental archives, with implications for their interpretation worldwide.

THE EFFECT OF ALKYL AMINE TYPE ON THE EXTRACTION OF NITRIC ACID AND NITROSYLRUTHENIUM NITRATO COMPLEXES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Timmins, T.H.; Mason, E.A.

1963-04-01

An investigation of the solvent extraction characteristics of nitric acid and the nitrato complexes of nitrosylruthenium was conducted, using alkyl amines as extractants. The alkyl amines used were a primary amine Primene JMT, a tertiary amine trilaurylamine (TLA), and a quaternary amine Aliquat 336. The organic phase concentrations of HNO/sub 3/ resulting during extraction by alkyl amines were found to correlate well on the basis of the undissociated aqueous HNO/ sub 3/ activity for both salted (NaNO/sub 3/) and unsalted aqueous phases. The distribution ratios for Ru extraction showed better correlation on this basis than on the basis of aqueousmore » phase nitrate and nitric acid. The order of decreasing Ru extraction at low HNO/sub 3/ concentration (2N) was found to be Aliquat 336, TLA, and Primene JMT. At high HNO/sub 3/ concentration (9N). Primene JMT had the highest Ru extractability. Hapid dilution experiments were utilized to determine the number and aqueous phase concentrations of the extractable species of Ru, and the amine partition coefficients for the species. It was found that two Ru species are extractable, and the more extractable species is present in the aqueous phase at lower concentration than the less extractable species. The mole fractions of both species were found to increase with increasing HNO/sub 3/ concentration. The TLA partition coefficients for the extractable species were found to decrease with increasing HNO/sub 3/ concentration. The quaternary amine, Aliquat 336, was found to have partition coefficients an order of magnitude greater than the tertiary amine, TLA. Equations for the mole fractions and TLA partition coefficients in the region of HNO/sub 3/ concentration investigated were developed. (auth)« less

Chemical characteristics, including stable-isotope ratios, of surface water and ground water from selected sources in and near East Fork Armells Creek basin, southeastern Montana, 1985

USGS Publications Warehouse

Ferreira, R.F.; Lambing, J.H.; Davis, R.E.

1989-01-01

Water samples were collected from 29 sites to provide synoptic chemical data, including stable-isotope ratios, for an area of active surface coal mining and to explore the effectiveness of using the data to chemically distinguish water from different aquifers. Surface-water samples were collected from one spring, four sites on East Armells Creek, one site on Stocker Creek, and two fly-ash ponds. Streamflows in East Fork Armells Creek ranged from no flow in several upstream reaches to 2.11 cu ft/sec downstream from Colstrip, Montana. Only one tributary, Stocker Creek, was observed to contribute surface flow in the study area. Groundwater samples were collected from wells completed in Quaternary alluvium or mine spoils, Rosebud overburden, Rosebud coal bed, McKay coal bed, and sub-McKay deposits of the Tongue River Member, Paleocene Fort Union Formation. Dissolved-solids concentrations, in mg/L, were 840 at the spring, 3,100 to 5,000 in the streams, 13,000 to 22,000 in the ash ponds, and 690 to 4 ,100 in the aquifers. With few exceptions, water from the sampled spring, streams, and wells had similar concentrations of major constituents and trace elements and similar stable-isotope ratios. Water from the fly-ash ponds had larger concentrations of dissolved solids, boron, and manganese and were isotopically more enriched in deuterium and oxygen-18 than water from other sources. Water from individual aquifers could not be distinguished by either ion-composition diagrams or statistical cluster analyses. (USGS)

Estimation of F-3 and F-4 knock-limited performance ratings for ternary and quaternary blends containing triptane or other high-antiknock aviation-fuel blending agents

NASA Technical Reports Server (NTRS)

Barnett, Henry C

1948-01-01

Charts are presented that permit the estimation of F-3 and F-4 knock-limited performance ratings for certain ternary and quaternary fuel blends. Ratings for various ternary and quaternary blends estimated from these charts compare favorably with experimental F-3 and F-4 ratings. Because of the unusual behavior of some of the aromatic blends in the F-3 engine, the charts for aromatic-paraffinic blends are probably less accurate than the charts for purely paraffinic blends.

Stereoselective preparation of quaternary 2-vinyl sphingosines and ceramides and their effect on basal sphingolipid metabolism.

PubMed

Calderón, Raquel; Mercadal, Nerea; Abad, José Luis; Ariza, Xavier; Delgado, Antonio; Garcia, Jordi; Rodríguez, Aleix; Fabriàs, Gemma

2017-06-01

The dicyclohexylborane-mediated addition of allene 1 to (E)-2-tridecenal affords a quaternary protected 2-amino-2-vinyl-1,3-diol in good yield as a single diastereomer. This compound is readily transformed into the four stereoisomers of the quaternary (E)-2-vinyl analogs of sphingosine. The metabolic fate and the effect of these compounds on the basal sphingolipid metabolism in human A549 lung adenocarcinoma cells has been studied, together with the ceramide analog of the most relevant vinylsphingosine derivative. Copyright © 2017 Elsevier B.V. All rights reserved.

Using Generic and Pesticide DRASTIC GIS-based models for vulnerability assessment of the Quaternary aquifer at Sohag, Egypt

NASA Astrophysics Data System (ADS)

Ahmed, Ayman A.

2009-07-01

Groundwater resources in the Sohag area, Egypt are currently threatened by contamination from municipal and industrial activities, and agricultural pesticides. To cope with the growing population, there has been development in the desert zone on both sides of the Nile Valley including agricultural investment areas, wastewater disposal sites, new urban areas, and industry. Use of agrochemicals in the old cultivated and newly reclaimed lands and wastewater disposal sites in the study area represent the most hazardous contamination sources. Prevention of contamination and management of the Quaternary aquifer is urgently needed. To address vulnerability assessment of the Quaternary aquifer, the Generic and Pesticide DRASTIC GIS-based models have been used. The Generic DRASTIC index ranged between 94 and 189, and the Pesticide DRASTIC index ranged between 94 and 226. The results showed that 83% of the Quaternary aquifer is characterized by the high and very high vulnerability classes to municipal, industrial and agricultural pesticides contamination. It was found that nearly all the development projects are located in the very high vulnerability class areas. Management alternatives for the Quaternary aquifer may be improved by application of these models, allowing sensitive groundwater sources to be protected for continuing use in the future.

Water quality of the Quaternary and Ada-Vamoosa aquifers on the Osage Reservation, Osage County, Oklahoma, 1997

USGS Publications Warehouse

Abbott, Marvin M.

2000-01-01

The project was to provide information on the quality of ground water from rural-domestic-water wells within the Osage Reservation and compare the water-quality to proximity to oil wells. About 38,500 oil wells have been drilled in the Reservation since drilling began in 1896. About 1,480 square miles or 64 percent of the Reservation is within a quarter mile of an oil well. The unconfined Quaternary sand aquifer covers about 315 square miles or about 14 percent of the Reservation and the confined Ada-Vamoosa sandstone aquifer covers about 800 square miles or about 35 percent of the Reservation. Fifty-eight percent of the Quaternary aquifer and 69 percent of the outcrop area of the Ada-Vamoosa aquifer are within a quarter mile of an oil well . One hundred twenty domestic ground-water wells were sampled from the Quaternary and Ada-Vamoosa aquifers. Forty-nine percent of the Reservation is underlain by the aquifers. Ground-water quality is good on most of the Reservation, but the use of domestic water-supply wells tend to minimize water-quality problems. Existing water-supply wells commonly are located in areas that produce usable volumes of potable water. Several constituents in samples from the Ada-Vamoosa-aquifer within a quarter mile of an oil well were significantly greater than from the aquifer not near oil wells. The constituents include specific conductance, dissolved solids, sodium, sulfate, chloride, bromide, and silica. These ions are probably derived from brine water. In the Ada-Vamoosa aquifer subgroups, 57 percent of the samples near oil wells and 24 percent of the samples not near oil wells had dissolved-solids concentrations greater than 500 milligrams per liter. The water quality in the Quaternary and Ada-Vamoosa aquifers is similar in areas where no oil wells have been drilled but is significantly different for several constituents. Median concentrations of major constituents from the Ada-Vamoosa aquifer not near oil wells were less than or equal to values from the Quaternary aquifer. Sixty-four percent of the water-quality samples from the Quaternary and 51 percent from the Ada-Vamoosa aquifers have dissolved-solids concentrations less than the secondary drinking water regulations of 500 milligrams per liter. Fifty-nine percent of the aquifer samples in the Quaternary aquifer subgroups not near oil wells and 70 percent of the samples near oil wells had dissolved solids less than 500 milligrams per liter. Areas in the Ada-Vamoosa aquifer near Hominy, Pershing, and Hula Lake have dissolved-solids concentrations greater than the secondary drinking water regulations. Water-quality samples from the Quaternary aquifer in these areas also have dissolved-solids concentrations greater than 500 milligrams per liter.

Competition of hydrogen bonds and halogen bonds in complexes of hypohalous acids with nitrogenated bases.

PubMed

Alkorta, Ibon; Blanco, Fernando; Solimannejad, Mohammad; Elguero, Jose

2008-10-30

A theoretical study of the complexes formed by hypohalous acids (HOX, X = F, Cl, Br, I, and At) with three nitrogenated bases (NH 3, N 2, and NCH) has been carried out by means of ab initio methods, up to MP2/aug-cc-pVTZ computational method. In general, two minima complexes are found, one with an OH...N hydrogen bond and the other one with a X...N halogen bond. While the first one is more stable for the smallest halogen derivatives, the two complexes present similar stabilities for the iodine case and the halogen-bonded structure is the most stable one for the hypoastatous acid complexes.

Electrically active induced energy levels and metastability of B and N vacancy-complexes in 4H–SiC

NASA Astrophysics Data System (ADS)

Igumbor, E.; Olaniyan, O.; Mapasha, R. E.; Danga, H. T.; Omotoso, E.; Meyer, W. E.

2018-05-01

Electrically active induced energy levels in semiconductor devices could be beneficial to the discovery of an enhanced p or n-type semiconductor. Nitrogen (N) implanted into 4H–SiC is a high energy process that produced high defect concentrations which could be removed during dopant activation annealing. On the other hand, boron (B) substituted for silicon in SiC causes a reduction in the number of defects. This scenario leads to a decrease in the dielectric properties and induced deep donor and shallow acceptor levels. Complexes formed by the N, such as the nitrogen-vacancy centre, have been reported to play a significant role in the application of quantum bits. In this paper, results of charge states thermodynamic transition level of the N and B vacancy-complexes in 4H–SiC are presented. We explore complexes where substitutional N/N or B/B sits near a Si (V) or C (V) vacancy to form vacancy-complexes (NV, NV, NV, NV, BV, BV, BV and BV). The energies of formation of the N related vacancy-complexes showed the NV to be energetically stable close to the valence band maximum in its double positive charge state. The NV is more energetically stable in the double negative charge state close to the conduction band minimum. The NV on the other hand, induced double donor level and the NV induced a double acceptor level. For B related complexes, the BV and BV were energetically stable in their single positive charge state close to the valence band maximum. As the Fermi energy is varied across the band gap, the neutral and single negative charge states of the BV become more stable at different energy levels. B and N related complexes exhibited charge state controlled metastability behaviour.

The role of faulting on surface deformation patterns from pumping-induced groundwater flow (Las Vegas Valley, USA)

NASA Astrophysics Data System (ADS)

Hernandez-Marin, Martin; Burbey, Thomas J.

2009-12-01

Land subsidence and earth fissuring can cause damage in semiarid urbanized valleys where pumping exceeds natural recharge. In places such as Las Vegas Valley (USA), Quaternary faults play an important role in the surface deformation patterns by constraining the migration of land subsidence and creating complex relationships with surface fissures. These fissures typically result from horizontal displacements that occur in zones where extensional stress derived from groundwater flow exceeds the tensile strength of the near-surface sediments. A series of hypothetical numerical models, using the finite-element code ABAQUS and based on the observed conditions of the Eglington Fault zone, were developed. The models reproduced the (1) long-term natural recharge and discharge, (2) heavy pumping and (3) incorporation of artificial recharge that reflects the conditions of Las Vegas Valley. The simulated hydrostratigraphy consists of three aquifers, two aquitards and a relatively dry vadose zone, plus a normal fault zone that reflects the Quaternary Eglington fault. Numerical results suggest that a 100-m-wide fault zone composed of sand-like material produces: (1) conditions most similar to those observed in Las Vegas Valley and (2) the most favorable conditions for the development of fissures to form on the surface adjacent to the fault zone.

Extraction of information on macromolecular interactions from fluorescence micro-spectroscopy measurements in the presence and absence of FRET.

PubMed

Raicu, Valerică

2018-06-15

Investigations of static or dynamic interactions between proteins or other biological macromolecules in living cells often rely on the use of fluorescent tags with two different colors in conjunction with adequate theoretical descriptions of Förster Resonance Energy Transfer (FRET) and molecular-level micro-spectroscopic technology. One such method based on these general principles is FRET spectrometry, which allows determination of the quaternary structure of biomolecules from cell-level images of the distributions, or spectra of occurrence frequency of FRET efficiencies. Subsequent refinements allowed combining FRET frequency spectra with molecular concentration information, thereby providing the proportion of molecular complexes with various quaternary structures as well as their binding/dissociation energies. In this paper, we build on the mathematical principles underlying FRET spectrometry to propose two new spectrometric methods, which have distinct advantages compared to other methods. One of these methods relies on statistical analysis of color mixing in subpopulations of fluorescently tagged molecules to probe molecular association stoichiometry, while the other exploits the color shift induced by FRET to also derive geometric information in addition to stoichiometry. The appeal of the first method stems from its sheer simplicity, while the strength of the second consists in its ability to provide structural information. Copyright © 2018 Elsevier B.V. All rights reserved.

Extraction of information on macromolecular interactions from fluorescence micro-spectroscopy measurements in the presence and absence of FRET

NASA Astrophysics Data System (ADS)

Raicu, Valerică

2018-06-01

Investigations of static or dynamic interactions between proteins or other biological macromolecules in living cells often rely on the use of fluorescent tags with two different colors in conjunction with adequate theoretical descriptions of Förster Resonance Energy Transfer (FRET) and molecular-level micro-spectroscopic technology. One such method based on these general principles is FRET spectrometry, which allows determination of the quaternary structure of biomolecules from cell-level images of the distributions, or spectra of occurrence frequency of FRET efficiencies. Subsequent refinements allowed combining FRET frequency spectra with molecular concentration information, thereby providing the proportion of molecular complexes with various quaternary structures as well as their binding/dissociation energies. In this paper, we build on the mathematical principles underlying FRET spectrometry to propose two new spectrometric methods, which have distinct advantages compared to other methods. One of these methods relies on statistical analysis of color mixing in subpopulations of fluorescently tagged molecules to probe molecular association stoichiometry, while the other exploits the color shift induced by FRET to also derive geometric information in addition to stoichiometry. The appeal of the first method stems from its sheer simplicity, while the strength of the second consists in its ability to provide structural information.

Amazonian Amphibian Diversity Is Primarily Derived from Late Miocene Andean Lineages

PubMed Central

Santos, Juan C; Coloma, Luis A; Summers, Kyle; Caldwell, Janalee P; Ree, Richard; Cannatella, David C

2009-01-01

The Neotropics contains half of remaining rainforests and Earth's largest reservoir of amphibian biodiversity. However, determinants of Neotropical biodiversity (i.e., vicariance, dispersals, extinctions, and radiations) earlier than the Quaternary are largely unstudied. Using a novel method of ancestral area reconstruction and relaxed Bayesian clock analyses, we reconstructed the biogeography of the poison frog clade (Dendrobatidae). We rejected an Amazonian center-of-origin in favor of a complex connectivity model expanding over the Neotropics. We inferred 14 dispersals into and 18 out of Amazonia to adjacent regions; the Andes were the major source of dispersals into Amazonia. We found three episodes of lineage dispersal with two interleaved periods of vicariant events between South and Central America. During the late Miocene, Amazonian, and Central American-Chocoan lineages significantly increased their diversity compared to the Andean and Guianan-Venezuelan-Brazilian Shield counterparts. Significant percentage of dendrobatid diversity in Amazonia and Chocó resulted from repeated immigrations, with radiations at <10.0 million years ago (MYA), rather than in situ diversification. In contrast, the Andes, Venezuelan Highlands, and Guiana Shield have undergone extended in situ diversification at near constant rate since the Oligocene. The effects of Miocene paleogeographic events on Neotropical diversification dynamics provided the framework under which Quaternary patterns of endemism evolved. PMID:19278298

Late Quaternary environmental dynamics in the Atacama Desert reconstructed from rodent midden pollen records

USGS Publications Warehouse

de Porras, M.E.; Maldonado, A.; De Pol-Holz, R.; Latorre, C.; Betancourt, Julio L.

2017-01-01

In the past two decades, much has been learned about the late Quaternary climate history of the Atacama Desert with some details still unclear about the seasonality, timing and extent of wet and dry phases. Modern climate studies reveal that, far from exhibiting a unique pattern, seasonal precipitation originates from many sources and mechanisms. For the last 16 ka, we attempt to sort out these complexities in pollen records from four fossil rodent midden series spanning 22°–25°S in northern Chile. Widespread wet conditions prevailed during the late Pleistocene and early Holocene, particularly between 13 and 9 ka, evidenced by <400 m lowering of pollen zones (plant communities) compared to today. Regional differences in the timing and magnitude of this displacement may be related to the prevailing source (tropical/extra‐tropical) or mode (NNW/SE) of tropical precipitation through time. Wet conditions persisted well into the early Holocene, lasting ∼1–1.5 ka longer than previously suggested. The pollen record suggests extreme drying ∼8 ka, possibly associated with a northward shift of the Inter Tropical Convergence Zone, tracking minimum insolation values at subtropical latitudes during the austral summer. The establishment of conditions similar to today happened ∼4 ka. 

An application of the geophysical methods and ALS DTM for the identification of the geological structure in the Kraśnik region - Lublin Upland, Poland

NASA Astrophysics Data System (ADS)

Kamiński, Mirosław

2017-11-01

The purpose of the study was the assessment of the viability of selected geophysical methods and the Airborne Laser Scanning (ALS) for the identification and interpretation of the geological structure. The studied area is covered with a dense forest. For this reason, the ALS numerical terrain model was applied for the analysis of the topography. Three geophysical methods were used: gravimetric, in the form of a semi-detailed gravimetric photograph, Vertical Electrical Sounding (VES), and Electrical Resistivity Tomography (ERT). The numerical terrain model enabled the identification of Jurassic limestone outcrops and interpretation of the directions of the faults network. The geological interpretation of the digitally processed gravimetric data enabled the determination of the spatial orientation of the synclines and anticlines axes and of the course directions of main faults. Vertical Electrical Sounding carried along the section line perpendicular to the Gościeradów anticline axis enabled the interpretation of the lithology of this structure and identification of its complex tectonic structure. The shallow geophysical surveys using the ERT method enabled the estimation of the thickness of Quaternary formations deposited unconformably on the highly eroded Jurassic limestone outcrop. The lithology of Quaternary, Cretaceous and Jurassic rocks was also interpreted.

Surficial geologic map of the Charleston region, Berkeley, Charleston, Colleton, Dorchester, and Georgetown Counties, South Carolina

USGS Publications Warehouse

Weems, Robert E.; Lewis, William C.; Lemon, Earl M.

2014-01-01

This map portrays the surface and shallow subsurface geology of the greater Charleston, S.C. region east of 80°30′ west and south of 33°15′ north. The region covers the entirety of Charleston County and portions of Berkeley, Colleton, Dorchester, and Georgetown Counties. Units locally exposed at the surface range in age from middle Eocene to Holocene, but most of the area is covered by Quaternary interglacial deposits. These are, from oldest to youngest, the Okefenokee, Waccamaw(?), Penholoway, Ladson, Ten Mile Hill, and Wando Formations and the Silver Bluff beds. Two cross sections, one running southeast from Harleyville to the coastline on James Island and the other running along the coastal barrier islands from the town of Edisto Beach to the northeast end of Bull Island at the southwest edge of Bull Bay, portray the complex geometry of the Paleogene and Neogene marine units that directly lie beneath the Quaternary units. These older units include the Santee Limestone, Tupelo Bay, Parkers Ferry, Ashley, Chandler Bridge, Edisto, Parachucla, and Marks Head Formations, the Goose Creek Limestone, and the Raysor Formation. The estimated locations of deeply buried active basement faults are shown which are responsible for ongoing modern seismicity in the Charleston, S.C. area.

Formation of toxic 2-nonyl-p-benzoquinones from α-tertiary 4-nonylphenol isomers during microbial metabolism of technical nonylphenol.

PubMed

Gabriel, Frédéric L P; Mora, Mauricio Arrieta; Kolvenbach, Boris A; Corvini, Philippe F X; Kohler, Hans-Peter E

2012-06-05

In many environmental compartments, microbial degradation of α-quaternary nonylphenols proceeds along an ipso-substitution pathway. It has been reported that technical nonylphenol contains, besides α-quaternary nonylphenols, minor amounts of various α-H, α-methyl substituted tertiary isomers. Here, we show that potentially toxic metabolites of such minor components are formed during ipso-degradation of technical nonylphenol by Sphingobium xenophagum Bayram, a strain isolated from activated sewage sludge. Small but significant amounts of nonylphenols were converted to the corresponding nonylhydroquinones, which in the presence of air oxygen oxidized to the corresponding nonyl-p-benzoquinones-yielding a complex mixture of potentially toxic metabolites. Through reduction with ascorbic acid and subsequent analysis by gas chromatography-mass spectrometry, we were able to characterize this unique metabolic fingerprint and to show that its components originated for the most part from α-tertiary nonylphenol isomers. Furthermore, our results indicate that the metabolites mixture also contained several α, β-dehydrogenated derivatives of nonyl-p-benzoquinones that originated by hydroxylation induced rearrangement, and subsequent ring and side chain oxidation from α-tertiary nonylphenol isomers. We predict that in nonylphenol polluted natural systems, in which microbial ipso-degradation is prominent, 2-alkylquinone metabolites will be produced and will contribute to the overall toxicity of the remaining material.

Exploring the Molecular Design of Protein Interaction Sites with Molecular Dynamics Simulations and Free Energy Calculations†

PubMed Central

Liang, Shide; Li, Liwei; Hsu, Wei-Lun; Pilcher, Meaghan N.; Uversky, Vladimir; Zhou, Yaoqi; Dunker, A. Keith; Meroueh, Samy O.

2009-01-01

The significant work that has been invested toward understanding protein–protein interaction has not translated into significant advances in structure-based predictions. In particular redesigning protein surfaces to bind to unrelated receptors remains a challenge, partly due to receptor flexibility, which is often neglected in these efforts. In this work, we computationally graft the binding epitope of various small proteins obtained from the RCSB database to bind to barnase, lysozyme, and trypsin using a previously derived and validated algorithm. In an effort to probe the protein complexes in a realistic environment, all native and designer complexes were subjected to a total of nearly 400 ns of explicit-solvent molecular dynamics (MD) simulation. The MD data led to an unexpected observation: some of the designer complexes were highly unstable and decomposed during the trajectories. In contrast, the native and a number of designer complexes remained consistently stable. The unstable conformers provided us with a unique opportunity to define the structural and energetic factors that lead to unproductive protein–protein complexes. To that end we used free energy calculations following the MM-PBSA approach to determine the role of nonpolar effects, electrostatics and entropy in binding. Remarkably, we found that a majority of unstable complexes exhibited more favorable electrostatics than native or stable designer complexes, suggesting that favorable electrostatic interactions are not prerequisite for complex formation between proteins. However, nonpolar effects remained consistently more favorable in native and stable designer complexes reinforcing the importance of hydrophobic effects in protein–protein binding. While entropy systematically opposed binding in all cases, there was no observed trend in the entropy difference between native and designer complexes. A series of alanine scanning mutations of hot-spot residues at the interface of native and designer complexes showed less than optimal contacts of hot-spot residues with their surroundings in the unstable conformers, resulting in more favorable entropy for these complexes. Finally, disorder predictions revealed that secondary structures at the interface of unstable complexes exhibited greater disorder than the stable complexes. PMID:19113835

The Density and Compressibility of BaCO3-SrCO3-CaCO3-K2CO3-Na2CO3-Li2CO3 Liquids: New Measurements and a Systematic Trend with Cation Field Strength

NASA Astrophysics Data System (ADS)

Hurt, S. M.; Lange, R. A.; Ai, Y.

2015-12-01

The volumetric properties of multi-component carbonate liquids are required to extend thermodynamic models that describe partial melting of the deep mantle (e.g. pMELTS; Ghiorso et al., 2003) to carbonate-bearing lithologies. Carbonate in the mantle is an important reservoir of carbon, which is released to the atmosphere as CO2 through volcanism, and thus contributes to the carbon cycle. Although MgCO3 is the most important carbonate component in the mantle, it is not possible to directly measure the 1-bar density and compressibility of MgCO3 liquid because, like other alkaline-earth carbonates, it decomposes at a temperature lower than its melting temperature. Despite this challenge, Liu and Lange (2003) and O'Leary et al. (2015) showed that the one bar molar volume, thermal expansion and compressibility of the CaCO3 liquid component could be obtained by measuring the density and sound speeds of stable liquids in the CaCO3-Li2CO3-Na2CO3-K2CO3 quaternary system at one bar. In this study, this same strategy is employed on SrCO3- and BaCO3-bearing alkali carbonate liquids. The density and sound speed of seven liquids in the SrCO3-Li2CO3-Na2CO3-K2CO3 quaternary and three liquids in the BaCO3-Li2CO3-Na2CO3-K2CO3 quaternary were measured from 739-1367K, with SrCO3 and BaCO3 concentrations ranging from 10-50 mol%. The density measurements were made using the double-bob Archimedean method and sound speeds were obtained with a frequency-sweep acoustic interferometer. The molar volume and sound speed measurements were used to calculate the isothermal compressibility of each liquid, and the results show the volumetric properties mix ideally with composition. The partial molar volume and compressibility of the SrCO3 and BaCO3 components are compared to those obtained for the CaCO3 component as a function of cation field strength. The results reveal a systematic trend that allows the partial molar volume and compressibility of the MgCO3 liquid component to be estimated.

Lagoon microbialites on Isla Angel de la Guarda and associated peninsular shores, Gulf of California (Mexico)

NASA Astrophysics Data System (ADS)

Johnson, Markes E.; Ledesma-Vázquez, Jorge; Backus, David H.; González, Maria R.

2012-07-01

Examples of two closed lagoons with extensive growth of Recent microbialites showing variable surface morphology and internal structure are found on Isla Angel de la Guarda in the Gulf of California. Comparable lagoonal microbialites also occur ashore from Ensenada El Quemado on the adjacent peninsular mainland of Baja California. The perimeters of all three lagoons feature crusted structures indicative of thrombolites with a knobby surface morphology 2 cm to 3 cm in relief and internal clotting without any sign of laminations. Outward from this zone, thrombolitic construction thins to merge with a white calcified crust below which a soft substratum of dark organic material 4 cm to 6 cm in thickness is concealed. The substratum is laminated and heavily mucilaginous, as observed along the edges of extensive shrinkage cracks in the overlying crust. The thrombolitic crust is anchored to the shore, while the thinner crust and associated stromatolitic mats float on the surface of the lagoons. Laboratory cultures of the dark organic material yielded the solitary cyanobacterium Chroococcidiopsis as the predominant taxon interspersed with filamentous forms. In decreasing order of abundance, other morphotypes present include Phormidium, Oscillatoria, Geitlerinema, Chroococus, and probably Spirulina. The larger of the two island lagoons follows an east-west azimuth and covers 0.225 km2, while the smaller lagoon has a roughly north-south axis and covers only 0.023 km2. The salinity of water in the smaller lagoon was measured as148 ppt. Pliocene strata along the edge of the smaller modern lagoon include siltstone bearing calcified platelets suggestive of a microbial origin. Dry lagoons abandoned during the later Quaternary occur inland at higher elevations on the island, but retain no fossils except for sporadic white crusts cemented on cobbles around distinct margins. Raised Quaternary lagoons parallel to the big lagoon on Isla Angel de la Guarda are partly obscured by flood damage, but still easily mapped from aerial photos. These features suggest that Isla Angel de la Guarda experienced Quaternary uplift similar in scale to many other gulf islands on which marine terraces are preserved. Closed lagoons around the Gulf of California represent a stable oligotrophic ecosystem affected by extreme aridity and hypersalinity, punctuated episodically by the injection of floodwater from tropical storms. The taxonomic and geographic ranges of microbial communities throughout the larger region remain to be explored.

Coupling δ18O values of rodent tooth and mollusc shell carbonates: a new approach to reconstructing Pleistocene palaeotemperatures?

NASA Astrophysics Data System (ADS)

Peneycad, Elizabeth; Candy, Ian; Schreve, Danielle

2017-04-01

The ratio of stable oxygen isotopes in fossil rodent teeth (δ18Ort) can potentially provide valuable quantitative information about terrestrial palaeoclimate conditions. Grimes et al. (2004) suggested that δ18Ort could be usefully combined with the δ18O values of coeval biominerals, e.g. mollusc shells (δ18Oms), to estimate past summer temperatures during the Quaternary period. Nevertheless, until now, the application of this approach to Quaternary palaeoclimate reconstruction has remained unexplored. In addition, the success of this approach is dependent upon the establishment of a statistically robust relationship between δ18Ort and the δ18O of meteoric water (δ18Omw) in the modern environment. However, such a relationship is yet to be quantified in relation to rodent tooth carbonate. Here, we present the preliminary results of 2 studies investigating the validity of δ18Ort as a climate proxy. Firstly, isotope analyses were undertaken on modern vole (Microtus agrestis) teeth from 3 locations across the UK. The results of these analyses reveal a significant linear correlation between the mean δ18Ort and the mean δ18Omw. These findings therefore demonstrate that a quantifiable relationship exists between δ18Ort and δ18Omw, highlighting the potential of δ18Ort as an accurate recorder of local climatic conditions. This modern relationship was subsequently applied to the reconstruction of past δ18Omw values for two Pleistocene interglacial sites in the UK. The δ18Omw values were calculated using δ18Ort, and then combined with δ18Oms values derived from coeval fossil gastropod assemblages in order to estimate mean summer palaeotemperatures. The results of these calculations are in close agreement with multi-proxy temperature reconstructions derived from the same deposits. This suggests that coupling the δ18O values of rodent tooth and mollusc shell carbonates offers great potential as an approach to quantifying summer palaeotemperatures in Europe, particularly for carbonate-rich sites at which alternative temperature proxies may be unavailable. References: Grimes, S.T., Mattey, D.P., Collinson, M.E. & Hooker, J.J. (2004) Using mammal tooth phosphate with freshwater carbonate and phosphate palaeoproxies to obtain mean paleotemperatures. Quaternary Science Reviews, 23, pp.967-976.

40 CFR 721.655 - Ethoxylated alkyl quaternary ammonium compound.

Code of Federal Regulations, 2010 CFR

2010-07-01

...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.655 Ethoxylated alkyl quaternary ammonium compound. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically...

Ternary and Quaternary Composition Diagrams: An Overview of the Subject.

ERIC Educational Resources Information Center

MacCarthy, Patrick

1983-01-01

Reviews graphical methods for representing ternary and quaternary systems, focusing on use of triangular composition diagrams. Examines some of the relevant geometry of triangles in general, showing that right isosceles triangles possess some very advantageous features for representing ternary systems. (JN)

Solubility limits in quaternary SnTe-based alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siol, Sebastian; Holder, Aaron; Ortiz, Brenden R.

2017-01-01

A combined theoretical and experimental approach was used to determine the equilibrium as well as non-equilibrium solubility lines in the quaternary Sn 1-yMn yTe 1-xSe xalloy space, revealing a large area of accessible metastable phase space.

12. VIEW OF THE SOUTHWEST ELEVATION OF THE STABLES. THE ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

12. VIEW OF THE SOUTHWEST ELEVATION OF THE STABLES. THE STABLES ARE LOCATED AT THE EXTREME SOUTHWESTERN END OF THE MINE COMPLEX. - Tower Hill No. 2 Mine, Approximately 0.47 mile Southwest of intersection of Stone Church Road & Township Route 561, Hibbs, Fayette County, PA

Influences on the stable oxygen and carbon isotopes in gerbillid rodent teeth in semi-arid and arid environments: Implications for past climate and environmental reconstruction

NASA Astrophysics Data System (ADS)

Jeffrey, Amy; Denys, Christiane; Stoetzel, Emmanuelle; Lee-Thorp, Julia A.

2015-10-01

The stable isotope composition of small mammal tissues has the potential to provide detailed information about terrestrial palaeoclimate and environments, because their remains are abundant in palaeontological and archaeological sites, and they have restricted home ranges. Applications to the Quaternary record, however, have been sparse and limited by an acute lack of understanding of small mammal isotope ecology, particularly in arid and semi-arid environments. Here we document the oxygen and carbon isotope composition of Gerbillinae (gerbil) tooth apatite across a rainfall gradient in northwestern Africa, in order to test the relative influences of the 18O/16O in precipitation or moisture availability on gerbil teeth values, the sensitivity of tooth apatite 13C/12C to plant responses to moisture availability, and the influence of developmental period on the isotopic composition of gerbil molars and incisors. The results show that the isotopic composition of molars and incisors from the same individuals differs consistent with the different temporal periods reflected by the teeth; molar teeth are permanently rooted and form around the time of birth, whereas incisors grow continuously. The results indicate that tooth choice is an important consideration for applications as proxy Quaternary records, but also highlights a new potential means to distinguish seasonal contexts. The oxygen isotope composition of gerbil tooth apatite is strongly correlated with mean annual precipitation (MAP) below 600 mm, but above 600 mm the teeth reflect the oxygen isotope composition of local meteoric water instead. Predictably, the carbon isotope composition of the gerbil teeth reflected C3 and C4 dietary inputs, however arid and mesic sites could not be distinguished because of the high variability displayed in the carbon isotope composition of the teeth due to the microhabitat and short temporal period reflected by the gerbil. We show that the oxygen isotope composition of small mammal teeth strongly reflects moisture availability in semi-arid and arid environments and would provide an excellent record of palaeo-aridity in a terrestrial setting. The results illustrate that an understanding of an animal's physiology is essential for interpreting the animal's isotopic responses to external contexts, especially in arid zones.

Expedition 354 on the Bengal fan: a Neogene record of Himalayan erosion

NASA Astrophysics Data System (ADS)

France-Lanord, C.; Spiess, V.; Schwenk, T.; Klaus, A.; Galy, A.

2017-12-01

Drilling in the Bengal fan generated a comprehensive record of Himalayan erosion over the Neogene and Quaternary. It documents the interplay between Himalayan tectonic and the monsoon. The fan is predominantly composed of detrital turbiditic sediments originating from Himalayan rivers, and transported through the delta and shelf canyon, supplying turbidity currents loaded with a wide spectrum of grain sizes. Turbiditic deposition makes that record at a given site is discontinuous which was the reason for an E-W transect approach. Exp. 354 drilled seven sites along a 320 km E-W transect at 8°N allowing the restitution of an almost complete record of Himalayan erosion at the scale of the Neogene. In spite of the transect's extension, a long absence of deposition was observed between 0.6 to 1.2 Ma indicating that turbiditic depocenter was derived more to the West for ca. 600 kyr. Turbidites have clear Himalayan origin with close mineralogical and isotopic analogy with those of the modern Ganga-Brahmaputra river sediments. Geochemistry shows relatively stable compositions throughout the Neogene and Quaternary and reveal a very weak regime of chemical weathering with no significant variation through time. Concentrations in mobile elements such as Na and K relative to Al are significantly higher than in modern sediments suggesting that weathering is amplified in the modern time. Low weathering of the sediments at 8°N indicates that erosion was dominated by physical processes and that transport is rapid enough to prevent evolution of particles in the floodplain. In the modern Himalaya, low weathering is achieved primarily by landslides and rapid transfer through the floodplain, i.e. limited recycling of sediment deposited in the floodplain. Both processes are favoured by the seasonality and the intensity of the monsoon. Although relatively stable, source tracers such as Sr-Nd isotopic compositions, and detrital carbonate compositions show organised variations with time. They imply that exposure to erosion of the different Himalayan formations has evolved as a result of the evolution of the thrusting structures. Data suggest that (1) Tethys Himalaya exposure to erosion was higher during Miocene than after 5 Ma and (2) that the exhumation of the Lesser Himalaya was initiated around 8 Ma.

Climate and tectonic variability during Late Quaternary in western fringe of Tibetan Plateau: case study from Trans-Himalayan ranges of Ladakh, NW India

NASA Astrophysics Data System (ADS)

Phartiyal, B.

2016-12-01

The climate system plays an important role in the geomorphological dynamics of a region. The cold, arid, high altitude, tectonically active areas of Ladakh (India) in Trans Himalaya, western Tibetan Plateau is none exception. Noticeable change in the landscape with a shift from fluvial to lacustrine regime at 10000 yrs BP forming big open valley lakes occupying the present day river valleys is attributed to the early Holocene northward advancement of the mean latitudinal position of the summer ITCZ causing wetter conditions in this dry area. The glaciers of the Ladakh range are almost depleted and the northern range glaciers show andrastic retreat in the Quaternary time. Lakes were studied using multi-proxies, to record centennial and decadal scale climatic variability. Spatial and temporal setting of Spituk palaeolake (12600-240 cal yrs BP) along Indus River, was analyzed using multi proxies. The lake that extended for 40-50 km covering an area of 106 km2, was formed after Older Dryas as a result of river blockage by precipitation induced debris flow and seismicity. Two lake phases between 12600-9000 and 5500-3200 cal yrs BP show stable lake conditions and have synchronous relationship between high variation in monsoon intensity, high δ18O values in the Guliya core, rise in temperature and high solar insolation. High magnetic susceptibility and clay content along with diversified diatom and other freshwater algae and land derived organic matter are indicative of fresh water supply leading to high lake level from 4700 yr BP onwards in the present pro-glacial lakes studied. The multi-proxy data provides evidence of much higher and stable lake level during 3700 yr BP and 3000 yr BP onwards due to high water supply in these lake. It is in contrast to the records of weak ISM conditions and low lake level in rest of the part of Indian peninsula during the period. The study also suggests strong western disturbance activity during 4800-3000 yr BP leading to high lake level in this region. The ongoing researches aim to make an inventory/dataset of these records and address the climate-tectonics interaction with respect to the lake outburst consequences.

On the interconnection of stable protein complexes: inter-complex hubs and their conservation in Saccharomyces cerevisiae and Homo sapiens networks.

PubMed

Guerra, Concettina

2015-01-01

Protein complexes are key molecular entities that perform a variety of essential cellular functions. The connectivity of proteins within a complex has been widely investigated with both experimental and computational techniques. We developed a computational approach to identify and characterise proteins that play a role in interconnecting complexes. We computed a measure of inter-complex centrality, the crossroad index, based on disjoint paths connecting proteins in distinct complexes and identified inter-complex hubs as proteins with a high value of the crossroad index. We applied the approach to a set of stable complexes in Saccharomyces cerevisiae and in Homo sapiens. Just as done for hubs, we evaluated the topological and biological properties of inter-complex hubs addressing the following questions. Do inter-complex hubs tend to be evolutionary conserved? What is the relation between crossroad index and essentiality? We found a good correlation between inter-complex hubs and both evolutionary conservation and essentiality.

Paleontology to policy: the Quaternary history of Southeast Asian tapirs (Tapiridae) in relation to large mammal species turnover, with a proposal for conservation of Malayan tapir by reintroduction to Borneo.

PubMed

Cranbrook, Earl Of; Piper, Philip J

2013-03-01

The Southeast Asian zoogeographical region is divided into Indochinese, Sundaic and Philippine subregions. Two clades of tapirs, Tapirus spp., have been recognized in Quaternary Southeast Asia. A review of sites at which they occurred shows that representatives of both clades, one of which was the ancestral Malayan tapir Tapirus indicus, co-existed with a diversity of other Pleistocene mammal megafauna. The process of replacement of archaic large mammals was progressive and prolonged through the Quaternary. Zooarcheological investigation has extended knowledge of the former occurrence and distribution of tapirs and other large mammals of the region, with discoveries beyond the outer limits of their previously known ranges. These large mammals were subjected to paleoenvironmental changes as a consequence of the Quaternary cycles of glacial and interglacial periods. Archeological evidence suggests that hunting pressure has intensified the effects of altered environments, leading ultimately to the local disappearance of the Malayan tapir in most of Southeast Asia, including Borneo. The survival of the Malayan tapir through the Quaternary until the present shows that the species is both resilient to environmental change and flexible in its ecological re'uirements and, given proper protection, could continue to inhabit tropical Southeast Asia. To assist the species conservation, reintroduction is proposed from the remaining range of Malayan tapir in the wild, to suitable sites of past occurrence in Borneo, where these ancient survivors of the Quaternary megafauna can be accommodated and safeguarded alongside other forms of land usage. © 2012 Wiley Publishing Asia Pty Ltd, ISZS and IOZ/CAS.

3D seismic evidence of buried iceberg ploughmarks from the mid-Norwegian continental margin reveals largely persistent North Atlantic Current through the Quaternary.

PubMed

Montelli, A; Dowdeswell, J A; Ottesen, D; Johansen, S E

2018-05-01

Over 7500 buried linear and curvilinear depressions interpreted as iceberg ploughmarks were identified within the Quaternary Naust Formation from an extensive three-dimensional seismic dataset that covers ~ 40,000 km 2 of the mid-Norwegian continental margin. The morphology and net orientation of ploughmarks were mapped and analysed. These features are up to 28 km long, 700 m wide and are incised up to 31 m deep. On average, ploughmarks are incised 5 m deep, with median width of 185 m and median lengths ranging from 1.2 to 2.7 km for individual palaeo-surfaces. Width to depth ratio ranges from 8:1 to 400:1 and is on average 36:1. The presence of ploughmarks buried deeply within some palaeo-slope surfaces implies the occasional presence of very large icebergs since the middle Quaternary, suggesting that thick ice-sheet margins with fast-flowing ice streams were present in order to calve icebergs of such dimensions into the Norwegian Sea. The wide geographical distribution of ploughmarks suggests unrestricted iceberg drift and an open Norwegian Sea during the periods of iceberg calving since the early Quaternary. Ploughmark trajectory analysis demonstrates that the ocean current circulation, now dominated by the northeasterly flowing Norwegian Atlantic Current (NwAC), has largely persisted throughout the Quaternary. Despite the overall strikingly consistent pattern of iceberg drift, ploughmark mapping also shows evidence for short-lived NwAC reductions possibly related to major phases of iceberg discharge and/or meltwater pulses from the Fennoscandian Ice Sheet during the middle and late Quaternary.

Ion-pair hollow-fiber liquid-phase microextraction of the quaternary ammonium surfactant dicocodimethylammonium chloride.

PubMed

Hultgren, Sofie; Larsson, Niklas; Nilsson, Bo F; Jönsson, Jan Ake

2009-02-01

A two-phase hollow-fiber (HF) liquid-phase microextraction (LPME) method was developed for determination of a quaternary ammonium compound surfactant, dicocodimethylammonium chloride, in aqueous samples. The porous HF was fixed on a metal rod support and was impregnated with approximately 6.6 microL of organic extractant, which was immobilized in the HF pores. Surfactant extraction was facilitated by addition of carboxylic acid to the sample forming neutral ion pairs with the quaternary ammonium compound. After extraction, the analyte was transferred from the organic extractant in the fiber pores by dissolving the 1-octanol into 100 microL methanol. The methanol extract was analyzed by liquid chromatography-mass spectrometry. The method was optimized (with optimized parameters in brackets) with regard to type of organic extractant (1-octanol), fiber length (2 cm), choice and concentration of anionic carrier (600 microg L(-1) octanoate), procedure of transfer to methanol (15-min sonication), sample volume (250 mL), extraction time (17 h), pH (10), and ionic strength (50 mM carbonate). Aspects influencing repeatability in LPME of (quaternary ammonium) surfactants are discussed. The enrichment factor achieved in 250-mL carbonate buffer was around 400. Due to matrix effects, the enrichment factors achieved when industrial process water was analyzed were 120 or about 30% of that in carbonate buffer. Detection limits of 0.3 microg L(-1) in carbonate buffer and 0.9 microg L(-1) in industrial process water were obtained. If the studied compound is seen as a model substance representing quaternary dialkylated dimethylated ammonium surfactants in general, the developed method may be applied to other quaternary ammonium surfactants.

Evaluating the Significance of Paleophylogeographic Species Distribution Models in Reconstructing Quaternary Range-Shifts of Nearctic Chelonians

PubMed Central

Flecks, Morris; Ahmadzadeh, Faraham; Dambach, Johannes; Engler, Jan O.; Habel, Jan Christian; Hartmann, Timo; Hörnes, David; Ihlow, Flora; Schidelko, Kathrin; Stiels, Darius; Polly, P. David

2013-01-01

The climatic cycles of the Quaternary, during which global mean annual temperatures have regularly changed by 5–10°C, provide a special opportunity for studying the rate, magnitude, and effects of geographic responses to changing climates. During the Quaternary, high- and mid-latitude species were extirpated from regions that were covered by ice or otherwise became unsuitable, persisting in refugial retreats where the environment was compatible with their tolerances. In this study we combine modern geographic range data, phylogeny, Pleistocene paleoclimatic models, and isotopic records of changes in global mean annual temperature, to produce a temporally continuous model of geographic changes in potential habitat for 59 species of North American turtles over the past 320 Ka (three full glacial-interglacial cycles). These paleophylogeographic models indicate the areas where past climates were compatible with the modern ranges of the species and serve as hypotheses for how their geographic ranges would have changed in response to Quaternary climate cycles. We test these hypotheses against physiological, genetic, taxonomic and fossil evidence, and we then use them to measure the effects of Quaternary climate cycles on species distributions. Patterns of range expansion, contraction, and fragmentation in the models are strongly congruent with (i) phylogeographic differentiation; (ii) morphological variation; (iii) physiological tolerances; and (iv) intraspecific genetic variability. Modern species with significant interspecific differentiation have geographic ranges that strongly fluctuated and repeatedly fragmented throughout the Quaternary. Modern species with low genetic diversity have geographic distributions that were highly variable and at times exceedingly small in the past. Our results reveal the potential for paleophylogeographic models to (i) reconstruct past geographic range modifications, (ii) identify geographic processes that result in genetic bottlenecks; and (iii) predict threats due to anthropogenic climate change in the future. PMID:24130664

Climatic, geomorphic, and archaeological implications of a late Quaternary alluvial chronology for the lower Salt River, Arizona, USA

NASA Astrophysics Data System (ADS)

Huckleberry, Gary; Onken, Jill; Graves, William M.; Wegener, Robert

2013-03-01

Recent archaeological excavations along the lower Salt River, Arizona resulted in the unexpected discovery of buried late Pleistocene soils and cultural features dating 5800-7100 cal YBP (Early Archaic), the latter representing the earliest evidence of human activity in the lower Salt River floodplain thus far identified. Because the lower Salt River floodplain has been heavily impacted by recent agriculture and urbanization and contains few stratigraphic exposures, our understanding of the river's geological history is limited. Here we present a late Quaternary alluvial chronology for a segment of the lower Salt River based on 19 accelerator mass spectrometry 14C and four optically stimulated luminescence ages obtained during two previous geoarchaeological investigations. Deposits are organized into allostratigraphic units and reveal a buried late Pleistocene terrace inset into middle-to-late Pleistocene terrace deposits. Holocene terrace fill deposits unconformably cap the late Pleistocene terrace tread in the site area, and the lower portion of this fill contains the Early Archaic archaeological features. Channel entrenchment and widening ~ 900 cal YBP eroded much of the older terrace deposits, leaving only a remnant of fill containing the buried latest Pleistocene and middle-to-late Holocene deposits preserved in the site area. Subsequent overbank deposition and channel filling associated with a braided channel system resulted in the burial of the site by a thin layer of flood sediments. Our study confirms that the lower Salt River is a complex mosaic of late Quaternary alluvium formed through vertical and lateral accretion, with isolated patches of buried soils preserved through channel avulsion. Although channel avulsion is linked to changes in sediment load and discharge and may have climatic linkages, intrinsic geomorphic and local base level controls limit direct correlations of lower Salt River stratigraphy to other large rivers in the North American Southwest.

Unliganded HIV-1 gp120 core structures assume the CD4-bound conformation with regulation by quaternary interactions and variable loops

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kwon, Young Do; Finzi, Andrés; Wu, Xueling

2013-03-04

The HIV-1 envelope (Env) spike (gp120{sub 3}/gp41{sub 3}) undergoes considerable structural rearrangements to mediate virus entry into cells and to evade the host immune response. Engagement of CD4, the primary human receptor, fixes a particular conformation and primes Env for entry. The CD4-bound state, however, is prone to spontaneous inactivation and susceptible to antibody neutralization. How does unliganded HIV-1 maintain CD4-binding capacity and regulate transitions to the CD4-bound state? To define this mechanistically, we determined crystal structures of unliganded core gp120 from HIV-1 clades B, C, and E. Notably, all of these unliganded HIV-1 structures resembled the CD4-bound state. Conformationalmore » fixation with ligand selection and thermodynamic analysis of full-length and core gp120 interactions revealed that the tendency of HIV-1 gp120 to adopt the CD4-bound conformation was restrained by the V1/V2- and V3-variable loops. In parallel, we determined the structure of core gp120 in complex with the small molecule, NBD-556, which specifically recognizes the CD4-bound conformation of gp120. Neutralization by NBD-556 indicated that Env spikes on primary isolates rarely assume the CD4-bound conformation spontaneously, although they could do so when quaternary restraints were loosened. Together, the results suggest that the CD4-bound conformation represents a 'ground state' for the gp120 core, with variable loop and quaternary interactions restraining unliganded gp120 from 'snapping' into this conformation. A mechanism of control involving deformations in unliganded structure from a functionally critical state (e.g., the CD4-bound state) provides advantages in terms of HIV-1 Env structural diversity and resistance to antibodies and inhibitors, while maintaining elements essential for entry.« less

Late Quaternary Faulting in Southeastern Louisiana: A Natural Laboratory for Understanding Shallow Faulting in Deltaic Materials

NASA Astrophysics Data System (ADS)

Dawers, N. H.; McLindon, C.

2017-12-01

A synthesis of late Quaternary faults within the Mississippi River deltaic plain aims to provide a more accurate assessment of regional and local fault architecture, and interactions between faulting, sediment loading, salt withdrawal and compaction. This effort was initiated by the New Orleans Geological Society and has resulted in access to industry 3d seismic reflection data, as well as fault trace maps, and various types of well data and biostratigraphy. An unexpected outgrowth of this project is a hypothesis that gravity-driven normal faults in deltaic settings may be good candidates for shallow aseismic and slow-slip phenomena. The late Quaternary fault population is characterized by several large, highly segmented normal fault arrays: the Baton Rouge-Tepetate fault zone, the Lake Pontchartrain-Lake Borgne fault zone, the Golden Meadow fault zone (GMFZ), and a major counter-regional salt withdrawal structure (the Bay Marchand-Timbalier Bay-Caillou Island salt complex and West Delta fault zone) that lies just offshore of southeastern Louisiana. In comparison to the other, more northerly fault zones, the GMFZ is still significantly salt-involved. Salt structures segment the GMFZ with fault tips ending near or within salt, resulting in highly localized fault and compaction related subsidence separated by shallow salt structures, which are inherently buoyant and virtually incompressible. At least several segments within the GMFZ are characterized by marsh breaks that formed aseismically over timescales of days to months, such as near Adams Bay and Lake Enfermer. One well-documented surface rupture adjacent to a salt dome propagated over a 3 day period in 1943. We suggest that Louisiana's coastal faults make excellent analogues for deltaic faults in general, and propose that a series of positive feedbacks keep them active in the near surface. These include differential sediment loading and compaction, weak fault zone materials, high fluid pressure, low elastic stiffness in surrounding materials, and low confining pressure.

Coastal Geomorphology, Growth Patterns and Stratigraphy of Uplifted Coral-Reef Terraces of Sumba Island, Indonesia: Towards a Re-Evaluation of Quaternary Sea-Level Highstands

NASA Astrophysics Data System (ADS)

Rigaud, S.; Leclerc, F.; Abidin, H. Z.; Bijaksana, S.; Chiang, H. W.; Ginting Munthe, F. A.; Liu, X.; Meilano, I.; Pradipta, G. C.; Ramdhani, B. D.; Tapponnier, P.; Wang, X.

2016-12-01

The island of Sumba (Indonesia) is uniquely located within the Sunda-Banda forearc, at the transition between oceanic subduction and arc-continent collision, and has experienced vertical movements for the last 7 Myrs (Fortuin et al., 1997). The spectacular flights of coral-reef terraces exposed on the northern coast have served as benchmarks to reconstruct Quaternary sea-level highstands (stages 5 to 23). Sea-level paleo-elevations were established using reef crests and marine notches as geomorphological markers, assuming a constant uplift rate of 0.49 mm/yr and neglecting erosion and weathering processes (Pirazzoli et al., 1991, 1993). Recent and fossil coral reefs of the northern coast of Sumba Island are fringing, leeward reefs. A new examination of the morphology and stratigraphy of fossil terraces shows that they are primarily built by prograding complexes formed during forced regressions. The current geomorphological expression of reef crests, therefore, does not correspond to the highest position of past sea-levels. The same is true for marine notches, which may only indicate intermediary still-stand phases and are barely distinguishable from weathering surfaces in terraces older than stages 5-7. In our study, we use the elevation of the inner edges of coral terraces as indicators of the highest position of the sea-level during Quaternary highstands. At the island scale, our geomorphological investigations, U/Th dating and high-resolution correlations point to high discrepancies in the deformation patterns, especially at Cape Laundi where the position of past sea-level highstands was established. Through a multi-disciplinary study involving geomorphology, stratigraphy, tectonic, sedimentology, paleontology and geochronology, we offer new estimates for uplift rates at the island scale and re-evaluate the elevation of past sea-level highstands. References : Fortuin et al. 1997. Journal of Asian Earth Sciences 15, p. 61-88. Pirazzoli et al. 1991. Science 252, p. 1834-1836. Pirazzoli et al. 1993. Marine Geology 109, p. 221-236.

Mohawk Lake or Mohawk meadow Sedimentary facies and stratigraphy of Quaternary deposits in Mohawk Valley, upper Middle Fork of the Feather River, California

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yount, J.C.; Harwood, D.S.; Bradbury, J.P.

1993-04-01

Mohawk Valley (MV) contain thick, well-exposed sections of Quaternary basin-fill sediments, with abundant interbedded tephra and a diverse assemblage of sedimentary facies. The eastern arm of MV, extending from Clio to Portola, contains as much as 100 m of trough cross-bedded cobble to pebble gravel and planar and trough cross-bedded coarse and medium sand, interpreted as braided stream deposits. Sections exposed in the western arm of MV consist in their lower parts of massive organic-rich silt and clay interbedded with blocky to fissile peat beds up to 1 m thick. Diatom assemblages are dominated by benthic species indicating fresh marshmore » environments with very shallow water depths of one meter or less. Proglacial lacustrine deposits of limited lateral extent are present within the outwash complexes as evidenced by varved fine sand and silt couplets, poorly sorted quartz-rich silt beds containing dropstones, and contorted beds of diamict grading laterally into slump blocks surrounded by wood-bearing silt and silty sand. The Rockland Ash (400 ka) is a prominent marker in the middle or lower part of many sections throughout MV, indicating that at least half of the basin-fill sequence is Late Quaternary in age. A log buried in diamict slumped into a proglacial lake lying approximately 3 km downstream from the Tioga Stage ice termini in Jamison and Gray Eagle Creeks yields an age of 18,715 [+-]235 C[sup 14] years BP. Previous interpretations of MV deposits originating in a large, deep lake with water depths in excess of 150 m are untenable given the sedimentary facies and diatom floras that dominate the valley. Unexhumed valleys such as Sierra Valley to the east and Long Valley to the northwest which contain large meadows traversed by braided streams are probably good analogs for the conditions that existed during the accumulation of the Mohawk Valley deposits.« less

Geochemical characterization of a Quaternary monogenetic volcano in Erciyes Volcanic Complex: Cora Maar (Central Anatolian Volcanic Province, Turkey)

NASA Astrophysics Data System (ADS)

Gencalioglu-Kuscu, Gonca

2011-11-01

Central Anatolian Volcanic Province (CAVP) is a fine example of Neogene-Quaternary post-collisional volcanism in the Alpine-Mediterranean region. Volcanism in the Alpine-Mediterranean region comprises tholeiitic, transitional, calc-alkaline, and shoshonitic types with an "orogenic" fingerprint. Following the orogenic volcanism, subordinate, within-plate alkali basalts ( sl) showing little or no orogenic signature are generally reported in the region. CAVP is mainly characterized by widespread calc-alkaline andesitic-dacitic volcanism with orogenic trace element signature, reflecting enrichment of their source regions by subduction-related fluids. Cora Maar (CM) located within the Erciyes pull-apart basin, is an example to numerous Quaternary monogenetic volcanoes of the CAVP, generally considered to be alkaline. Major and trace element geochemical and geochronological data for the CM are presented in comparison with other CAVP monogenetic volcanoes. CM scoria is basaltic andesitic, transitional-calc-alkaline in nature, and characterized by negative Nb-Ta, Ba, P and Ti anomalies in mantle-normalized patterns. Unlike the "alkaline" basalts of the Mediterranean region, other late-stage basalts from the CAVP monogenetic volcanoes are classified as tholeiitic, transitional and mildly alkaline. They display the same negative anomalies and incompatible element ratios as CM samples. In this respect, CM is comparable to other CAVP monogenetic basalts ( sl), but different from the Meditterranean intraplate alkali basalts. Several lines of evidence suggest derivation of CM and other CAVP monogenetic basalts from shallow depths within the lithospheric mantle, that is from a garnet-free source. In a wider regional context, CAVP basalts ( sl) are comparable to Apuseni (Romania) and Big Pine (Western Great Basin, USA) volcanics, except the former have depleted Ba contents. This is a common feature for the CAVP volcanics and might be related to crustal contamination or source characteristics. Indeed, HFS and other incompatible element ratios suggest the role of crustal contamination in the genesis of the CAVP monogenetic basalts.

Theoretical study of X⁻ · 1 · YF (1 = triazine, X = Cl, Br and I, Y = H, Cl, Br, I, PH₂ and AsH₂): noncovalently electron-withdrawing effects on anion-arene interactions.

PubMed

Chen, Yishan; Yao, Lifeng

2014-01-01

The ternary complexes X(-) · 1 · YF (1 = triazine, X = Cl, Br and I, Y = H, Cl, Br, I, PH2 and AsH2) have been investigated by MP2 calculations to understand the noncovalently electron-withdrawing effects on anion-arene interactions. The results indicate that in binary complexes (1 · X(-)), both weak σ-type and anion-π complexes can be formed for Cl(-) and Br(-), but only anion-π complex can be formed for I(-). Moreover, the hydrogen-bonding complex is the global minimum for all three halides in binary complexes. However, in ternary complexes, anion-π complex become unstable and only σ complex can retain in many cases for Cl(-) and Br(-). Anion-π complex keeps stable only when YF = HF. In contrast with binary complexes, σ complex become the global minimum for Cl(-) and Br(-) in ternary complexes. These changes in binding mode and strength are consistent with the results of covalently electron-withdrawing effects. However, in contrast with the covalently electron-withdrawing substituents, Cl(-) and Br(-) can attack the aromatic carbon atom to form a strong σ complex when the noncovalently electron-withdrawing effect is induced by halogen bonding. The binding behavior for I(-) is different from that for Cl(-) and Br(-) in two aspects. First, the anion-π complex for I(-) can also keep stable when the noncovalent interaction is halogen bonding. Second, the anion-π complex for I(-) is the global minimum when it can retain as a stable structure.

Non-site-specific allosteric effect of oxygen on human hemoglobin under high oxygen partial pressure

PubMed Central

Takayanagi, Masayoshi; Kurisaki, Ikuo; Nagaoka, Masataka

2014-01-01

Protein allostery is essential for vital activities. Allosteric regulation of human hemoglobin (HbA) with two quaternary states T and R has been a paradigm of allosteric structural regulation of proteins. It is widely accepted that oxygen molecules (O2) act as a “site-specific” homotropic effector, or the successive O2 binding to the heme brings about the quaternary regulation. However, here we show that the site-specific allosteric effect is not necessarily only a unique mechanism of O2 allostery. Our simulation results revealed that the solution environment of high O2 partial pressure enhances the quaternary change from T to R without binding to the heme, suggesting an additional “non-site-specific” allosteric effect of O2. The latter effect should play a complementary role in the quaternary change by affecting the intersubunit contacts. This analysis must become a milestone in comprehensive understanding of the allosteric regulation of HbA from the molecular point of view. PMID:24710521

Analysis of Predominance of Sexual Reproduction and Quadruplicity of Bases by Computer Simulation

NASA Astrophysics Data System (ADS)

Dasgupta, Subinay

We have presented elsewhere a model for computer simulation of a colony of individuals reproducing sexually, by meiotic parthenogenesis and by cloning. Our algorithm takes into account food and space restriction, and attacks of some diseases. Each individual is characterized by a string of L ``base'' units, each of which can be of four types (quaternary model) or two types (binary model). Our previous report was for the case of L=12 (quaternary model) and L=24 (binary model) and contained the result that the fluctuation of population was the lowest for sexual reproduction with four types of base units. The present communication reports that the same conclusion also holds for L=10 (quaternary model) and L=20 (binary model), and for L=8 (quaternary model) and L=16 (binary model). This model however, suffers from the drawback that it does not show the effect of aging. A modification of the model was attempted to remove this drawback, but the results were not encouraging.

Phase and Physicochemical Properties Diagrams of Quaternary System Li2B4O7 + Na2B4O7 + Mg2B6O11 + H2O

NASA Astrophysics Data System (ADS)

Wang, Shi-qiang; Du, Xue-min; Jing, Yan; Guo, Ya-fei; Deng, Tian-long

2017-12-01

The phase and physicochemical properties diagrams of the quaternary system (Li2B4O7 + Na2B4O7 + Mg2B6O11) at 288.15 K and 0.1 MPa were constructed using the solubilities, densities, and refractive indices measured. In the phase diagrams of the system there are one invariant point, three univariant isothermic dissolution curves, and three crystallization regions corresponding to Li2B4O7 · 3H2O, Na2B4O7 · 10H2O, and Mg2B6O11 · 15H2O, respectively. The solution density, refractive index of the quaternary system changes regularly with the increasing of Li2B4O7 concentration. The calculated values of density and refractive index using empirical equations of the quaternary system are in good agreement with the experimental values.

Hydrolysis of cellulose catalyzed by quaternary ammonium perrhenates in 1-allyl-3-methylimidazolium chloride.

PubMed

Wang, Jingyun; Zhou, Mingdong; Yuan, Yuguo; Zhang, Quan; Fang, Xiangchen; Zang, Shuliang

2015-12-01

Quaternary ammonium perrhenates were applied as catalyst to promote the hydrolysis of cellulose in 1-allyl-3-methylimidazolium chloride ([Amim]Cl). The quaternary ammonium perrhenates displayed good catalytic performance for cellulose hydrolysis. Water was also proven to be effective to promote cellulose hydrolysis. Accordingly, 97% of total reduced sugar (TRS) and 42% of glucose yields could be obtained under the condition of using 5mol% of tetramethyl ammonium perrhenate as catalyst, 70μL of water, ca. 0.6mmol of microcrystalline cellulose (MCC) and 2.0g of [Amim]Cl as solvent under microwave irradiation for 30min at 150°C (optimal conditions). The influence of quaternary ammonium cation on the efficiency of cellulose hydrolysis was examined based on different cation structures of perrhenates. The mechanism on perrhenate catalyzed cellulose hydrolysis is also discussed, whereas hydrogen bonding between ReO4 anion and hydroxyl groups of cellulose is assumed to be the key step for depolymerization of cellulose. Copyright © 2015. Published by Elsevier Ltd.

Anticholinesterase inhibitory activity of quaternary alkaloids from Tinospora crispa.

PubMed

Yusoff, Mashitah; Hamid, Hazrulrizawati; Houghton, Peter

2014-01-20

Quaternary alkaloids are the major alkaloids isolated from Tinospora species. A previous study pointed to the necessary presence of quaternary nitrogens for strong acetylcholinesterase (AChE) inhibitory activity in such alkaloids. Repeated column chromatography of the vine of Tinospora crispa extract led to the isolation of one new protoberberine alkaloid, 4,13-dihydroxy-2,8,9-trimethoxydibenzo[a,g]quinolizinium (1), along with six known alkaloids-dihydrodiscretamine (2), columbamine (3), magnoflorine (4), N-formylannonaine (5), N-formylnornuciferine (6), and N-trans-feruloyltyramine (7). The seven compounds were isolated and structurally elucidated by spectroscopic analysis. Two known alkaloids, namely, dihydrodiscretamine and columbamine are reported for the first time for this plant. The compounds were tested for AChE inhibitory activity using Ellman's method. In the AChE inhibition assay, only columbamine (3) showed strong activity with IC50 48.1 µM. The structure-activity relationships derived from these results suggest that the quaternary nitrogen in the skeleton has some effect, but that a high degree of methoxylation is more important for acetylcholinesterase inhibition.

Why is quaternary prevention important in prevention?

PubMed Central

Tesser, Charles Dalcanale

2017-01-01

ABSTRACT Quaternary prevention consists in the identification of persons at risk of excessive medicalization and their protection against new unnecessary interventions, avoiding iatrogenic damages. Here, we argue about the importance of quaternary prevention in specific primary and secondary prevention. The recent great development of preventive medicine, biomedicalization of risks and their treatment as if they were diseases, and the powerful influence of the commercial interests of pharmaceutical industries on the production of medical-sanitary knowledge alter classifications, create diseases and pre-diseases, lower cutoff points, and erase the distinction between prevention and healing. This situation converts larger amounts of asymptomatic persons into sick individuals and diverts clinical attention and resources from sick persons to the healthy, from older adults to young persons, and from the poor to the rich. Quaternary prevention facilitates and induces the development and systematization of operational knowledge and guidelines to contain hypermedicalization and the damages of preventive actions in professional care, especially in primary health care. PMID:29211199

Non-site-specific allosteric effect of oxygen on human hemoglobin under high oxygen partial pressure.

PubMed

Takayanagi, Masayoshi; Kurisaki, Ikuo; Nagaoka, Masataka

2014-04-08

Protein allostery is essential for vital activities. Allosteric regulation of human hemoglobin (HbA) with two quaternary states T and R has been a paradigm of allosteric structural regulation of proteins. It is widely accepted that oxygen molecules (O2) act as a "site-specific" homotropic effector, or the successive O2 binding to the heme brings about the quaternary regulation. However, here we show that the site-specific allosteric effect is not necessarily only a unique mechanism of O2 allostery. Our simulation results revealed that the solution environment of high O2 partial pressure enhances the quaternary change from T to R without binding to the heme, suggesting an additional "non-site-specific" allosteric effect of O2. The latter effect should play a complementary role in the quaternary change by affecting the intersubunit contacts. This analysis must become a milestone in comprehensive understanding of the allosteric regulation of HbA from the molecular point of view.

Quaternary bimodal volcanism in the Niğde Volcanic Complex (Cappadocia, central Anatolia, Turkey): age, petrogenesis and geodynamic implications

NASA Astrophysics Data System (ADS)

Aydin, Faruk; Schmitt, Axel K.; Siebel, Wolfgang; Sönmez, Mustafa; Ersoy, Yalçın; Lermi, Abdurrahman; Dirik, Kadir; Duncan, Robert

2014-11-01

The late Neogene to Quaternary Cappadocian Volcanic Province (CVP) in central Anatolia is one of the most impressive volcanic fields of Turkey because of its extent and spectacular erosionally sculptured landscape. The late Neogene evolution of the CVP started with the eruption of extensive andesitic-dacitic lavas and ignimbrites with minor basaltic lavas. This stage was followed by Quaternary bimodal volcanism. Here, we present geochemical, isotopic (Sr-Nd-Pb and δ18O isotopes) and geochronological (U-Pb zircon and Ar-Ar amphibole and whole-rock ages) data for bimodal volcanic rocks of the Niğde Volcanic Complex (NVC) in the western part of the CVP to determine mantle melting dynamics and magmatic processes within the overlying continental crust during the Quaternary. Geochronological data suggest that the bimodal volcanic activity in the study area occurred between ca. 1.1 and ca. 0.2 Ma (Pleistocene) and comprises (1) mafic lavas consisting of basalts, trachybasalts, basaltic andesites and scoria lapilli fallout deposits with mainly basaltic composition, (2) felsic lavas consisting of mostly rhyolites and pumice lapilli fall-out and surge deposits with dacitic to rhyolitic composition. The most mafic sample is basalt from a monogenetic cone, which is characterized by 87Sr/86Sr = 0.7038, 143Nd/144Nd = 0.5128, 206Pb/204Pb = 18.80, 207Pb/204Pb = 15.60 and 208Pb/204Pb = 38.68, suggesting a moderately depleted signature of the mantle source. Felsic volcanic rocks define a narrow range of 143Nd/144Nd isotope ratios (0.5126-0.5128) and are homogeneous in Pb isotope composition (206Pb/204Pb = 18.84-18.87, 207Pb/204Pb = 15.64-15.67 and 208Pb/204Pb = 38.93-38.99). 87Sr/86Sr isotopic compositions of mafic (0.7038-0.7053) and felsic (0.7040-0.7052) samples are similar, reflecting a common mantle source. The felsic rocks have relatively low zircon δ18O values (5.6 ± 0.6 ‰) overlapping mantle values (5.3 ± 0.3 %), consistent with an origin by fractional crystallization from a mafic melt with very minor continental crustal contamination. The geochronological and geochemical data suggest that mafic and felsic volcanic rocks of the NVC are genetically closely related to each other. Mafic rocks show a positive trend between 87Sr/86Sr and Th, suggesting simultaneous assimilation and fractional crystallization, whereas the felsic rocks are characterized by a flat or slightly negative variation. High 87Sr/86Sr gneisses are a potential crustal contaminant of the mafic magmas, but the comparatively low and invariant 87Sr/86Sr in the felsic volcanics suggests that these evolved dominantly by fractional crystallization. Mantle-derived basaltic melts, which experienced low degree of crustal assimilation, are proposed to be the parent melt of the felsic volcanics. Geochronological and geochemical results combined with regional geological and geophysical data suggest that bimodal volcanism of the NVC and the CVP, in general, developed in a post-collisional extensional tectonic regime that is caused by ascending asthenosphere, which played a key role during magma genesis.

3D decompaction and sequential restoration: a tool to quantify sedimentary and tectonic control on elusive Quaternary structures

NASA Astrophysics Data System (ADS)

D'Ambrogi, Chiara; Emanuele Maesano, Francesco

2015-04-01

Basin-wide detailed 3D model, deeply constrained by the interpretation of an impressive dense seismic dataset (12.000 km, provided confidentially by ENI S.p.A.) and 136 well stratigraphies, is the core of a workflow of decompaction and sequential restoration in 3D aimed to quantify the sedimentation and uplift rate in the central part of the Po Plain (northern Italy), during Quaternary. The Po basin is the common foredeep of two opposite verging chains, the Southern Alps, to the north, and the Northern Apennines, to the south, that influenced the evolution of the foreland basin from Paleogene onward. In this particular setting there are many examples of interaction of sedimentary processes and tectonics, both at regional and local scale. During the Quaternary the complex interaction of tectonic processes, sea-level fluctuations, climate changes, and sediment supply produced the filling of the basin with the progradation of the fluvio-deltaic system, from west toward east. The most important tectonic phases can be easily recognized along the basin margin marked by the deformation and tilting of river terraces and of exposed syntectonic sediments; conversely their detection is particularly difficult in the central-distal part of the basin. In such structurally complex area analysis of syntectonic deposits and growth strata are strategic to describe the basin evolution and tectonic control; in their analysis 3D decompaction and regional tilting must be taken into account to assess the residual vertical separation that can be attributed to tectonic processes only. The Pleistocene portion of a detailed 3D model, build in the framework of the EU-funded GeoMol Project, is the starting point of a sequential restoration workflow in 3D that included the unfolding and decompaction of 6, chronologically constrained, sedimentary units ranging from 1.5 to 0.45 Myr. This previously unavailable detail in the definition of the geometry of Quaternary bodies in the central part of the Po Basin provided a set of detailed pictures that show the topography and the evolution of the infilling at different point during time. As a matter of fact the resulting 3D surfaces describe the basin configuration and the changes and migration of regional depocentres controlled by thrust activity up to the Pleistocene but also allow to highlight the interference of active tectonic and sedimentation in the central portion of the Po basin, an area considered less affected by the main structures (e.g. the Emilia and Ferrara-Romagna arcs). In the analysis of this structure also the foreland tilting has been subtracted from the topography resulting after unfolding and decompaction, for the 6 time intervals; we obtained a residual signal related to the growing anticline, and the uplift rate of the structure during its Pleistocene evolution. The project GeoMol is co-funded by the Alpine Space Program as part of the European Territorial Cooperation 2007-2013. The project integrates partners from Austria, France, Germany, Italy, Slovenia and Switzerland and runs from September 2012 to June 2015. Further information on www.geomol.eu

Map and Database of Probable and Possible Quaternary Faults in Afghanistan

USGS Publications Warehouse

Ruleman, C.A.; Crone, A.J.; Machette, M.N.; Haller, K.M.; Rukstales, K.S.

2007-01-01

The U.S. Geological Survey (USGS) with support from the U.S. Agency for International Development (USAID) mission in Afghanistan, has prepared a digital map showing the distribution of probable and suspected Quaternary faults in Afghanistan. This map is a key component of a broader effort to assess and map the country's seismic hazards. Our analyses of remote-sensing imagery reveal a complex array of tectonic features that we interpret to be probable and possible active faults within the country and in the surrounding border region. In our compilation, we have mapped previously recognized active faults in greater detail, and have categorized individual features based on their geomorphic expression. We assigned mapped features to eight newly defined domains, each of which contains features that appear to have similar styles of deformation. The styles of deformation associated with each domain provide insight into the kinematics of the modern tectonism, and define a tectonic framework that helps constrain deformational models of the Alpine-Himalayan orogenic belt. The modern fault movements, deformation, and earthquakes in Afghanistan are driven by the collision between the northward-moving Indian subcontinent and Eurasia. The patterns of probable and possible Quaternary faults generally show that much of the modern tectonic activity is related to transfer of plate-boundary deformation across the country. The left-lateral, strike-slip Chaman fault in southeastern Afghanistan probably has the highest slip rate of any fault in the country; to the north, this slip is distributed onto several fault systems. At the southern margin of the Kabul block, the style of faulting changes from mainly strike-slip motion associated with the boundary between the Indian and Eurasian plates, to transpressional and transtensional faulting. North and northeast of the Kabul block, we recognized a complex pattern of potentially active strike-slip, thrust, and normal faults that form a conjugate shear system in a transpressional region of the Trans-Himalayan orogenic belt. The general patterns and orientations of faults and the styles of deformation that we interpret from the imagery are consistent with the styles of faulting determined from focal mechanisms of historical earthquakes. Northwest-trending strike-slip fault zones are cut and displaced by younger, southeast-verging thrust faults; these relations define the interaction between northwest-southeast-oriented contraction and northwest-directed extrusion in the western Himalaya, Pamir, and Hindu Kush regions. Transpression extends into north-central Afghanistan where north-verging contraction along the east-west-trending Alburz-Marmul fault system interacts with northwest-trending strike-slip faults. Pressure ridges related to thrust faulting and extensional basins bounded by normal faults are located at major stepovers in these northwest-trending strike-slip systems. In contrast, young faulting in central and western Afghanistan indicates that the deformation is dominated by extension where strike-slip fault zones transition into regions of normal faults. In addition to these initial observations, our digital map and database provide a foundation that can be expanded, complemented, and modified as future investigations provide more detailed information about the location, characteristics, and history of movement on Quaternary faults in Afghanistan.

Design, synthesis, and biological evaluation of air-stable nafuredin-γ analogs as complex I inhibitors.

PubMed

Ohtawa, Masaki; Matsunaga, Mari; Fukunaga, Keiko; Shimizu, Risa; Shimizu, Eri; Arima, Shiho; Ohmori, Junko; Kita, Kiyoshi; Shiomi, Kazuro; Omura, Satoshi; Nagamitsu, Tohru

2015-03-01

Nafuredin-γ (2), converted from nafuredin (1) under mild basic conditions, demonstrates potent and selective inhibitory activity against helminth complex I. However, 2 is unstable in air because the conjugated dienes are oxygen-labile. To address this, we designed and synthesized air-stable nafuredin-γ analogs. Although the complex I inhibitory activities of all the new nafuredin-γ analogs were lower than that of 2, all were in the high nM range (IC50: 300-820nM). Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis of the first radiolabeled 188Re N-heterocyclic carbene complex and initial studies on its potential use in radiopharmaceutical applications

PubMed Central

Wagner, Thomas; Zeglis, Brian M.; Groveman, Sam; Hille, Claudia; Pöthig, Alexander; Francesconi, Lynn C.; Herrmann, Wolfgang A.; Kühn, Fritz E.; Reiner, Thomas

2015-01-01

A novel approach towards the synthesis of radiolabeled organometallic rhenium complexes is presented. We successfully synthesized and analyzed the first 188Re-labeled N-heterocyclic biscarbene complex, trans-dioxobis(1,1′-methylene-bis(3,3′-diisopropylimidazolium-2-ylidene))188rhenium(V) hexafluorophosphate (188Re-4) via transmetalation using an air-stable and moisture-stable silver(I) biscarbene complex. In order to assess the viability of this complex as a potential lead structure for in vivo applications, the stability of the 188Re-NHC complex was tested in physiologically relevant media. Ultimately, our studies illustrate that the complex we synthesized dissociates rapidly and is therefore unsuitable for use in radiopharmaceuticals. However, it is clear that the transmetalation approach we have developed is a rapid, robust, and mild method for the synthesis of new 188Re-labeled carbene complexes. PMID:24889257

Cs2Bi(PO4)(WO4)

PubMed Central

Terebilenko, Kateryna V.; Zatovsky, Igor V.; Baumer, Vyacheslav N.; Slobodyanik, Nikolay S.

2009-01-01

Dicaesium bis­muth(III) phosphate(V) tungstate(VI), Cs2Bi(PO4)(WO4), has been synthesized during complex investigation in a molten pseudo-quaternary Cs2O–Bi2O3–P2O5–WO3 system. It is isotypic with K2Bi(PO4)(WO4). The three-dimensional framework is built up from [Bi(PO4)(WO4)] nets, which are organized by adhesion of [BiPO4] layers and [WO4] tetra­hedra above and below of those layers. The inter­stitial space is occupied by Cs atoms. Bi, W and P atoms lie on crystallographic twofold axes. PMID:21577386

Asymmetric intramolecular Pauson-Khand reaction mediated by a remote sulfenyl or sulfinyl group.

PubMed

García Ruano, José Luis; Torrente, Esther; Parra, Alejandro; Alemán, José; Martín-Castro, Ana M

2012-08-03

In this work, we report the use of the asymmetric intramolecular Pauson-Khand reactions of 4-aryl-4-cyano-1,6-enynes for obtaining enantiomerically enriched bicyclo[3.3.0]octenones, and the influence of both the quaternary stereocenter and the sulfur functions located at ortho-position of the aryl group, on their stereoselectivity and reactivity. The sulfenyl derivatives bearing substituted or unsubstituted triple bonds and mono- and disubstituted alkene moieties afford bicyclo[3.3.0]octenones in high yields with complete diastereocontrol. These results are explained by assuming the association of the lone electron pair at sulfur to the Co-alkyne complexes.

Data without Frontiers - the International Quaternary Map of Europe (IQUAME 2500)

NASA Astrophysics Data System (ADS)

Asch, Kristine

2017-04-01

The Federal German Geological Survey (Bundesanstalt für Geowissenschaften und Rohstoffe, BGR) is leading the review of the International Quaternary Map of Europe (IQUAME 2500) and its transformation into a geographical information system (GIS) under the umbrella of the CGMW and INQUA. It is a long-standing policy of BGR to lead international cooperation of European geological survey mapping projects. These particularly include projects under the umbrella of organisations including CGMW, UNESCO, INQUA, EGU and IUGS. The aim of IQUAME 2500 is to build a geological information system (GIS) of Europe's Quaternary geology where relevant information can be retrieved, combined and applied across international boundaries. Cross-border mapping poses specific challenges, in particular data harmonisation, for the presentation of regional geology. Overcoming these obstacles demands international cooperation with national geological survey organisations. Based on the previous BGR & UNESCO co-produced International Quaternary Map of Europe (at a 1 : 2,5 million scale; completed in 1995), revision was begun by BGR in 2011 to review the information available from an international group of experts from European geological survey organisations. This group is supported by an international academic Advisory Board. The work requires re-evaluation and digitization of the 14 paper sheets. For this purpose BGR developed a pragmatic procedure to classify, deliver and combine the reviewed Quaternary data in a harmonized and uniform manner. The project is applying the vocabularies and data model of the EC Directive INSPIRE Directive and is creating additional vocabularies and definitions for necessary features such as geomorphology (with the EMODnet project) and glaciogenic elements. An academic scientific advisory board is overseeing the process. Subjects of the map include: geological boundaries and classifications of Quaternary rocks, extension and boundaries of permafrost, last glacial maximum, genetic descriptions of the rocks, faults, key localities (geologically and palaeontologically significant sites, anthropological sites, impact craters, etc.) and more detailed off-shore geology (in cooperation with the EMODnet project). Ultimately, the IQUAME project will summarise the current status quo of European Quaternary geological research in a digitally available GIS synthesis and introduce practically applicable new vocabularies to describe the results and share those with the science community.

Optimization of the high-performance liquid chromatographic separation of a complex mixture containing urinary steroids, boldenone and bolasterone: application to urine samples.

PubMed

Gonzalo-Lumbreras, R; Izquierdo-Hornillos, R

2000-05-26

An HPLC separation of a complex mixture containing 13 urinary anabolics and corticoids, and boldenone and bolasterone (synthetic anabolics) has been carried out. The applied optimization method involved the use of binary, ternary and quaternary mobile phases containing acetonitrile, methanol or tetrahydrofuran as organic modifiers. The effect of different reversed-phase packings and temperature on the separation was studied. The optimum separation was achieved by using a water-acetonitrile (60:40, v/v) mobile phase in reversed-phase HPLC at 30 degrees C, allowing the separation of all the analytes in about 24 min. Calibration graphs were obtained using bolasterone or methyltestosterone as internal standards. Detection limits were in the range 0.012-0.107 microg ml(-1). The optimized separation was applied to the analysis, after liquid-liquid extraction, of human urine samples spiked with steroids.

Enzyme-catalyzed cationic epoxide rearrangements in quinolone alkaloid biosynthesis.

PubMed

Zou, Yi; Garcia-Borràs, Marc; Tang, Mancheng C; Hirayama, Yuichiro; Li, Dehai H; Li, Li; Watanabe, Kenji; Houk, K N; Tang, Yi

2017-03-01

Epoxides are highly useful synthons and biosynthons for the construction of complex natural products during total synthesis and biosynthesis, respectively. Among enzyme-catalyzed epoxide transformations, a reaction that is notably missing, in regard to the synthetic toolbox, is cationic rearrangement that takes place under strong acid. This is a challenging transformation for enzyme catalysis, as stabilization of the carbocation intermediate upon epoxide cleavage is required. Here, we discovered two Brønsted acid enzymes that can catalyze two unprecedented epoxide transformations in biology. PenF from the penigequinolone pathway catalyzes a cationic epoxide rearrangement under physiological conditions to generate a quaternary carbon center, while AsqO from the aspoquinolone pathway catalyzes a 3-exo-tet cyclization to forge a cyclopropane-tetrahydrofuran ring system. The discovery of these new epoxide-modifying enzymes further highlights the versatility of epoxides in complexity generation during natural product biosynthesis.

Crystal structures of C4 form maize and quaternary complex of E. coli phosphoenolpyruvate carboxylases.

PubMed

Matsumura, Hiroyoshi; Xie, Yong; Shirakata, Shunsuke; Inoue, Tsuyoshi; Yoshinaga, Takeo; Ueno, Yoshihisa; Izui, Katsura; Kai, Yasushi

2002-12-01

Phosphoenolpyruvate carboxylase (PEPC) catalyzes the first step in the fixation of atmospheric CO(2) during C(4) photosynthesis. The crystal structure of C(4) form maize PEPC (ZmPEPC), the first structure of the plant PEPCs, has been determined at 3.0 A resolution. The structure includes a sulfate ion at the plausible binding site of an allosteric activator, glucose 6-phosphate. The crystal structure of E. coli PEPC (EcPEPC) complexed with Mn(2+), phosphoenolpyruvate analog (3,3-dichloro-2-dihydroxyphosphinoylmethyl-2-propenoate), and an allosteric inhibitor, aspartate, has also been determined at 2.35 A resolution. Dynamic movements were found in the ZmPEPC structure, compared with the EcPEPC structure, around two loops near the active site. On the basis of these molecular structures, the mechanisms for the carboxylation reaction and for the allosteric regulation of PEPC are proposed.

Bottom-up construction of a superstructure in a porous uranium-organic crystal

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Peng; Vermeulen, Nicolaas A.; Malliakas, Christos D.

Bottom-up construction of highly intricate structures from simple building blocks remains one of the most difficult challenges in chemistry. We report a structurally complex, mesoporous uranium-based metal-organic framework (MOF) made from simple starting components. The structure comprises 10 uranium nodes and seven tricarboxylate ligands (both crystallographically nonequivalent), resulting in a 173.3-angstrom cubic unit cell enclosing 816 uranium nodes and 816 organic linkers—the largest unit cell found to date for any nonbiological material. The cuboctahedra organize into pentagonal and hexagonal prismatic secondary structures, which then form tetrahedral and diamond quaternary topologies with unprecedented complexity. This packing results in the formation ofmore » colossal icosidodecahedral and rectified hexakaidecahedral cavities with internal diameters of 5.0 nanometers and 6.2 nanometers, respectively—ultimately giving rise to the lowest-density MOF reported to date.« less

Seismic anisotropy and slab dynamics from SKS splitting recorded in Colombia

NASA Astrophysics Data System (ADS)

Porritt, Robert W.; Becker, Thorsten W.; Monsalve, Gaspar

2014-12-01

The Nazca, Caribbean, and South America plates meet in northwestern South America where the northern end of the Andean volcanic arc and Wadati-Benioff zone seismicity indicate ongoing subduction. However, the termination of Quaternary volcanism at ~5.5°N and eastward offset in seismicity underneath Colombia suggest the presence of complex slab geometry. To help link geometry to dynamics, we analyze SKS splitting for 38 broadband stations of the Colombian national network. Measurements of fast polarization axes in western Colombia close to the trench show dominantly trench-perpendicular orientations. Orientations measured at stations in the back arc, farther to the east, however, abruptly change to roughly trench parallel anisotropy. This may indicate along-arc mantle flow, possibly related to the suggested "Caldas" slab tear, or a lithospheric signature, but smaller-scale variations in anisotropy remain to be explained. Our observations are atypical globally and challenge our understanding of the complexities of subduction zone seismic anisotropy.

New evidence of the nonglaciated development of the northern part of the Western Siberian lowland in the Quaternary period

NASA Astrophysics Data System (ADS)

Sheinkman, V. S.; Melnikov, V. P.; Sedov, S. N.; Parnachev, V. P.

2017-12-01

To solve the controversially debated problem related to the areal extent of the ice sheet in Western Siberia in the Quaternary period, we have studied the development of cold born objects of this area estimating the relationships between them in terms of cryogenic diversity. We have obtained a field of new cross data related to the development of cryogenic and glacial phenomena, their relationship, and traces they left. The research showed that, in this area, the trend of rock freezing is clearly reflected in the Quaternary formations, but there were no conditions for ice sheet development even during the cryochrons.

The last interglacial period at Guantanamo Bay, Cuba and an estimate of late Quaternary tectonic uplift rate in a strike-slip regime

NASA Astrophysics Data System (ADS)

Schweig, E. S.; Muhs, D. R.; Simmons, K. R.; Halley, R. B.

2015-12-01

Guantanamo Bay, Cuba is an area dominated by a strike-slip tectonic regime and is therefore expected to have very low Quaternary uplift rates. We tested this hypothesis by study of an unusually well preserved emergent reef terrace around the bay. Up to 12 m of unaltered, growth-position reef corals are exposed at about 40 sections examined around ˜40 km of coastline. Maximum reef elevations in the protected, inner part of the bay are ˜11-12 m, whereas outer-coast shoreline angles of wave-cut benches are as high as ˜14 m. Fifty uranium-series analyses of unrecrystallized corals from six localities yield ages ranging from ˜134 ka to ˜115 ka, when adjusted for small biases due to slightly elevated initial 234U/238U values. Thus, ages of corals correlate this reef to the peak of the last interglacial period, marine isotope stage (MIS) 5.5. Previously, we dated the Key Largo Limestone to the same high-sea stand in the tectonically stable Florida Keys. Estimates of paleo-sea level during MIS 5.5 in the Florida Keys are ~6.6 to 8.3 m above present. Assuming a similar paleo-sea level in Cuba, this yields a long-term tectonic uplift rate of 0.04-0.06 m/ka over the past ~120 ka. This estimate supports the hypothesis that the tectonic uplift rate should be low in this strike-slip regime. Nevertheless, on the southeast coast of Cuba, east of our study area, we have observed flights of multiple marine terraces, suggesting either (1) a higher uplift rate or (2) an unusually well-preserved record of pre-MIS 5.5 terraces not observed at Guantanamo Bay.

New Sedimentary Records from Contourite Drifts on the West Antarctic Continental Margin: Reconstruction of Palaeoenvironmental Changes during the Late Quaternary by Combining an Integrated Chronostratigraphic Approach with Multi-Proxy Investigations

NASA Astrophysics Data System (ADS)

Hillenbrand, C. D.; Crowhurst, S.; Channell, J. E. T.; Williams, M.; Hodell, D. A.; Xuan, C.; Allen, C. S.; Ehrmann, W. U.; Graham, A. G. C.; Larter, R. D.

2016-12-01

Giant sediment drifts located on the continental rise west of the Antarctic Peninsula and in the Bellingshausen Sea contain a high-resolution archive of ice sheet history in West Antarctica and of palaeoceanographic changes in the Southern Ocean. However, previous studies on sediment cores recovered from these contourite drifts, including Ocean Drilling Program (ODP) Leg 178, were compromised by lack of reliable high-resolution chronological control. This shortcoming is mainly caused by the very low abundance of calcareous microfossils in the sediments that are required for applying radiocarbon dating and stable oxygen isotope (δ18O) stratigraphy. Moreover, sediments assumed to have been deposited during glacial periods consist almost entirely of terrigenous detritus, i.e. they lack even siliceous microfossils that could be utilised for biostratigraphic purposes. International Ocean Discovery Program (IODP) proposal 732-Full2 aims to obtain continuous, high-resolution records from sites on the West Antarctic sediment drifts and to develop reliable age models for them. The strategy for achieving the second objective is to use a range of chronostratigraphic techniques, including relative geomagnetic palaeointensity (RPI) and δ18O stratigraphy, on sedimentary sequences recovered from the shallowest parts of the drift crests, where the preservation of calcareous microfossils is expected be higher than in deeper water. Here we present preliminary results of multi-proxy investigations on new piston and box cores recovered from the proposed drill sites during site survey investigation cruise JR298 of the RRS James Clark Ross in 2015. Apart from the integrated chronological approach, the new cores augment previous assessments of palaeoenvironmental change on the West Antarctic continental margin during glacial-interglacial cycles of the Late Quaternary.

Late-Middle Quaternary lithostratigraphy and sedimentation patterns on the Alpha Ridge, central Arctic Ocean: Implications for Arctic climate variability on orbital time scales

NASA Astrophysics Data System (ADS)

Wang, Rujian; Polyak, Leonid; Xiao, Wenshen; Wu, Li; Zhang, Taoliang; Sun, Yechen; Xu, Xiaomei

2018-02-01

We use sediment cores collected by the Chinese National Arctic Research Expeditions from the Alpha Ridge to advance Quaternary stratigraphy and paleoceanographic reconstructions for the Arctic Ocean. Our cores show a good litho/biostratigraphic correlation to sedimentary records developed earlier for the central Arctic Ocean, suggesting a recovered stratigraphic range of ca. 0.6 Ma, suitable for paleoclimatic studies on orbital time scales. This stratigraphy was tested by correlating the stacked Alpha Ridge record of bulk XRF manganese, calcium and zirconium (Mn, Ca, Zr), to global stable-isotope (LR04-δ18O) and sea-level stacks and tuning to orbital parameters. Correlation results corroborate the applicability of presumed climate/sea-level controlled Mn variations in the Arctic Ocean for orbital tuning. This approach enables better understanding of the global and orbital controls on the Arctic climate. Orbital tuning experiments for our records indicate strong eccentricity (100-kyr) and precession (∼20-kyr) controls on the Arctic Ocean, probably implemented via glaciations and sea ice. Provenance proxies like Ca and Zr are shown to be unsuitable as orbital tuning tools, but useful as indicators of glacial/deglacial processes and circulation patterns in the Arctic Ocean. Their variations suggest an overall long-term persistence of the Beaufort Gyre circulation in the Alpha Ridge region. Some glacial intervals, e.g., MIS 6 and 4/3, are predominated by material presumably transported by the Transpolar Drift. These circulation shifts likely indicate major changes in the Arctic climatic regime, which yet need to be investigated. Overall, our results demonstrate applicability of XRF data to paleoclimatic studies of the Arctic Ocean.

Late quaternary temperature record from buried soils of the North American Great Plains

USGS Publications Warehouse

Nordt, L.; Von Fischer, J.; Tieszen, L.

2007-01-01

We present the first comprehensive late Quaternary record of North American Great Plains temperature by assessing the behavior of the stable isotopic composition (δ13C) of buried soils. After examining the relationship between the δ13C of topsoil organic matter and July temperature from 61 native prairies within a latitudinal range of 46°–38°N, we applied the resulting regression equation to 64 published δ13C values from buried soils of the same region to construct a temperature curve for the past 12 k.y. Estimated temperatures from 12 to 10 ka (1 k.y. = 1000 14C yr B.P.) fluctuated with a periodicity of ∼1 k.y. with two cool excursions between −4.5 and −3.5 °C and two warmer excursions between −1 and 0 °C, relative to modern. Early Holocene temperatures from ca. 10–7.5 ka were −1.0 to −2.0 °C before rising to +1.0 °C in the middle Holocene between 6.0 and 4.5 ka. After a cool interlude from 4.2 to 2.6 ka, when temperatures dropped to slightly below modern, another warm interval ensued from 2.6 to 1 ka as temperatures increased to ∼+0.5 °C. A final decline in temperature to below modern occurred beginning ca. 0.5 ka. Cooler than present temperatures in the Great Plains indicate telecommunications with cool-water episodes in the Gulf of Mexico and North Atlantic potentially governed by a combination of glacial meltwater pulses and low solar irradiance.